TWI245773B - Catalyst composition and use thereof in polymerizing olefin(s), and polymer therefrom - Google Patents

Abstract

The present invention provides catalyst compositions useful in polymerization processes, including a Group 15 containing metal compound, mixed catalyst compositions including the Group 15 containing metal compound and a second metal compound which is preferably a bulky ligand metallocene catalyst, supported and unsupported catalyst systems thereof, and a process for polymerizing olefin(s) utilizing them. The invention also discloses a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

Description

經濟部智慧財產局員工消費合作社印製 1245773 A7 ——-------— B7_________ 五、發明說明（1 ) 發明的領域 本發明係有關一種含第1 5族金屬化合物的觸媒組成 物’和一種含有至少兩種金屬化合物的混合觸媒組成物。 較佳者，這種混合組成物中有至少一金屬化合物是含第 1 5族金屬化合物。更佳者，另一金屬化合物是龐大配位 子茂合金屬（metallocene )觸媒化合物。本發明也有關使 用該觸媒組成物的觸媒系統，以及彼等在烯烴聚合中的用 途。本發明更有關一種新穎聚烯烴，通常是聚乙烯，特別 是一種多峰型聚合物，更特別的是一種雙峰型聚合物，和 其在多種最終用途應用例如膜，模製品和管件等中的用途 發明背景 聚合反應和催化作用的進展導致製造許多具有改良物 理和化學特性而可用於廣多種優良產品和應用中的新聚合 物之能力。隨著新觸媒的發展，爲產生特定聚合物所用聚 合類型（溶液，泥漿，高壓或氣）的選擇已大爲擴張。而 且，聚合技術的進展提供了更有效，（¾效率且經濟上增進 的方法。這些發展中尤其須闡述的是應用龐大配位子茂合 金屬觸媒系統技術的發展。 最近，這些發展導致陰離子，多齒型雜原子配位子之 發現，如下列文章對其所討論者：（1 ) Kempe et al.， '、 Aminopyridinato Ligands-New Directions and Limitations /r 80l1' Canadian Society for Chemistry Meeting, Windosr, 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -4 - ------------•裝--------訂-! (請先閱讀背面之注意事項再填寫本頁) 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（2 )Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1245773 A7 ------------ B7_________ V. Description of the Invention (1) Field of Invention The present invention relates to a catalyst composition containing a Group 15 metal compound 'And a mixed catalyst composition containing at least two metal compounds. Preferably, at least one metal compound in this mixed composition is a Group 15 metal-containing compound. More preferably, the other metal compound is a bulky ligand metallocene catalyst compound. The present invention also relates to a catalyst system using the catalyst composition and their use in olefin polymerization. The present invention is more about a novel polyolefin, usually polyethylene, especially a multimodal polymer, and more particularly a bimodal polymer, and its use in a variety of end-use applications such as films, moldings, and fittings. BACKGROUND OF THE INVENTION Advances in polymerization and catalysis have led to the ability to make many new polymers with improved physical and chemical properties that can be used in a wide variety of excellent products and applications. With the development of new catalysts, the choice of the type of polymer (solution, mud, high pressure or gas) used to produce a particular polymer has greatly expanded. Moreover, advances in polymerization technology have provided more efficient, efficient and economically-improved methods. Among these developments, it is important to elaborate on the development of technologies using massive ligand metallocene catalyst systems. Recently, these developments have led to anions The discovery of polydentate heteroatom ligands, as discussed in the following articles: (1) Kempe et al., ', Aminopyridinato Ligands-New Directions and Limitations / r 80l1' Canadian Society for Chemistry Meeting, Windosr, This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) -4------------- • Installation -------- Order-! (Please first Read the notes on the back and fill in this page) 1245773 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (2)

Ontario, Canada, June 1 -4 , 1 99 7 » ( 2 ) Kempt et a 1., Iηorg .Ontario, Canada, June 1 -4, 1 99 7 »(2) Kempt et a 1., Iηorg.

Chem., 1996 vol 3 5 6742 ； ( 3 ) Jordan et al ·係以羥基 〇奎 啉爲基的聚烯烴觸媒 （Bei，X，； Swenson, D.C; Jordan, R.F., Organometallics 1 997, 1 6, 3282 ) ； ( 4) Horton et al. 、、Cationic Alkylzirconium Complexes Based on a Tndentate Diamide Ligand: New Alkene Polymerization Catalysts -，Organometallics, 1996，15，2672-2674，係有關 三齒錯錯合物；（5) Baumann,et al., Synthesis of Titanium and Zirconium Complexes that Contain the TridentateDiamino Ligand [ ( ( t-Bu-da ) N-O-CsEN) 2〇 ]2. {[NON] 2·}" and the Living Polymerization of 1-Hexene by Activated [NON]ZrMe2、、 Journal of the American Chemical Society, Vol. 119，pp. 3830-3831 ; ( 6) Cloke et al.，〃Chem., 1996 vol 3 5 6742; (3) Jordan et al. Polyolefin catalysts based on hydroxyoquinoline (Bei, X ,; Swenson, DC; Jordan, RF, Organometallics 1 997, 1 6, 3282); (4) Horton et al., Cationic Alkylzirconium Complexes Based on a Tndentate Diamide Ligand: New Alkene Polymerization Catalysts-, Organometallics, 1996, 15, 2672-2674, related to tridentate complexes; (5) Baumann, et al., Synthesis of Titanium and Zirconium Complexes that Contain the TridentateDiamino Ligand [((t-Bu-da) NO-CsEN) 2〇] 2. {[NON] 2 ·} " and the Living Polymerization of 1 -Hexene by Activated [NON] ZrMe2, Journal of the American Chemical Society, Vol. 119, pp. 3830-3831; (6) Cloke et al., 〃

Zirconium Complexes incorporating the New Tridentate Diamide Ligand[ ( Me〕Si ) N{CH2CH2N ( SiMeO h]2- ( L ) ;the Crystal Structure of [Zr ( BHO 2L] and [ZrCl {CH ( Si Me3 ) 2 }L]” ，J. Chem. S oc, Dalton Trans., pp.25-30, 1 995 ; (7) Clark et al., 、、Titanium ( IV ) complexes incorporating the aminodiamide ligand [ ( Si Me：)Zirconium Complexes incorporating the New Tridentate Diamide Ligand [(Me) Si) N {CH2CH2N (SiMeO h) 2- (L); the Crystal Structure of [Zr (BHO 2L) and [ZrCl {CH (Si Me3) 2} L] ", J. Chem. S oc, Dalton Trans., Pp. 25-30, 1 995; (7) Clark et al., Titanium (IV) complexes incorporate the aminodiamide ligand [(Si Me :)

NfCHiCHzN ( SiMe： ) }2]2* ( L ) ； the X-ray crystal structure of [TiMe] ( L ) ] and [TiCl {CH ( SiMeO 】} ( L )]〃 ，Journal of Organometallic Chemistry, Vol 50， pp. 3 3 3 - 3 40，1995 ; ( 8) Scollard et al·，、' LivingNfCHiCHzN (SiMe:)} 2] 2 * (L); the X-ray crystal structure of [TiMe] (L)] and [TiCl {CH (SiMeO)} (L)] 〃, Journal of Organometallic Chemistry, Vol 50 , Pp. 3 3 3-3 40, 1995; (8) Scollard et al., "Living

Polymerization of alpha- ole fin by Chelating Diamide 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -5 - -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1245773 A7 B7 五、發明說明f )Polymerization of alpha- ole fin by Chelating Diamide This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -5------------ install ------- -Order --------- (Please read the notes on the back before filling out this page) 1245773 A7 B7 V. Description of the invention f)

Complexes of Titanium ， J. Am. Chem. S oc ., V o 1 118, No. 41，1 0008- 1 0009，1 996 ;和（9) Guerin et al·，'' Conformational Rigid Diamide Complexes: Synthesis and Structure of Titanium ( IV) Alkyl Derivatives"， Organometallics, Vol 15, No. 24, pp. 5085-5089, 1996 o 而且，美國專利第5，576，460號述及芳胺配 位子的製備；美國專利第5，8 8 9，1 2 8號揭示烯烴 的活聚合方法，其係使用具有一金屬原子和一含有2第 1 5族原子及一第1 6族原子或3第1 5族原子的配位子 °EP 8 9 3 4 5 4 A1也述及更爲較佳的鈦過渡 金屬醯胺化合物。此外，美國專利第5，3 1 8，9 3 5 號討論到特別爲製造順聯聚丙烯所用的醯胺基過渡金屬化 合物和觸媒系統。美國專利第5，5 0 6，1 8 4號進一 步討論含有雙齒和三齒配位子的聚合觸媒。 傳統的龐大配位子茂合金屬觸媒系統製造的聚合物在 某些情況下很難加工成膜，如使用老式擠壓設備者。一種 改良這些聚合物的技術是把彼等與其他聚合物摻合起來， 以製造出一種摻合物，其具有每種成分別具有的合意性質 。雖然兩種聚合物摻合物傾向於更可加工，但卻是昂貴者 且對製造/成形加工過程添加一道繁瑣的摻合步驟。 較高分子量可賦予合意的聚合物機械性質和在膜製造 中的穩定泡沬形成。但是，這種性能同時也增加了擠壓機 內的反壓從而抑制擠壓加工，並且促進充氣泡沬中的熔體 破裂缺陷，且潛在地’可能在成品膜中促進過高的定向度 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 零·裝 (請先閱讀背面之注意事項再填寫本頁) 訂——.------ 經濟部智慧財產局員工消費合作社印製 1245773 A7 B7 五、發明說明（4 ) (請先閱讀背面之注意事項再填寫本頁) 。含有陰離子多齒雜原子的觸媒系統傾向於製造非常高分 子量的聚合物。爲解決此項，可以形成較低分子量聚合物 的次級少量成分以減低擠壓機的反壓並抑制熔體破裂。數 種工業方法依據此原則操作而使用多反應器技術製造出適 合加工的雙峰型（bimodal )分子量分佈（M W D )型高密 度聚乙嫌（HDPE)產品。ΗΙΖΕΧτΜ，一 種 Mitsui Chemicals的H D P E產品，即被認爲是世界標準。 Η I Ζ Ε X τ Μ係以昂貴的二或更多反應器程序中產生的。 在一多反應器程序中，各反應器製造出最終產品的單一成 分。 技藝中的其他方法是試圖經由使用兩種不同的觸媒在 同一反應器中同時製造出兩種聚合物。P C Τ專利申請 W 0 9 9/0 3 8 9 9揭示出在同一反應器裏使用典型 經濟部智慧財產局員工消費合作社印製 的龐大配位子茂合金屬觸媒和一習用類型的戚格勒一納塔 (Ziegler-Natta )觸媒製造出一雙峰型聚烯烴。但是，使 用兩種不同類型的觸媒系統會導致一種聚合物其特性不能 從分別使用每種觸媒製得的聚合物所具特性預測出。這種 不可預測性係自，例如，所用觸媒或觸媒系統之間的競爭 或其他影響而發生的。 具有較高密度和較高分子量的聚乙烯在要求高勁度， 好韌性和高通料率的膜應用中是受到重視者。此類聚合物 也在要求高勁度，好韌性和長期耐用性，及特別是對環境 應力的抗性之管件應用也受到重視。 因此，有需要有一種改良的觸媒化合物和觸媒組合其 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -7 - 1245773 經 濟 部 智 慧 財 產 局 員 X .消 費 合 作 社 印 製 B7 五、發明說明（5 ) 能製造出可加工的聚烯烴聚合物，較佳者是在單一反應器 中，其具有理想的加工’機械和光學性質組合。 發明槪述 本發明提出觸媒化合物，觸媒系統和混合觸媒系統， 以及彼等在聚合程序中的用途，及由其所製得之聚合物和 由該聚合物製得的產品。 在一實施例中，本發明係有關一種包括含第1 5族金 屬化合物的觸媒化合物，也有關含有至少兩種金屬化合物. 的混合觸媒組成物，其中該混合組成物所含至少一種金屬 化合物爲含第1 5族金屬化合物，且另外一種金屬化合物 爲一龐大配位子茂合金屬化合物，一傳統的過渡金屬觸媒 或其組合，還有關含有這些觸媒的觸媒系統，及彼等在烯 烴聚合中的用途和由其產生的聚合物。 在另一實施例中，本發明係有關一種含第1 5族的雙 齒或三齒配位子其經拼合著一第3至1 4族金屬化合物， 較佳者一第3到7族，更佳者一第4到6族，且甚至更佳 者一第4族金屬觸媒化合物’及有關一種含有至少兩種金 屬化合物的混合觸媒組成物，其至少一種金屬化合物是上 述的含有第1 5族觸媒化合物，且另一種金屬化合物爲龐 大配位子茂合金屬化合物，一傳統的過渡金屬觸媒或其組 合’及有關包括适些觸媒的觸媒系統，彼等在嫌煙聚合中 的用途和由其產生的聚合物。於此實施例中，較佳的是另 一金屬化合物爲龐大配位子茂合金屬化合物。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -8 - « 11 m i_i an ·ϋ n in 一 I m ·ϋ> n an n (請先閱讀背面之注意事項再填寫本頁) #- 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（6 ) 在另一實施例中，本發明係有關一種第3至1 4族金 屬原子’其與至少一種脫離基結合且也與至少兩種第1 5 族原子結合’其中，至少一種原子係透過另一觸媒化合物 與第1 ‘5或1 6族原子結合；及有關包含至少兩種金屬化 合物的混合觸媒組成物，其中一種金屬化合物是上述的含 第1 5族觸媒化合物，而第二種金屬化合物，不同於第一 種金屬化合物者，爲龐大配位子茂合金屬觸媒，一種傳統 的過渡金屬觸媒或其組合；也有關包含這些觸媒的觸媒系 統，以及彼等在烯烴聚合中的用途和由其產生的聚合物。 在另一竇施例中，本發明係有關承載本文所述觸媒組 成物的方法，承載觸媒系統本身和彼等在烯烴聚合中的用 途。 在另一實施例中，本發明係有關含有路以士酸鋁的活 化劑和本文所述的觸媒組成物及觸媒系統的用途。 在另一實施例中，本發明係有關將本文所述觸媒組成 物和系統在液體載體中給入聚合反應器的方法。 在另一實施例中，本發明係有關聚合烯烴的方法，特 別是在氣相或漿相程序中者，其係使用本文所述的任何一 種觸媒系統或承載觸媒系統。 在另一實施例中，本發明係有關使用上述混合觸媒組 成物的烯烴聚合方法，特別是在單一的聚合反應器中者。 更佳者，該方法係利用一連續氣相單反應器程序來製造一 多峰型聚合物。 在另一實施例中’本發明係有關使用上述的混合觸媒 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -9 - -----------裝 *--------訂-------- (請先閱讀背面之注意事項再填寫本頁) 1245773 A7 _ B7__ 五、發明說明（7 ) 組成物所製備的烯烴，且較佳者有關一種新的雙峰型 M W D H D Ρ Ε。 (請先閱讀背面之注意事項再填寫本頁) 發明之詳細說明 導論 本發明係有關含有第1 5族金屬觸媒化合物在烯烴聚 合中之用途。此外，本案申請人發現使用彼等含有第1 5 族金屬觸媒與另一種觸媒，較佳者一種龐大配位子茂合金 屬化合物，之組合可製得一種新的雙峰型M W D H D Ρ Ε產品。驚訝地，本發明混合觸媒組成物可用於單 一反應器系統中。 含第15族金屬化合物 經濟部智慧財產局員工消費合作社印製 含第15族金屬化合物通常包括一第3至14族金屬 原子，較佳者，第3到7族，更佳者第4到6族，且甚至 更佳者第4族金屬原子，與至少一脫離基結合，且也與至 少兩第1 5族原子結合，其中至少一原子是透過另一基也 與一第1 5族或第1 6族原子結合。 在另一實施例中，至少一第1 5族原子也透過另一基 與一第1 5或1 6族原子結合，其中該另一基可爲Ci至 C 2 Q烴基，含雜原子基，矽，鍺，錫，鉛或磷，其中該第 1 5或1 6族原子也可能不結合，或與氫，含有第1 4族 原子的基，鹵素’含雜原子基結合且其中兩第1 .5族原子 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公* ) 1245773 Α7 Β7 五、發明說明（8 ) 也與一環狀基結合，且也視情況與氫，鹵素，雜原子或烴 基，或含雜原子基結合。 在另一實施例中，本發明含第1 5族金屬化合物可由 下式表出： R4 R1. R6 R3- \r2Complexes of Titanium, J. Am. Chem. Soc., Vo 1 118, No. 41, 1 0008- 1 0009, 1 996; and (9) Guerin et al., `` Conformational Rigid Diamide Complexes: Synthesis and Structure of Titanium (IV) Alkyl Derivatives ", Organometallics, Vol 15, No. 24, pp. 5085-5089, 1996 o Moreover, US Patent No. 5,576,460 describes the preparation of arylamine ligands; US Patent No. 5, 8 8 9, 1 2 8 discloses a living polymerization method of an olefin, which uses a compound having one metal atom and one containing two Group 1 5 atoms and one Group 16 atom or 3 Group 15 atom. The position ° EP 8 9 3 4 5 4 A1 also refers to the more preferred titanium transition metal amide compounds. In addition, U.S. Patent No. 5,3,18,95,5 discusses amido-based transition metal compounds and catalyst systems especially for the manufacture of cis-polypropylene. U.S. Patent No. 5,506,184 further discusses polymeric catalysts containing bidentate and tridentate ligands. Polymers made by traditional bulky ligand metallocene catalyst systems are difficult to process into films in some cases, such as those using older extrusion equipment. One technique to improve these polymers is to blend them with other polymers to make a blend that has the desirable properties of each component. Although two polymer blends tend to be more processable, they are expensive and add a cumbersome blending step to the manufacturing / forming process. Higher molecular weights can impart desirable polymer mechanical properties and stable foam formation in film manufacturing. However, this performance also increases the back pressure in the extruder to suppress the extrusion process, and promotes melt fracture defects in the air-filled puppet, and potentially 'may promote excessively high degree of orientation in the finished film. Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) Zero-pack (please read the precautions on the back before filling this page) Order --------- Staff of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives 1245773 A7 B7 V. Description of Invention (4) (Please read the precautions on the back before filling this page). Catalyst systems containing anionic polydentate heteroatoms tend to make very high molecular weight polymers. To address this, secondary minor components of lower molecular weight polymers can be formed to reduce the back pressure of the extruder and suppress melt fracture. Several industrial methods operate in accordance with this principle and use multi-reactor technology to produce bimodal (MWD) high-density polyethylene (HDPE) products suitable for processing. ZIZZE × τM, a H D PE product of Mitsui Chemicals, is considered to be the world standard. Η I Ε X τ Μ is produced in expensive two or more reactor procedures. In a multiple reactor process, each reactor produces a single component of the final product. Other methods in the art are trying to make two polymers simultaneously in the same reactor by using two different catalysts. PC T patent application W 0 9 9/0 3 8 9 9 reveals that in the same reactor, a large ligand, a metallocene catalyst printed by a typical consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and a conventional type of geiger Ziegler-Natta catalyst produces a bimodal polyolefin. However, the use of two different types of catalyst systems results in a polymer whose properties cannot be predicted from the properties of polymers made using each catalyst separately. This unpredictability arises, for example, from competition or other influences between the catalysts or catalyst systems used. Polyethylene with higher density and higher molecular weight is valued in film applications that require high stiffness, good toughness, and high throughput. Such polymers are also receiving attention for pipe applications requiring high stiffness, good toughness and long-term durability, and especially resistance to environmental stress. Therefore, there is a need for an improved catalyst compound and catalyst combination whose paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -7-1245773 printed by the Intellectual Property Bureau of the Ministry of Economic Affairs X. Consumer Cooperative B7 V. Description of the invention (5) A processable polyolefin polymer can be produced, preferably in a single reactor, which has an ideal combination of processing 'mechanical and optical properties. Summary of the Invention The present invention proposes a catalyst compound, a catalyst system and a mixed catalyst system, and their uses in a polymerization process, and a polymer made therefrom and a product made from the polymer. In one embodiment, the present invention relates to a catalyst compound including a Group 15 metal compound, and also to a mixed catalyst composition containing at least two metal compounds, wherein the mixed composition contains at least one metal. The compound is a Group 15 metal compound, and the other metal compound is a large ligand metallocene metal compound, a traditional transition metal catalyst or a combination thereof, and also related to a catalyst system containing these catalysts, and other Uses in the polymerization of olefins and the polymers produced by them. In another embodiment, the present invention relates to a bidentate or tridentate ligand containing Group 15 which is compounded with a Group 3 to 14 metal compound, preferably a Group 3 to 7, More preferred are Groups 4 to 6, and even more preferred are Group 4 metal catalyst compounds' and related mixed catalyst compositions containing at least two metal compounds, the at least one metal compound of which is Group 15 catalyst compounds, and another metal compound is a massive ligand metallocene compound, a traditional transition metal catalyst or a combination thereof, and related catalyst systems including suitable catalysts, and they are polymerizing in smoke. And the polymers produced by it. In this embodiment, it is preferred that the other metal compound is a bulky ligand metallocene compound. This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) -8-«11 m i_i an · ϋ n in Yim · ϋ > n an n (Please read the notes on the back before filling (This page) #-1245773 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (6) In another embodiment, the present invention relates to a group 3 to 14 metal atom 'which is related to at least one A leaving group is also bonded to at least two Group 1 5 atoms, wherein at least one atom is bonded to a Group 1 5 or 16 atom through another catalyst compound; and a mixture containing at least two metal compounds A catalyst composition in which one of the metal compounds is the above-mentioned group 15-containing catalyst compound, and the second metal compound, unlike the first metal compound, is a large ligand-metallocating metal catalyst, a traditional Transition metal catalysts or combinations thereof; it also relates to catalyst systems containing these catalysts, and their use in olefin polymerization and the polymers they produce. In another sinus embodiment, the present invention relates to a method for carrying the catalyst composition described herein, the catalyst system itself and their use in the polymerization of olefins. In another embodiment, the present invention relates to the use of an activator containing aluminum leosite and the catalyst composition and catalyst system described herein. In another embodiment, the present invention relates to a method for feeding a catalyst composition and system described herein into a polymerization reactor in a liquid carrier. In another embodiment, the invention is a method for polymerizing olefins, particularly in a gas phase or slurry phase process, which uses any of the catalyst systems or supported catalyst systems described herein. In another embodiment, the present invention relates to a method for polymerizing olefins using the above mixed catalyst composition, particularly in a single polymerization reactor. More preferably, the method utilizes a continuous gas phase single reactor process to make a multimodal polymer. In another embodiment, the present invention is related to the use of the above-mentioned mixed catalyst. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) -9------------ Packing * -------- Order -------- (Please read the notes on the back before filling this page) 1245773 A7 _ B7__ V. Description of the invention (7) The olefin prepared by the composition, And the better one relates to a new bimodal MWDHD PE. (Please read the notes on the back before filling out this page) Detailed Description of the Invention Introduction The present invention relates to the use of a Group 15 metal catalyst compound in the polymerization of olefins. In addition, the applicant of this case found that a new bimodal MWDHD PF can be obtained by using a combination of metal catalysts containing Group 15 and another catalyst, preferably a bulky ligand, and a metallocene compound. product. Surprisingly, the mixed catalyst composition of the present invention can be used in a single reactor system. Contains Group 15 metal compounds Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Group 15 Metal compounds usually include a Group 3 to 14 metal atom, preferably, Groups 3 to 7, and more preferably Groups 4 to Group, and even better, a Group 4 metal atom is bound to at least one leaving group, and is also bonded to at least two Group 15 atoms, of which at least one atom is through another group and also to a Group 15 or Group Group 6 atom bonding. In another embodiment, at least one Group 15 atom is also bonded to a Group 15 or 16 atom through another group, wherein the other group may be a Ci to C 2 Q hydrocarbon group, a heteroatom-containing group, Silicon, germanium, tin, lead, or phosphorus, where the Group 15 or 16 atom may not be bonded, or with hydrogen, a group containing a Group 1 4 atom, halogen 'heteroatom-containing group and two of the first .5 Atoms This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 male *) 1245773 A7 B7 5. Description of the invention (8) is also combined with a cyclic group, and also with hydrogen, halogen, as appropriate, Heteroatom or hydrocarbyl, or heteroatom-containing groups. In another embodiment, the Group 15 metal-containing compound of the present invention can be represented by the following formula: R4 R1. R6 R3- \ r2

MnXn+mMnXn + m

Z R7 R5 式I或 R* R3_\. R4 Y； z〆 R5 / R6:，Xn-2、R7Z R7 R5 Formula I or R * R3_ \. R4 Y; z〆 R5 / R6 :, Xn-2, R7

式I I 其中 -----------裝---------訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智"財產局員工消費合作社印炎 M爲第3至12族過渡金屬或第13至14主族金屬 ’較佳者第4，5或6族金屬，且更佳者，第4族金屬， 且最佳者爲鉻，鈦或給， 各X獨立地爲一脫離基，較佳者，陽離子脫離基，且 更佳者氫’烴基，雜原子或鹵素，且最佳者爲烷基， y爲0或1 (於y爲〇時，基不存在）， η爲Μ的氧化態，較佳者+3，+ 4，或+5，更佳 者+ 4 ， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）-11- 1245773 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（0 ) Μ爲Y Z L或Y Z L /配位子的式電荷，較佳者爲〇 ’一 1 ，一 2 ，或一 3 ，且更佳者爲—2 ， L爲第1 5或1 6族元素，較佳者氮， L /爲含第1 5或1 6族元素或第1 4族的基’較佳 者碳，砂或鍺， Υ爲第1 5族元素，較佳者氮或磷，且更佳者氮’ Ζ爲第1 5族元素，較佳者氮或磷，且更佳者氮’ R1和R2獨立地爲（^至^^烴基，含有多達2 0個 碳原子的含雜原子基，矽，鍺，錫，鉛或磷，較佳者C 2到 C2〇烷基，芳基或芳烷基，更佳者線形，分枝或環狀C2 到C 2 〇烷基，更佳者C 2到C 6烴基· R 3不存在或爲烴基，氫，鹵素，含雜原子基，較佳者 有1到2 0個碳原子的線形，分枝或環狀烷基，更佳者R 3 不存在，爲氫或烷基，且最佳者爲氫， R 4和R 5獨立地爲烷基，芳基，經取代芳基，環狀烷 基，經取代環狀烷基，環狀芳烷基，經取代環狀芳烷基或 多環系統，較佳者其含有多達2 0個碳原子，更佳者3到 1 0個碳原子，且甚至更佳者一（：1至〇20烴基，（^至 C2Q芳基，（^至（：2。芳烷基，或含雜原子基，如PRs ，其中R是烷基， R 1和R 2可彼此連接，及/或R 4和R 5可彼此連接， R6和R7獨立地爲不存在，或爲氫，烷基，鹵素，雜 原子或烴基，較佳者爲含1到2 〇個碳原子的線形，分枝 或環狀烷基，更佳者R6和R7不存在且 (請先閱讀背面之注意事 項再填 裝ill----訂---I 寫本頁) # 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公爱）-12- 1245773Formula II of which ----------- install --------- order --------- (please read the precautions on the back before filling this page) " Industrial Consumer Employees 'Cooperative Co., Ltd. Yin Yan M is a Group 3 to 12 transition metal or Group 13 to 14 main group metal' preferably a group 4, 5 or 6 metal, and more preferably, a group 4 metal, and The most preferred is chromium, titanium, or each, each X is independently a leaving group, more preferably, a cationic leaving group, and more preferably a hydrogen 'hydrocarbon group, a heteroatom or a halogen, and the most preferably an alkyl group, and y is 0 or 1 (the group does not exist when y is 0), η is the oxidation state of M, preferably +3, +4, or +5, and more preferably +4 ) A4 specification (210 X 297 public love) -11- 1245773 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (0) M is the formula charge of YZL or YZL / ligand. 〇′-1, -2, or-3, and more preferably -2, L is a Group 15 or 16 element, more preferably nitrogen, L / is a group containing an element 15 or 16 or Carbons, sand, or germanium are the preferred bases of Group 4, and europium is a Group 15 element. Preferably nitrogen or phosphorus, and more preferably nitrogen'Z is a Group 1 element, more preferably nitrogen or phosphorus, and more preferably nitrogen 'R1 and R2 are independently (^ to ^^ hydrocarbon groups, containing up to 2 A heteroatom-containing group of 0 carbon atoms, silicon, germanium, tin, lead or phosphorus, preferably C 2 to C 2 0 alkyl, aryl or aralkyl, more preferably linear, branched or cyclic C 2 to C 2 0 alkyl, more preferably C 2 to C 6 hydrocarbyl · R 3 is absent or is a hydrocarbyl, hydrogen, halogen, heteroatom-containing group, preferably linear, branched or branched having 1 to 20 carbon atoms Cyclic alkyl, more preferably R 3 is absent, is hydrogen or alkyl, and most preferably hydrogen, R 4 and R 5 are independently alkyl, aryl, substituted aryl, cyclic alkyl, A substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, or a polycyclic ring system, preferably it contains up to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and Even better is one (: 1 to 020 hydrocarbon group, (^ to C2Q aryl group, (^ to (: 2. aralkyl group, or heteroatom-containing group, such as PRs, where R is an alkyl group, R 1 and R 2 may be connected to each other, and / or R 4 and R 5 may be connected to each other, and R 6 and R 7 are independently Does not exist, or is hydrogen, alkyl, halogen, heteroatom or hydrocarbyl, preferably a linear, branched or cyclic alkyl group containing 1 to 20 carbon atoms, more preferably R6 and R7 are absent and ( Please read the precautions on the back before filling ill ---- Order --- I write this page) # This paper size is applicable to China National Standard (CNS) A4 specification (21〇X 297 public love) -12- 1245773

五、發明說明（10 ) R*爲不存在，或爲氫，含第丄4族原子基，鹵素， 含雜原子基。 '' Y Z L·或Y Z L· 配位子〃意指不含金屬和脫離基 X的整個配位子的電荷。 '' R i和R 2也可相連〃意指R 1和R 2可能直接相互結 合或透過其他基相互結合。'、R 4和r 5也可相連〃意指 R 4和R。可能直接相互結合或透過其他基相互結合。 烷基可爲線形’分枝或環狀基，或烯烴基，炔基，環 烷基或芳基’醯基’芳醯基，烷氧基，芳氧基，烷硫基， 二烷胺基，烷氧鑛基，芳氧羰基，胺基甲醯基，烷基一或 二烷基-胺基甲醯基，醯氧基，醯胺基，芳醯胺基，線形 ’分枝或環狀伸烷基，或彼等的組合。芳烷基係經定義爲 經取代芳基。 在一較佳實施例中，R 4和R 5獨立地爲下式所表之基V. Description of the invention (10) R * is absent or is hydrogen, containing a group 丄 atomic group, halogen, and a heteroatom-containing group. '' Y Z L · or Y Z L · ligand 〃 means the charge of the entire ligand without the metal and leaving the group X. '' R i and R 2 may also be connected, which means that R 1 and R 2 may be directly bonded to each other or through other groups. ', R 4 and r 5 may also be connected, meaning R 4 and R. It may be directly combined with each other or through other groups. Alkyl may be a linear 'branched or cyclic group, or an alkynyl, alkynyl, cycloalkyl or aryl'fluorenyl'arylfluorenyl, alkoxy, aryloxy, alkylthio, dialkylamino group , Alkoxide, aryloxycarbonyl, aminoformyl, alkylmono- or dialkyl-aminoformyl, fluorenyloxy, fluorenylamino, aryleneamino, linear 'branched or cyclic Alkyl, or a combination thereof. Aralkyl is defined as a substituted aryl. In a preferred embodiment, R 4 and R 5 are independently the bases represented by

鍵結列Z到Y 其中 R 8至R 1 2獨立地各爲氫，C 1到C 4 q院基，鹵化物 雜原子，含有高達4 0個碳原子的含雜原子基，較佳者 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-13- I I — III1III I ·1111111 ·11111111 (請先閱讀背面之注意事項再填寫本頁)Bonding columns Z to Y where R 8 to R 1 2 are each independently hydrogen, C 1 to C 4 q radicals, halide heteroatoms, heteroatom-containing radicals containing up to 40 carbon atoms, preferably this radical Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -13- II — III1III I · 1111111 · 11111111 (Please read the precautions on the back before filling this page)

式 經濟部智慧財產局員工消費合作社印製 1245773 A7 B7 五、發明說明（11 ) (請先閱讀背面之注意事項再填寫本頁) ，C 1至C 2 〇線形或分枝烷基，較佳者，甲基，乙基，丙 基’或丁基，任何兩R基可形成一環狀基及/或雜環基。 環狀基可爲芳族者。在一較佳實施例中，R 9，R i 〇和 R12獨立地爲甲基，乙基，丙基’或丁基（包括所有的異 構物）。在一較佳實施例中，R 9，R 1 Q和R 1 2爲甲基， 且R 8和R 1 1爲氫。 在一特別較佳實施例中，R 4和R 5兩者皆爲下式所表 者：Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1245773 A7 B7 V. Description of Invention (11) (Please read the notes on the back before filling this page), C 1 to C 2 0 linear or branched alkyl, preferably That is, methyl, ethyl, propyl 'or butyl, and any two R groups may form a cyclic group and / or a heterocyclic group. The cyclic group may be aromatic. In a preferred embodiment, R 9, R i 0 and R 12 are independently methyl, ethyl, propyl 'or butyl (including all isomers). In a preferred embodiment, R 9, R 1 Q and R 1 2 are methyl, and R 8 and R 1 1 are hydrogen. In a particularly preferred embodiment, both R 4 and R 5 are represented by:

/ 鍵結列Y到Z CJ5^L^CH3 ch3 式2 在此實施例中，Μ爲第4族金屬，較佳者鉻，鈦或給 ，且甚至更佳者爲鉻；L，Υ，和Ζ分別爲氮；R1和R2 爲CH2— CH2 ; R3爲氫；R6和R7不存在。 經濟部智慧財產局員工消費合作社印製 在一較佳實施例中，至少一 X爲經取代烴基，較佳者 含6個以上碳原子的經取代烷基，最佳者爲一芳基經取代 烷基。最佳的芳基經取代烷基爲苄基。 在一特別較佳實施例中，該含第1 5族金屬化合物係 由下式所表者： 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） -14 - 1245773 A7 B7 五 、發明說明（I2/ Bonding column Y to Z CJ5 ^ L ^ CH3 ch3 Formula 2 In this embodiment, M is a Group 4 metal, preferably chromium, titanium, or iron, and even more preferably chromium; L, Υ, and Z is nitrogen respectively; R1 and R2 are CH2-CH2; R3 is hydrogen; R6 and R7 do not exist. Printed by a Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy alkyl. The most preferred aryl substituted alkyl is benzyl. In a particularly preferred embodiment, the Group 15-containing metal compound is represented by the following formula: The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21 × X 297 mm) -14-1245773 A7 B7 V. Description of Invention (I2

(請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

於化合物I中， 本發明含第 所製備的，如E 利第5，8 8 9 5，8 8 9，1 1 9 9 9年5月 0 9/312, 或漿相聚合方法 這些化合物 見例如式I或I p h表苯基。 1 5族金屬化合物是由技藝上已知的方法 P 〇 893 454 A1，美國專 ，1 2 8號和該美國專利第 2 8號所引參考文獻所揭示者，彼等都。 1 7日提出申請的美國專利申請序號 8 7 8揭示出使用承載雙醯胺觸媒的氣相 ，其亦倂於本文作爲參考。 的一種較佳直接合成包括用中性配位子（ I 的 YZL 或 YZL / )與MnXn (M 爲 一第3至1 4族金屬’ η是Μ的氧化態’各X都是陰離子 脫離基，如鹵離子），在非配位性或微弱配位性溶劑，如 醚，甲苯，二甲苯，苯，二氯甲烷，及/或己院或其他沸 點高於6 0 °C的溶劑’於約2 0到約1 5 0 °C (更佳者 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- 1245773 A7 B7 五、發明說明（13 ) (請先閱讀背面之注意事項再填寫本頁) 2 0到1 0 0 °C )的溫度下反應，較佳者2 4小時或更久 ，然後用超量的（如4或更多當量）烷化劑，如溴化甲基 鎂在醚中處理混合物。過濾去除鎂鹽，並用標準技術分離 金屬錯合物。 在一實施例中，含第1 5族金屬化合物的製備方法包 括用一中性配位子（見式1或2的Y Z L或Y Z L > )與 式Μ 11 X n表的化合物，（其中，Μ爲一第3至1 4族的金 屬，η是Μ的氧化態，各X都是陰離子脫離基），在非配 位性或微弱配位性溶劑中，於約2 0 °C或更高者，較佳者 約2 0到約1 0 0 °C溫度下反應，然後用超量的烷化劑處 理混合物，再回收金屬錯合物。在一較佳實施例中，溶劑 的沸點係高於6 0 °C者，例如甲苯，二甲苯，苯，及/或 己烷。於另一實施例中，溶劑包括醚及/或二氯甲烷，兩 者皆爲較佳者。 龐大配位子茂合金屬化合物 經濟部智慧財產局員工消費合作社印製 在一實施例中，上述含第1 5族金屬化合物可與第二 種金屬化合物組合形成混合觸媒組成物。該第二種金屬化 合物較佳者爲龐大配位子茂合金屬化合物。 通常，龐大配位子茂合金屬化合物包括半夾層和全夾 層化合物，其有經鍵結到至少一金屬原子的一或多龐大配 位子。通常將典型龐大配位子茂合金屬化合物描述成含有 經鍵結到至少一金屬原子的一或多個龐大配位子和一或多 個脫離基。在一較佳實施例中，至少一龐大配位子係經 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16- 1245773 Α7 Β7 五、發明說明（14 ) -鍵結到該金屬原子’最佳者其係經77 5 -鍵結到該金屬 原子。 (請先閱讀背面之注意事項再填寫本頁) 龐大配位子通常係由一或多種開放，非環狀，或稠合 環或環系統或彼等的組合。這些龐大配位子，較佳者，環 或環系統典型者係由選自元素週期表的第13至16族原 子中的原子所構成’較佳者這些原子是從下列所構成的組 合中選出者：碳，氮，氧，矽，硫，磷，鍺，硼和鋁或彼 等的組合。最佳者該環或環系統係由碳原子所構成，例如 ’但不限於彼等些茂基（cyclopentadiene，環戊二烯基） 配位子或茂基型配位子結構物或其他相似功能性配位子結 構物如戊二烯，環辛四烯基或醯亞胺配位子。該金屬原子 較佳者是選自元素週期表的第3至15族和鑭系或锕係元 素之中者。較佳者該金屬是從第4到1 2族，更佳者從第 4，5和6族，且最佳者爲從第4族中選出的過渡金屬。 在一實施例中，該龐大配位子茂合金屬化合物爲下式 所表者： LALBMQn (III) 經濟部智慧財產局員工消費合作社印製 其中，Μ從元素週期表中選出的金屬原子且可爲元素週期 表中的第3至12族金屬或鑭系或锕系元素選出的金屬原 子，較佳者Μ爲第4，5或6族過渡金屬，更佳者Μ爲第 4族過渡金屬，甚至更佳者Μ爲鉻，給或鈦。龐大配位子 ，L Α和L Β，爲開放，非環狀’或稠合環或環系統和任何 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-17 - 1245773 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明（15 ) 輔助的配位子系統，包括未經取代的或經取代的’茂基配 位子或茂基型配位子’含經取代雜原子及/或雜原子的茂 基型配位子。龐大配位子的非限制性例子包括茂基配位子 ，環茂菲基配位子，茚基配位子，苯並茚基配位子，苐基 配位子，八氫苐基配位子，環辛四烯基配位子，環茂環十 二碳烯配位子，氮烯基（azenyl )配位子，葜基配位子’ 戊搭烯配位子，二氧磷基（phosphoyl )配位子，磷醯亞胺 (W〇 99/40125)，吡咯基配位子，pyrozolyl 配位子，咔唑基配位子，硼雜苯配位子和類似者，包括其 氫化形式，如四氫茚基配位子。在一實施例中，L A和L B 可爲可以與Μ 7? -鍵結較佳者與Μ 7? 3 —鍵結且最佳者爲 7? 5 -鍵結的任何其他配位子結構物。在又另一實施例中， L λ或L Β的原子分子量（M W )超過6 0原子質量單位， 較佳者大於6 5原子質量單位。在另一實施例中，L Α和 L Β可包含一或多雜原子，如氮，矽，硼，鍺，硫和磷，其 與碳原子組合形成一開放，非環狀，或較佳者稠合，環或 環系統，例如雜茂基輔助配位子。其他的L Α和L Β龐大配 位子包括但並不局限于龐大醯胺，磷化物，烷氧化物，芳 氧化物，醯亞胺，咔啉化物（carboHde )，硼啉化物（ borollides )，卟啉，酞花青，咕淋（corrins )和其他多氮 雜巨環類。L A和L B可獨立地爲與Μ鍵結的同一種或不同 類型的龐大配位子。在式（I I I )的一實施例中，只有 L八或1^ 8任一者存在。 L Α和L β可獨立地爲未經取代者或含R取代基者。取 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -18- Λ n n ·ϋ n I I *n 一.· I ·ϋ n (請先閱讀背面之注意事項再填寫本頁) 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（16 ) 代基R的非限制性例子包括一或多種從下列選出的基：氫 ’或線形’分枝烷基，或烯烴基，炔基’環烷基或芳基， 醯基，芳醯基，烷氧基’芳氧基，烷硫基，二烷胺基，烷 氧羰基’芳氧羰基，胺基甲醯基，烷基-或二烷基一胺基 甲醯基，醯氧基，醯胺基，芳醯胺基，線形，分枝或環狀 的伸烷基，或彼等的.組合。在一較佳的實施例中，取代基 R具有多達5 0個非氫原子，較佳者1至3 0個碳。烷基 取代基R的非限制性例子包括甲基，乙基，丙基，丁基， 戊基，己基，環戊基，環己基，苄基，或苯基和類似者， 包括所有彼等的異構物，如第三丁基，異丙基和類似者。 其他烴基包括氟甲基，氟乙基，二氟乙基，碘丙基，溴己 基，氯苄基與經烴基取代的有機金屬基包括三甲矽烷基， 三甲鍺烷基，甲基二乙基矽烷基和類似者；類及經鹵烴基 取代的有機類金屬基包括三（三氟甲基）矽烷基，甲基-二（二氟甲基）矽烷基，溴甲基二甲基鍺烷基和類似者； 和經二取代的硼基，如包括二甲硼；和經二取代的氮族元 素基包括二甲胺，二甲膦，二苯胺，甲苯膦；硫族元素基 包括甲氧基，乙氧基，丙氧基，苯氧基’甲硫化物和乙硫 化物。非一氫取代基R包括碳原子’砂’硼’錯’氮’磷 ，氧，錫，硫，鍺和類似者，包括烯烴例如但不限制於乙 烯型不飽和取代基包括乙烯-終端的配位子，如丁- 3 -烯基，丙一 2 —烯基和類似者。此外，兩R基’較佳者兩 相鄰的R基係經結合形成一含3到3 0從碳’氮，氧’憐 ，矽，鍺，鋁，硼或其組合中選出的原子之環結構。而且 丨本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱)-19: *--. n ϋ n n n n ϋ n 0 ϋ n ·ϋ n ϋ n n 一 0, · n ϋ n n ϋ n n I # (請先閱讀背面之注意事項再填寫本頁) 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（17 ) ’取代基R，如1 -丁烷基可形成一接到金屬Μ的碳σ鍵 〇 其他配位子可與金屬Μ結合，如至少一種脫離基Q。 在一實施例中，Q是含有一接到Μ的σ鍵之一陰離子不穩 定配位子。依金屬的氧化態而定，η値爲〇，1或2，使 得上述式（I I I )表一中性龐大配位子茂合金屬觸媒化 合物。 Q配位子的非限制性例子包括弱鹼如胺，膦，醚，羧 酸鹽’二烯，含有1到2 0個碳原子的烴基，氫化物，或 鹵素和類似者或彼等的結合。在另一實施例中，兩或多個 Q形成稠合環或稠合環系統的一部分。Q配位子的其他例 子包括那些上述的R取代基且包括環丁基，環己基，庚基 ，甲苯基，三氟甲基，四亞甲基，五亞甲基，次甲基，甲 氧基，乙氧基，丙氧基，苯氧基，二（Ν —甲基醯基苯胺 )，二甲醯胺，二甲磷化物等基和類似者。 在一實施例中，本發明龐大配位子茂合金屬觸媒化合 物包括式（I I I )化合物，其中L Α和L Β經由至少一橋 基，A，相互橋聯，使得該式由式（I V )所表 L A A L B M Q , (IV) 由式（I V )所表的彼等橋聯化合物係已知爲經橋聯 的龐大配位子茂合金屬觸媒化合物。L A，L B，Μ，Q和 η皆如上所定義。橋基Α的非限制性例子包括含至少一第 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）-20 - -裝----l·---訂---------- (請先閱讀背面之注意事項再填寫本頁) 1245773 有二或更多 A7 五、發明說明（18 ) 1 3至1 6族原子的橋基，通常稱爲二價部份體者例如， 但又限於至少一碳，氧，氮’矽，鋁，硼，鍺和錫原子或 其組合。較佳者’橋基A含有碳’矽或鍺原子，最佳者爲 A含至少一矽原子或至少一碳原子。橋基a也可含有如上 所定義的取代基R ’包括鹵素和鐵。橋基A的非限制性例 子可由 R>2Ge ，R/p所表，其中，R>是獨立的基，其爲 氫化物’烴基’經取代烴基，鹵烴基，經取代鹵烴基，經 烴基取代有機類金屬，經鹵烴基取代有機類金屬，經二取 代硼’一取代磷族兀素，取代硫族元素，或鹵素或二或更 多的R 可結合形成一環或環系統。在—'實施例中，式（ I V )經橋聯龐大配位子茂合金屬觸媒化合 的橋基A(EP 664 301 B1)。 在一實施例中’龐大配位子茂合金屬化合物爲在式（ 1 1 1 )和（I V )龐大配位子L A和L B上的R取代基亦 經相同或不同數量的在各龐大配位子上的取代基取代者。 在另一實施例中，式（I I I )和（I V )龐大配位子L ; 和L B互不相同。 在本發明中可用的其他龐大配位子茂合金屬觸媒化合 物和觸媒系統可包括在美國專利第5，0 6 4，8 0 2， 5’145，819，5，149，819， 5’243，〇〇1，5，239，〇22， 5，276，2〇8，5，296，434， 5，329，〇31，5，304，614， (請先閱讀背面之注意事項再填寫本頁) 訂-------- 經 濟 部 智 慧 財 產 局 員 工 消 費 合 社 印 製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） •21 - 1245773 A7 B7 五 '發明說明o9 ) 請 先 閱 讀 背 s 之 注 意 事 項 再 填 本 頁 5’677，4〇1，5，723’398， 5’753，578，5，854’363， 5’856，547，5，858，9〇3， 5’859，158，5，90〇’517 和 5 ’ 939 ，5〇3號；和PCT公報 w 0 93/08221 jW〇 93/08199’ w〇 95/07140 »W0 98/11144’ w〇 98/41530 ，W〇 98/41529’ w〇 98/46650 ，W〇 99 / 0 2540 和 W 〇 9 9 / 1 4 2 2 1 和 歐 洲 公 報 E P - ~ A — 〇 5 7 8 8 3 8 E P - ~ A — 〇 6 3 8 5 9 5 ， E P 一 ~ B — 〇 5 1 3 3 8 0 y E P - -A 1 一 0 8 1 6 3 7 2 j E P - -A 2 一 〇 8 3 9 8 3 4 j E P - - B 1 — 〇 6 3 2 8 1 9 E P - - B 1 一 0 7 4 8 8 2 1 和 E P - - B 1 — 〇 7 5 7 9 9 6 中 所敘述的，彼等全部 都倂於本文作爲參考。 經濟部智慧財產局員工消費合作社印製 在一實施例中，可用於本發明龐大配位子茂合金屬觸 媒化合物包括經橋聯雜原子，單-龐大配位子茂合金屬觸 媒化合物。這類的觸媒和觸媒系統述於P C T公報 W 0 92/0 0333 ，w〇 94/07928， W 0 91/04257 >W0 94/03506， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 22 1245773 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明) W 0 96/00244 ，W〇 97/15602 和 w 0 99/20637及美國專利第 5，〇57，475，5’〇96，867， 5’〇55，438，5，198，401， 5 ’ 227，440和5，264 ’ 405號與歐洲公報 EP— A — 0 4 2 0 436中，彼等全部皆倂於本文 作爲參考。 於此實施例中’龐大配位子茂合金屬觸媒化合物係由 下式所表： L c A J M Q η (V) 其中Μ爲從兀素週期表中的第3至16族金屬原子或銅系 和鑭系元素選出的金屬，較佳者Μ爲第4到1 2族過渡金 屬’更佳者Μ爲第4，5或6族過渡金屬，且最佳者爲Μ 爲任何氧化態的第4族過渡金屬，特別是鈦；L。是與μ鍵 結的經取代或未經取代龐大配位子；J係鍵結到Μ，· Α係 鍵結到Μ及J ; J爲雜原子輔助配位子·，且a爲一橋基； Q爲單價陰離子配位子；Sn爲整數〇，1或2。在上面 的式（V )中，L c，A和J形成一稠合環系統。在一實施 例中，式（V )的L。係上面對L A所定義者且式（v )的 A，Μ和Q係上文對式（I I I )所定義者。 在式（V)中J是含雜原子的配位子，其中j是—種 元素週期表第15族中配位數爲3的元素或第16族中配 (請先閱讀背面之注意事項再填寫本頁) I裝-----^----tT----------In compound I, the present invention contains a compound prepared by, for example, Eri 5, 8 8 9 5, 8 8 9, 1 1 9 9 May 9 9/312, or a slurry phase polymerization method. These compounds can be found in, for example, Formula I or Iph represents phenyl. Group 15 metal compounds are disclosed by methods known in the art P 893 454 A1, U.S.A., No. 128, and references cited in this U.S. Patent No. 28, both of which are disclosed. U.S. Patent Application Serial No. 8 7 8 filed on the 17th reveals the use of a gas phase bearing a bisphosphonium catalyst, which is also incorporated herein by reference. A preferred direct synthesis includes using neutral ligands (YZL or YZL / of I) and MnXn (M is a Group 3 to 14 metal 'η is the oxidation state of M', each X is an anionic leaving group, (Such as halide ions), in non-coordinating or weakly coordinating solvents, such as ether, toluene, xylene, benzene, dichloromethane, and / or solvents or other solvents with a boiling point higher than 60 ° C. 2 0 to about 15 0 ° C (better paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -15- 1245773 A7 B7 V. Description of the invention (13) (please read the back first) Note: Please fill in this page again) at a temperature of 20 to 100 ° C), preferably 24 hours or more, and then use an excess (such as 4 or more equivalents) of an alkylating agent, such as The mixture was treated with methylmagnesium bromide in ether. The magnesium salt was removed by filtration and the metal complexes were separated using standard techniques. In one embodiment, the method for preparing a Group 15-containing metal compound includes using a neutral ligand (see YZL or YZL of Formula 1 or 2) and a compound of the formula M 11 X n, (wherein, M is a group 3 to 14 metal, η is the oxidation state of M, and each X is an anionic leaving group), in a non-coordinating or weakly coordinating solvent, at about 20 ° C or higher Preferably, the reaction is carried out at a temperature of about 20 to about 100 ° C, and then the mixture is treated with an excess of an alkylating agent to recover the metal complex. In a preferred embodiment, the boiling point of the solvent is above 60 ° C, such as toluene, xylene, benzene, and / or hexane. In another embodiment, the solvent includes ether and / or dichloromethane, both of which are preferred. Huge coordinating metallocene compound Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In one embodiment, the aforementioned Group 15 metal compound can be combined with a second metal compound to form a mixed catalyst composition. The second metal compound is preferably a bulky ligand metallocene compound. Generally, bulky ligand metallocene compounds include semi- and fully sandwiched compounds that have one or more bulky ligands bonded to at least one metal atom. A typical bulky ligand metallocene compound is generally described as containing one or more bulky ligands and one or more leaving groups bonded to at least one metal atom. In a preferred embodiment, at least one large ligand is adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) via this paper size. -16-1245773 Α7 B7 5. Description of the invention (14)-Bonding To the metal atom 'best' it is bound to the metal atom via 77 5-. (Please read the notes on the back before filling out this page.) Large ligands are usually composed of one or more open, non-cyclic, or fused ring or ring systems or a combination of them. These bulky ligands, preferably, rings or ring systems are typically composed of atoms selected from Groups 13 to 16 of the periodic table of the elements. 'Preferred, these atoms are selected from the following combinations: Of: carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, and aluminum or a combination thereof. The best is that the ring or ring system is composed of carbon atoms, such as' but not limited to some cyclopentadiene (cyclopentadienyl) ligands or methacrylic type ligand structures or other similar functional ligands Positional structures such as pentadiene, cyclooctatetraenyl or fluorenimine ligands. The metal atom is preferably selected from Groups 3 to 15 of the periodic table and lanthanide or actinide elements. Preferably, the metal is from Groups 4 to 12, and more preferably from Groups 4, 5, and 6, and the most preferred is a transition metal selected from Group 4. In one embodiment, the bulky ligand metallocene compound is represented by the following formula: LALBMQn (III) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where M is a metal atom selected from the periodic table and can be A metal atom selected for a group 3 to 12 metal or lanthanide or actinide element in the periodic table of the elements, preferably M is a group 4, 5 or 6 transition metal, and more preferably M is a group 4 transition metal, Even more preferred M is chromium, or titanium. The massive ligands, L Α and L Β, are open, non-cyclic 'or fused rings or ring systems and any paper size applicable to China National Standard (CNS) A4 (210 X 297 mm) -17-1245773 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives A7, B7 V. Description of the invention (15) Auxiliary coordination subsystems, including unsubstituted or substituted 'methylene-based ligands or methylene-based ligands' containing substituted Heteroatoms and / or heteroatom molybdenum type ligands. Non-limiting examples of bulky ligands include fluorenyl ligands, cyclophenanthryl ligands, indenyl ligands, benzoindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands , Cyclooctatetraenyl ligands, cyclocenecyclododecene ligands, azenyl ligands, fluorenyl ligands' pentenyl ligands, phosphoyl ) Ligands, phosphinoimine (WO99 / 40125), pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borazabenzene ligands and the like, including their hydrogenated forms, Such as tetrahydroindenyl ligands. In one embodiment, L A and L B may be any other ligand structures that can be preferably bonded to M 7?-With M 7? 3-and most preferably 7-5-. In yet another embodiment, the atomic molecular weight (M W) of L λ or L B is more than 60 atomic mass units, and preferably more than 65 atomic mass units. In another embodiment, L A and L B may contain one or more heteroatoms, such as nitrogen, silicon, boron, germanium, sulfur, and phosphorus, which are combined with carbon atoms to form an open, acyclic, or better Fused, cyclic or ring systems, such as heterocene-based auxiliary ligands. Other L A and L B bulky ligands include, but are not limited to, bulky amidines, phosphides, alkoxides, aryl oxides, amidoimines, carboHde, borollides, Porphyrins, phthalocyanines, corrins and other polyaza macrocycles. L A and L B may independently be bulky ligands of the same or different type bonded to M. In one embodiment of the formula (I I I), only one of L8 or 1 ^ 8 exists. L A and L β may independently be unsubstituted or R-containing substituents. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -18- Λ nn · ϋ n II * n I. · I · ϋ n (Please read the precautions on the back before filling this page ) 1245773 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the Invention (16) Non-limiting examples of the radical R include one or more radicals selected from: hydrogen 'or linear' branched alkyl, or Alkenyl, alkynyl 'cycloalkyl or aryl, fluorenyl, arylfluorenyl, alkoxy' aryloxy, alkylthio, dialkylamino, alkoxycarbonyl 'aryloxycarbonyl, aminoformyl , Alkyl- or dialkyl monoaminomethylamidino, fluorenyloxy, fluorenylamino, arylamidoamine, linear, branched or cyclic alkylene, or a combination thereof. In a preferred embodiment, the substituent R has up to 50 non-hydrogen atoms, preferably 1 to 30 carbons. Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, or phenyl and the like, including all of them Isomers, such as third butyl, isopropyl and the like. Other hydrocarbyl groups include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl-substituted organometallic groups including trimethylsilyl, trimethylgermanyl, methyldiethylsilane And similar; organic and metalloids substituted with halogenated hydrocarbon groups include tris (trifluoromethyl) silyl, methyl-bis (difluoromethyl) silyl, bromomethyldimethylgermanyl and And similar; and di-substituted boron groups, such as including dimethyl boron; and di-substituted nitrogen group element groups include dimethylamine, dimethylphosphine, diphenylamine, tolyphosphine; chalcogen group includes methoxy, Ethoxy, propoxy, phenoxy 'methyl sulfide and ethyl sulfide. Non-monohydrogen substituents R include carbon atoms' sand'boron 'nitrogen'nitrogen' phosphorus, oxygen, tin, sulfur, germanium and the like, including olefins such as but not limited to ethylenically unsaturated substituents including ethylene-terminated compounds Positions, such as butan-3-alkenyl, propane-2-alkenyl and the like. In addition, two R groups are preferred, and two adjacent R groups are combined to form a ring containing 3 to 30 atoms selected from carbon 'nitrogen, oxygen', silicon, germanium, aluminum, boron, or a combination thereof. structure. Moreover, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) -19: *-. N ϋ nnnn ϋ n 0 ϋ n · ϋ n ϋ nn-0, · n ϋ nn ϋ nn I # (Please read the notes on the back before filling out this page) 1245773 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (17) 'Substituent R, such as 1-butane can form a Carbon sigma bond to metal M. Other ligands can bind to metal M, such as at least one leaving group Q. In one embodiment, Q is an anionic labile ligand containing one sigma bond to M. Depending on the oxidation state of the metal, η 値 is 0, 1 or 2, so that the neutral bulky ligand-metallocene compound of the formula (I I I) shown in Table 1 above is used. Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates' diene, hydrocarbyl groups containing 1 to 20 carbon atoms, hydrides, or halogens and the like or combinations thereof . In another embodiment, two or more Qs form a fused ring or part of a fused ring system. Other examples of Q ligands include those R substituents described above and include cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methine, methoxy Groups, ethoxy, propoxy, phenoxy, bis (N-methylfluorenylaniline), dimethylamidamine, dimethylphosphide and the like and the like. In one embodiment, the bulky ligand metallocene catalyst compound of the present invention includes a compound of formula (III), wherein L A and L B are bridged to each other via at least one bridge group, A, so that the formula is represented by formula (IV) The listed LAALBMQ, (IV) Their bridging compounds represented by formula (IV) are known as bridged bulky ligand-metallocene catalyst compounds. L A, L B, M, Q and η are as defined above. Non-limiting examples of bridge base A include at least one of the first paper sizes that apply Chinese National Standard (CNS) A4 specifications (210 X 297 public love) -20--installed ---- l · --- order --- ------- (Please read the notes on the back before filling this page) 1245773 There are two or more A7 V. Description of the invention (18) 1 3 to 16 bridge group of atom, usually called divalent Some examples include, but are not limited to, at least one carbon, oxygen, nitrogen 'silicon, aluminum, boron, germanium, and tin atoms, or combinations thereof. Preferably, the 'bridge group A contains carbon' silicon or germanium atoms, and most preferably, A contains at least one silicon atom or at least one carbon atom. The bridging group a may also contain a substituent R 'as defined above including halogen and iron. Non-limiting examples of the bridging group A can be represented by R > 2Ge, R / p, where R > is an independent group, which is a hydride 'hydrocarbyl' substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, and substituted with a hydrocarbon group Organic metal, which is substituted with halohydrocarbyl group, substituted with boron ′, substituted with phosphorus group element, substituted with chalcogen element, or halogen or two or more R may be combined to form a ring or ring system. In the-'embodiment, the formula (IV) is bridged by a bulky ligand metallocene bridged bridge A (EP 664 301 B1). In one embodiment, the "macrocoordinated metallocene compounds are the formulae (1 1 1) and (IV) the R substituents on the macromolecular ligands LA and LB are also subjected to the same or different numbers of coordinating complexes in each macromolecule. Substituents on the substituent. In another embodiment, the formulae (I I I) and (I V) bulky ligands L; and L B are different from each other. Other bulky ligand metallocene catalyst compounds and catalyst systems useful in the present invention may be included in U.S. Patent Nos. 5,0 6,4,8 0 2,5'145,819,5,149,819,5 '243, 〇〇1, 5, 239, 〇22, 5, 276, 208, 5, 296, 434, 5, 329, 〇31, 5, 304, 614, (Please read the precautions on the back before (Fill in this page) Order -------- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) • 21-1245773 A7 B7 5 'Invention note o9) Please read the precautions on the back and fill out this page 5'677, 4〇1, 5,723'398, 5'753,578, 5,854'363, 5'856,547,5 , 858, 903, 5'859, 158, 5, 90, 517 and 5 '939, 503; and PCT Gazette w 0 93/08221 jW〇93 / 08199' w〇95 / 07140 »W0 98/11144 'w〇98 / 41530, W98 / 41529' w〇 98/46650, W 99/0 2540 and W 0 9 9/1 4 2 2 1 and European Gazette EP-~ A — 〇 5 7 8 8 3 8 EP-~ A — 〇6 3 8 5 9 5 ， EP 1 ~ B — 〇5 1 3 3 8 0 y EP--A 1-0 8 1 6 3 7 2 j EP--A 2 108 8 9 8 3 4 j EP--B 1 — 〇6 3 2 8 1 9 EP--B 1-0 7 4 8 8 2 1 and EP--B 1-〇 7 5 7 9 9 6, all of which are incorporated herein by reference. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In one embodiment, the bulky ligand metallocene catalyst compounds that can be used in the present invention include bridged heteroatoms, mono-bulk ligand metallocene catalyst compounds. Such catalysts and catalyst systems are described in PCT Bulletins W 0 92/0 0333, WO 94/07928, W 0 91/04257 > WO 0 94/03506. This paper standard applies to China National Standard (CNS) A4 (210 X 297 mm) 22 1245773 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 5. Description of the invention) W 0 96/00244, W 97/15602 and W 0 99/20637 and US Patent No. 5, 〇 57,475,5'〇96,867, 5'〇55,438, 5,198,401, 5 '227,440 and 5,264' 405 and European Gazette EP-A-0 4 2 0 436, All of them are incorporated herein by reference. In this example, the 'massive ligand metallocene compound is represented by the formula: L c AJMQ η (V) where M is a metal atom from the Group 3 to 16 or copper system in the periodic table. And lanthanide selected metals, preferably M is a Group 4 to 12 transition metal 'more preferably M is a Group 4, 5 or 6 transition metal, and most preferably M is the 4th in any oxidation state Group transition metals, especially titanium; L. Is a substituted or unsubstituted bulky ligand bonded to μ; J is bonded to M, · A is bonded to M and J; J is a heteroatom auxiliary ligand; and a is a bridge group; Q is a monovalent anionic ligand; Sn is an integer of 0, 1 or 2. In the above formula (V), L c, A and J form a fused ring system. In one embodiment, L of formula (V). Are those defined above for L A and A, M and Q are those defined above for formula (I I I). In formula (V), J is a heteroatom-containing ligand, where j is an element with a coordination number of 3 in Group 15 of the periodic table or a coordination in Group 16 (please read the precautions on the back first) (Fill in this page) I installed ----- ^ ---- tT ----------

本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 23 1245773 A7 B7 五、發明說明) 位數爲2的元素。較佳者，J含有氮，磷，氧或硫原子， 其中以氮爲最佳。 在本發明一實施例中，該龐大配位子茂合金屬觸媒化 合物是雜環配位子錯合物，其中該龐大配位子，環或環系 統’包括一或多雜原子或其組合。雜原子的非限制性例子 包括第1 3至1 6族元素’較佳者氮，硼，硫，氧，鋁， ί夕’磷和錫。這些龐大配位子茂合金屬觸媒化合物的例子 在W〇 96/33202 »WO 96/34021， w Ο 97/ 1 7379 和W〇 98/22486 及 Ep — Al —〇 8 7 4 005和美國專利第 5，637，660，5，539，124, 5’554，775，5，756，611， 5 ’233，049，5，744，417，和 5 ’ 8 5 6，2 5 8號中都有敘述，彼等皆倂於本文作爲 參考。 在一實施例中，該龐大配位子茂合金屬觸媒化合物爲 已知以含有嘧啶或喹啉部份體的雙齒配位子爲基的過渡金 屬觸媒之彼等錯合物，如1 9 9 8年6月2 3日提出申請 的美國申請序號〇 9 / 1 0 3，6 2 0所述的，其倂於本 文作爲參考。在另一實施例中，該龐大配位子茂合金屬觸 媒化合物是如P C T公報W〇 9 9 / 0 1 4 8 1和 W 0 9 8/4 2 6 6 4中所述者，其倂於本文作爲參考 〇 在另一實施例中，該龐大配位子茂合金屬觸媒化合物 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -24 · (請先閱讀背面之注意事項再填寫本頁) 裝 寫太 經濟部智慧財產局員工消費合作社印製 1245773 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明户） 是金屬錯合物，較佳者過渡金屬，龐大配位子，較佳者經 取代的或未經取代的p i -鍵結配位子，和一或多雜嫌丙 基部份體’如美國專利第5，5 2 7，7 5 2和 5，747，4〇6號與 EP — B1 —〇 7 3 5 〇57中所述者，所有彼等皆 倂於本文作爲參考。 此外本發明任一龐大配位子茂合金屬觸媒化合物也包 括含有至少一氟離子或含氟脫離基者，如1 9 9 8年1 1 月13日提出申請的美國申請序號〇9/1 9.1 ，916 中所述者。 在另一實施例中，該另一種金屬化合物爲下式所表的 龐大配位子茂合金屬觸媒化合物： LDMQ2 (YZ) Χπ (VI) 其中Μ爲第3至1 6族金屬，較佳者第4到1 2族過渡金 屬，且最佳者爲第4，5和6族過渡金屬；LD是與Μ結合 的龐大配位子；各Q獨立地與Μ和Q 2 ( Υ Ζ )結合形成配 位子，較佳者單電荷多齒配位子；Α或Q爲也與Μ結合的 單價陰離子配位子；當η等於2時，X爲價陰離子基，當 η等於1時，X爲二價陰離子基；η爲1或2。 在式（VI)中，L和Μ爲如上式（I I I)所定義 者。Q如上式（I I I)所定義，較佳者Q是從包含 —〇一，一 NR —，一 CR2 —和一 S —的組合中選出者， ----------------^----11·-------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -25 - 1245773 A7 五、發明說明（?3 ) \ 爲 C 或 S ·，Z 從含一〇 R —，一 N R 2 —，— c R 3 〜 一 S R〜，一 S L R 3 一，— p R 2 —，〜H _和經取代或 未經取代芳基的組合中選出者，但其限制條件爲Q爲 —NR —時，Ζ 爲從一 OR —，一 NR2 —，一 SR 〜， 一 S 1 R3 —，一 PR2 —和一 Η的組合中選出者；r爲從 包括碳，矽’氮，氧及/或磷的組合中選出者，較佳者其 中R是含1到2 0個碳原子的烴基，最佳者爲烷基，環院 基或芳基；η爲一從1到4的整數，較佳者1或2 ;當η 爲2時，X爲一價陰離子基或當η爲1時，X爲二價陰離 子基；較佳者X爲胺基甲酸根，羧酸根或由Q，Υ和Ζ的 組合所述的其他異烯丙基部份體。 在一特別較佳實施例中，該龐大配位子茂合金屬觸媒 化合物係由下式所表：This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) 23 1245773 A7 B7 V. Description of the invention) Element with 2 digits. Preferably, J contains nitrogen, phosphorus, oxygen or sulfur atoms, with nitrogen being the most preferred. In one embodiment of the present invention, the bulky ligand metallocene compound is a heterocyclic ligand complex, wherein the bulky ligand, ring or ring system includes one or more heteroatoms or a combination thereof. . Non-limiting examples of heteroatoms include Groups 1 to 16 elements', preferably nitrogen, boron, sulfur, oxygen, aluminum, phosphorus and tin. Examples of these bulky ligand metallocene compounds are WO 96/33202 »WO 96/34021, WO 97/1 7379 and WO 98/22486 and Ep — Al — 08 7 4 005 and US patents. Nos. 5,637,660, 5,539,124, 5'554,775, 5,756,611, 5'233,049, 5,744,417, and 5 '8 5 6, 2 5 8 There are narratives, all of which are incorporated herein by reference. In one embodiment, the bulky ligand metallocene catalyst compound is a complex of transition metal catalysts known to be based on bidentate ligands containing a pyrimidine or quinoline moiety, such as US Application Serial No. 09 / 103,620, filed June 23, 1998, is incorporated herein by reference. In another embodiment, the bulky ligand metallocene compound is as described in PCT Publications W09 9/0 1 4 8 1 and W 0 9 8/4 2 6 6 4, and 倂This document is used as a reference. In another embodiment, the bulky ligand metallocene catalyst compound is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) -24. (Please read the back first Please fill in this page for the matters needing attention) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 1245773 Printed by the Employees’ Cooperative of the Intellectual Property Bureau of the Ministry of Economics, printed Α7 Β7 V. Inventors) are metal complexes, better transition Metals, bulky ligands, preferably substituted or unsubstituted pi-bonded ligands, and one or more heteropropyl groups, such as US Patent No. 5,5 2 7,7 5 Nos. 2 and 5,747,406 and EP — B1 — 07 3 5 057, all of which are incorporated herein by reference. In addition, any of the bulky ligand metallocene catalysts of the present invention also includes those containing at least one fluoride ion or fluorine-containing leaving group, such as US Application Serial No. 09/1, filed on November 13, 1998. 9.1, 916. In another embodiment, the another metal compound is a bulky ligand metallocene catalyst compound represented by the following formula: LDMQ2 (YZ) χπ (VI) where M is a Group 3 to 16 metal, preferably Groups 4 to 12 transition metals, and the best ones are Group 4, 5 and 6 transition metals; LD is a large ligand bound to M; each Q is independently bound to M and Q 2 (ΥZ) Forms a ligand, preferably a single-charged multidentate ligand; A or Q is a monovalent anionic ligand that also binds to M; when η is equal to 2, X is a valence anion group, and when η is equal to 1, X Is a divalent anionic group; η is 1 or 2. In formula (VI), L and M are as defined in the above formula (I I I). Q is as defined by the above formula (III). The better Q is selected from the combination consisting of -0, -NR-, -CR2-and -S. ------------- --- ^ ---- 11 · -------- (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -25-1245773 A7 V. Description of the invention (? 3) \ is C or S ·, Z from -0R —, -NR 2 —, — c R 3 ～ one SR ～, one SLR 3 one, — p R 2 —, ~ H — and a substituted or unsubstituted aryl group are selected, but the restriction is that when Q is —NR —, Z is from an OR —, —NR2 —, —SR —, —S 1 R3 —, a PR2 — and a tritium; r is selected from a combination including carbon, silicon, nitrogen, oxygen, and / or phosphorus, and preferably R is 1 to 20 carbons. Atomic hydrocarbon group, preferably alkyl, cycloalkyl or aryl; η is an integer from 1 to 4, preferably 1 or 2; when η is 2, X is a monovalent anionic group or when η When 1, X is a divalent anionic group; preferably X is amino formate and carboxylate Other portions of the allyl iso precursor composition Q, Υ and Ζ described. In a particularly preferred embodiment, the bulky ligand metallocene catalyst compound is represented by the following formula:

CH3 C H3c——C CH3 I CH3 / ch3 •ch3 rtt先閱讀背面之注意事項再填寫本頁) 裝 訂——------♦ 經濟部智慧財產局員工消費合作社印製 在一混合觸媒系統中，上述的第一種或第二種金屬化 合物可以用莫耳比1 : 1 0 0 0到1 0 〇 〇 : 1 ，較佳者 1 : 9 9到9 9 : 1 ，較佳者1〇：9〇到9〇：1〇， 更佳者2 0 ·· 8 0到8 0 : 2 0 ，更佳者3〇：7〇到 7 0 : 3 0 ，更佳者4 0 : 6 0到6〇：4〇組合。所選 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -26 - 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（24 ) 特定比係決定於所需的最終產物及/或活化方法。 活化劑和活化方法 本文所述金屬化合物一般是以不同的方式進行活化製 造出觸媒化合物，其含有一可配位，***和聚合燒烴的空 配位位置。 爲了本專利說明書和後附申請專利範圍之目的，、、活 化劑〃一詞經定義爲可以活化上述任何含第1 5族金屬化 合物及/或龐大配位子觸媒化合物的任何化合物或成分或 方法。非限制性的活化劑，可包括如路以士酸或非配位性 離子型活化劑或離子化活化劑或包括路以士酸，烷基鋁， 傳統型輔觸媒和其組合任何之其他化合物，其可將中性龐 大配位子茂合金屬觸媒化合物或含第1 5族金屬化合物轉 換成催化活性的含第1 5族金屬化合物或龐大配位子茂合 金屬陽離子。於本發明範圍內包括使用鋁氧烷或改質鋁氧 烷作爲活化劑，及/或ΐέ使用離子化活化劑，中性或離子 性者，如三（正丁基）銨四（五氟苯基）硼，三全氟苯基 硼非金屬前體或三全氟苯基硼非金屬前體，多鹵化的雜硼 烷陰離子（W0 98/43983)或其組合，其可電 離中性龐大配位子茂合金屬觸媒及/或含第1 5族金屬化 合物。 在一實施例中，也包括一種活化方法，其中係使用離 子化的離子型化合物，其不含有活性質子但能產生含第 1 5族金屬化合物陽離子或中性龐大配位子茂合金屬觸媒 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -27- _____·! (請先閱讀背面之注意事項再填寫本頁) 訂---Γ-- ·#· 1245773CH3 C H3c——C CH3 I CH3 / ch3 • ch3 rtt Please read the notes on the back before filling out this page) Binding ————---- ♦ Printed on a mixed catalyst by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs In the system, the above-mentioned first or second metal compound may use a molar ratio of 1: 1 to 10,000: 1, preferably 1:99 to 99: 1, and more preferably 1 〇: 90 to 90: 10, more preferably 20 · · 80 to 80: 20, more preferably 30: 70 to 70: 30, more preferably 40: 60 To 60:40 combination. The selected paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -26-1245773 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (24) The specific ratio is determined by the company Desired end products and / or activation methods. Activators and activation methods The metal compounds described herein are generally activated in different ways to produce catalyst compounds that contain an empty coordination site that can coordinate, insert, and polymerize a hydrocarbon burner. For the purposes of this patent specification and the scope of the attached patent application, the term "activator" is defined as any compound or component that can activate any of the aforementioned Group 15 metal compounds and / or bulky ligand catalyst compounds or method. Non-limiting activators may include, for example, leucoic acid or a non-coordinating ionic activator or ionizing activator or include leucoic acid, an aluminum alkyl, a conventional co-catalyst, and any other combination thereof A compound that can convert a neutral bulky ligand metallocene catalyst compound or a Group 15 metal-containing compound into a catalytically active Group 15 metal-containing compound or bulky ligand metallocene cation. It is within the scope of the present invention to use alumoxane or modified alumoxane as an activator, and / or to use an ionized activator, such as tris (n-butyl) ammonium tetrakis (pentafluorobenzene). Group) boron, triperfluorophenylboron nonmetallic precursor or triperfluorophenylboron nonmetallic precursor, polyhalogenated heteroborane anion (W0 98/43983) or a combination thereof, which can ionize neutral bulky compounds A metallocene catalyst and / or a Group 15 metal compound. In one embodiment, an activation method is also included, in which an ionized ionic compound is used, which does not contain active protons but can generate a metal catalyst containing a cation or a neutral bulky ligand containing a Group 15 metal compound This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -27- _____ ·! (Please read the precautions on the back before filling this page) Order --- Γ-- · # · 1245773

經濟部智慧財產局員工消費合作社印製 五、發明說明) 陽離子和彼等的非配位性陰離子，彼等在 EP - A - 〇 4 2 6 637， EP—A—〇 573 403和美國專利第 5，3 8 7，5 6 8號中都有敘述，所有彼等皆倂於本文 作爲參考。 還有許多方法可用來製備鋁氧烷和改質鋁氧烷，其非 限制性例子在美國專利第4，6 6，2 0 8， 4，952，54〇，5，〇91，352， 5，206，199，5，204，419， 4，874，734，4，924，018， 4，9〇8，463，4，968，827， 5，308，815，5，329，0 32， 5，248，801，5，235，081， 5，15了，137，5，1〇3，〇31， 5，391，793，5，391，5 29， 5，693，838，5，731，253， 5，731，451，5，744，656， 5，847，177，5，854，166， 5，856，256和5，939，346號及歐洲公報 EP - A — 0 561 476， ΕΡ — Β1 — 〇 2 7 9 586， EP — A-0 5 9 4 21 8 和 EP — Bl — 〇 5 8 6 665 ，與 PC 丁 公報 W〇 04/1 0 1 80中都有述及，所有彼等皆倂於本 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） ----------------：----訂—----- (請先閒讀背面之注意事項再填寫本頁) 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明P ) 文作爲參考。 可用爲活化劑的有機鋁化合物包括三甲銘，三乙銘， 二異丁基，三-正己鋁’三正辛鋁和類似者。 離子化化合物可包含一活性質子’或某種其他陽離子 其與該離子化化合物的剩餘離子相締合，但不配位或僅僅 是微弱的配位。彼等化合物在歐洲公報 EP — A — 〇 5 7 0 982， EP - A - 〇 5 2 5 732， EP - A - 0 495 375， EP - B1 — 0 5 0 0 944, EP - A-0 2 7 7 003 和 EP — A - 〇 2 7 7 004’及美國專利第 5’153，157，5，198，401， 5’2〇6，197，5，241，025， 5，384，299 和 5，502，124 號，與 1 9 9 4年8月3日提出申請的美國申請序號 〇 8 / 2 8 5，3 8 0中都有敘述，所有彼等皆倂於本文 作爲參考。 其他活化劑包括在P C T公報 w 0 98/ 0 7515中所述者如三（2 ，2一 ，2" -九氟聯苯基）氟代鋁酸酯，該公報倂於本文作爲參考。 本發明也涵槪活化劑組合，如鋁氧烷和離子化活化劑組合 ，參看例如，EP—B1 〇 573 12〇， PC丁公報w〇 94/07928和 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-29 - ------^----"1·裝----l·—訂 i· (請先閱讀背面之注意事項再填寫本頁) 舞 1245773 A7 B7 五、發明說明（27 ) W 0 95/14044及美國專利第 5 ’ 1 5 3 ，1 5 7和5 ，4 5 3 ，4 1〇號，所有彼等 皆倂於本文作爲參考。W〇 9 8 / 0 9 9 9 6 -其倂於 本文作爲參考-述及有過氯酸根，過碘酸根和碘酸根包括 其水合物的活化性龐大配位子茂合金屬觸媒化合物。 w 0 98/306 0 2 和W〇 98/306 0 3 —其 倂於本文作爲參考一述及使用鋰（2，2 / -聯苯基一二 -三甲基矽酸酯）· 4THF作爲龐大配位子茂合金屬觸 媒化合物的活化劑。W〇 9 9 / 1 8 1 3 5 —其倂於本 文作爲參考-述及使用有機硼-鋁活化劑。 E P - B 1 ~ 〇 781 299述及使用矽烷基陽離子 鹽組合非配位性可相容陰離子。此外，活化方法例如使用 輻射（參看EP — B1 - 0 6 1 5 981，其倂於本 經濟部智慧財產局員工消費合作社印製 |裝----l·---訂 (請先間讀背面之注意事頊再填寫本頁) 文作爲參考），電化學氧化反應，和類似者作爲可使中性 龐大配位子茂合金屬觸媒化合物或前體變成能夠聚合烯烴 的龐大配位子茂合金屬陽離子之目的所用的活化方法。用 以活化龐大配位子茂合金屬觸媒化合物的其他活化劑或方 法載於例如，美國專利第5，8 5 9，6 5 3和 5 ，869 ，723 號及WO 98/32775， W 0 99/42467 (二（三（五氟苯基）硼烷）苯 倂咪唑化二-十八烷基甲基銨）之中，彼此皆倂於本文作 爲參考。 於一實施例中，該活化劑爲一路以士酸化合物’更佳 者一以鋁爲基的路以士酸化合物，且最佳者一中性以銘爲 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -30 - 經濟部智慧財產局員工消費合作社印製 1245773 ____B7__ 五、發明說明P ) 基的路以士酸化合物，其具有至少一，較佳者二個，鹵化 芳基配位子與一或二個加添的不包括鹵化芳基配位子之單 陰離子配位子。此實施例的路以士酸化合物包括烯烴觸媒 活化劑以鋁爲基的路以士酸，其具有至少一龐大電子抽取 性輔助配位子例如三（全氟苯基）硼烷或三（全氟萘基） 硼烷的鹵化芳基配位子。彼等龐大輔助配位子爲足以使路 以士酸具有電子穩定性可相.容非配位性陰離子的作用者。 當該陰離子不再爲***聚合所用的強路以士酸陽離子性含 第1 5族過渡金屬陽離子之適當配位子供體，亦即，將可 中和陽離子且使彼等對聚合反應呈不活性之電子轉移，即 達到適當的離子性錯合物。 符合此較佳活化劑說明的路以士酸可用下式表之：Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention) Cations and their non-coordinating anions. They are in EP-A-〇4 2 6 637, EP-A-〇573 403 and US Patent No. There are narrations in Nos. 5, 3, 8 and 5, 68, all of which are incorporated herein by reference. There are many other methods that can be used to prepare alumoxane and modified alumoxane, non-limiting examples of which are described in U.S. Patent Nos. 4,6,6,208,4,952,54,5,091,352,5 , 206, 199, 5, 204, 419, 4, 874, 734, 4, 924, 018, 4, 809, 463, 4, 968, 827, 5, 308, 815, 5, 329, 0 32, 5,248,801,5,235,081,5,15,137,5,103,031,5,391,793,5,391,5 29, 5,693,838,5,731 Nos. 253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European Gazette EP-A — 0 561 476, EP — Β1 — 〇2 7 9 586, EP — A-0 5 9 4 21 8 and EP — Bl — 〇5 8 6 665, which are all described in PC Bulletin WO04 / 1 0 1 80, all They all know that the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) ----------------: ---- Order ----- -(Please read the precautions on the back before filling out this page) 1245773 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description P) Test. Organoaluminum compounds that can be used as the activator include trimethylammonium, triethylammonium, diisobutyl, tri-n-hexylaluminum 'tri-n-octyl aluminum and the like. The ionized compound may contain an active proton 'or some other cation which associates with the remaining ions of the ionized compound, but does not coordinate or is only weakly coordinated. Their compounds are listed in European Publication EP — A — 〇 5 7 0 982, EP-A-〇 5 2 5 732, EP-A-0 495 375, EP-B1 — 0 5 0 0 944, EP-A-0 2 7 7 003 and EP — A-〇 2 7 7 004 'and U.S. Patent Nos. 5'153,157,5,198,401, 5'2〇6,197,5,241,025, 5,384,299 and Nos. 5,502,124 and U.S. Application Serial Nos. 0/8 / 285,380, filed on August 3, 1994, are described, all of which are incorporated herein by reference. Other activators include those described in PCT Bulletin w 0 98/0 7515 such as tris (2,2,1,2 " -nonafluorobiphenyl) fluoroaluminate, which is incorporated herein by reference. The present invention also encompasses activator combinations, such as alumoxane and ionizing activator combinations, see, for example, EP-B1 〇573 12〇, PC D Bulletin WO 94/07928 and this paper size applies Chinese National Standards (CNS) A4 specifications (210 X 297 mm) -29------- ^ ---- " 1 · installation ---- l · —order i · (Please read the precautions on the back before filling in this page ) Dance 1245773 A7 B7 V. Description of the Invention (27) W 0 95/14044 and US Patent Nos. 5 '1 5 3, 1 5 7 and 5, 4 5 3, 4 10, all of which are hereby incorporated herein as reference. W〇 9 8/0 9 9 9 6-which is incorporated herein by reference-refers to metallocene compounds that have perchlorate, periodate and iodate, including their hydrates, activating bulky ligands. w 0 98/306 0 2 and WO 98/306 0 3 —which are described herein as a reference and use lithium (2, 2 / -biphenyl-bis-trimethylsilicate) · 4THF as bulky Activator of ligand metallocene catalyst. W9 9/1 8 1 3 5-which is incorporated herein by reference-describes the use of organoboron-aluminum activators. EP-B 1 to 〇 781 299 describes the use of silane-based cation salts in combination with non-coordinating compatible anions. In addition, the activation method uses, for example, radiation (see EP — B1-0 6 1 5 981, which is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed | installed ---- l · --- order (please read first Note on the back (please fill in this page again) The article is for reference), electrochemical oxidation reaction, and the like as a metal ligand that can make a neutral bulky ligand to a metallocene compound or precursor into a bulky ligand that can polymerize olefins Activation method for the purpose of metallocene cations. Other activators or methods for activating bulky ligand metallocene compounds are described in, for example, U.S. Patent Nos. 5,8 5 9,6 5 3 and 5,869,723 and WO 98/32775, W 0 99/42467 (bis (tris (pentafluorophenyl) borane) benzimidazolated di-octadecylmethylammonium), each of which is incorporated herein by reference. In one embodiment, the activator is a lanethanoic acid compound 'better'-an aluminum-based lanethanoic acid compound, and the best one is a neutral inscription-based paper standard applicable to Chinese national standards (CNS ) A4 size (210 X 297 mm) -30-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1245773 ____B7__ V. Description of the invention P) -based leucosic acid compounds, which have at least one, preferably two Halogenated aryl ligands and one or two additional anionic ligands that do not include halogenated aryl ligands. The Lewy acid compound of this embodiment includes an aluminium-based Lewy acid, an olefin catalyst activator, which has at least one large electron-extracting auxiliary ligand such as tris (perfluorophenyl) borane or tris ( Perfluoronaphthyl) halogenated aryl ligands of borane. Their bulky coordinating ligands are those which are sufficient to give the leucic acid electronic stability and compatibility with non-coordinating anions. When the anion is no longer a strong ligand for cationic acid used for insertion polymerization, a suitable ligand donor containing a Group 15 transition metal cation, that is, will neutralize the cation and render them inactive to the polymerization The electron transfer will reach the appropriate ionic complex. The leucoic acid that meets the description of this preferred activator can be expressed in the following formula:

RnAl (ArHal)3-n (VII) 其中R爲一單陰離子配位子且A r H a 1爲一鹵化c6芳族 或更高碳數的多環芳族烴或芳族環組合體，其中，兩或多 環（或稠合環系統）直接彼此或一起地接合著，且n=丄 至2，較佳者η = 1。 在另一貫施例中’至少一式（V I I ) ( A r H a 1 )爲一鹵化C 9芳族或更高者，較佳者爲一氟化萘基。合適 的非限制性R配位子包括：經取代或未經取代c ^至c 3 〇 烴基脂族或方族基’經取代意指至少有一在碳原子上的氫 係經置換成一烴基’鹵素’鹵烴基’經烴基或鹵烴基取代 $紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公爱1-TTfl-- l·-----.----^丨·裝----l·! (請先閱讀背面之注意事項再填寫本頁) 訂--- #· 1245773 A7 B7 五、發明說明f9 ) (請先閱讀背面之注意事項再填寫本頁) 有機類金屬，二烷醯胺基，烷氧基，矽烷氧基，芳氧基， 烷硫基，芳硫基，烷磷基’芳磷基或其他陰離子取代基； 氟；大體積烷氧基，其中大體積意指C 4及更高碳數的烴基 ，例如，多達約c 2 Q，例如，第三丁氧基及2，6 —二甲 基一苯氧基，及2，6 -二（第三丁基）苯氧基；—SR ;—NR2，及一PR‘2，其中各R獨立地爲一經取代或未 經取代烴基，如前面所定義者；及，經C i至C 3 Q烴基取 代有機類金屬，如三甲基矽烷基。 A r H a 1的例子包括：美國專利第 5，1 9 8，1 4 1號的苯基，萘基和蒽基及 W 0 9 7/2 9 8 5 4的鹵化聯苯基。用經鹵化或鹵化 這些詞，爲本申請案目的，係意指芳基取代的芳族配位子 的在碳原子上有至少1/3的氫原子經鹵素原子所取代， 且更佳者該芳族配位子經全鹵化。氟爲最佳的鹵素。 在另一實施例中，活化劑成分的金屬對經承載含第 1 5族觸媒化合物的金屬之莫耳比例範圍係在0 . 3 : 1 至1000 ·· 1之間，較佳者20 : 1至800 : 1，且 經濟部智慧財產局員工消費合作社印製 最佳者在5 0 : 1至5 0 0 : 1之間。於活化劑是一種電 離性活化劑，例如以陰離子肆（五氟苯基）硼爲基者之時 ，活化劑成分的金屬對含第1 5族給觸媒化合物的金屬之 莫耳比較佳者係在0 . 3 : 1至3 : 1的範圍。 也在本發明範圍內者爲前面所述含第15族金屬化合 物及/或龐大配位子茂合金屬觸媒化合物可與一或多種式 (I I I )至（V I )所表觸媒化合物或一或多種前面所 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） <32- 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（30 ) 述活化劑或活化方法組合。 在混合觸媒組成物的另一實施例中，改質鋁氧烷與本 發明第一及第二金屬化合物組合以形成一觸媒系統。在另 一實施例中，係將Μ M A〇 3 A (在庚烷中的改質甲基 鋁氧j：完，商業上可得自Akzo Chemicals，In.，商品名爲改質 甲基鋁氧烷3 A型，參看例如在美國專利第 5，0 4 1，5 8 4號中討論的甲基鋁氧烷，其倂於本文 作爲參考）與第一及第二金屬化合，物組合以形成一觸媒系 統。 在一特殊實施例中，當用兩者皆用同樣的活化劑活化 之式1及式2所表的金屬化合物時，較佳的重量百分比， 以兩種金屬化合物的重量爲基，而非以活化劑或任何承載 體爲基，爲1 0至重量9 5%的式1化合物和5至9 0重 量％的式2化合物，較佳者爲5 0至9 0重量％的式1化 合物和1 0至5 0重量％的式2化合物，更佳者6 0至 8 0重量％的式1化合物和4 0至2 0重量％的式2化合 物。在一特別較佳實施例中，式2化合物係用甲基鋁氧烷 活化，然後與式2化合物組合，再注射入反應器中。 在一特殊實施例中，當用兩者都用同一活化劑活化的 化合物I與茚基锆三一特戊酸鹽時，較佳重量百分比，以 兩種金屬化合物的重量爲基，而非以活化劑或任何承載體 的重量爲基，爲1 0至9 5重量％的化合物I和5至9〇 重量％的茚基锆三一特戊酸鹽，較佳者5 0和9 0重量％ 的化合物I和1 0至5 0重量％的茚基锆三一特戊酸鹽， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -33 - n 1 —ϋ ϋ· I n emaKm n n n ϋ· a n n >ϋ n n n n “。’ a n n an n n an n t I (請先閱讀背面之注意事項再填寫本頁) 1245773RnAl (ArHal) 3-n (VII) where R is a monoanionic ligand and Ar H a 1 is a polycyclic aromatic hydrocarbon or aromatic ring combination of a halogenated c6 aromatic or higher carbon number, where , Two or more rings (or fused ring systems) are directly bonded to each other or together, and n = 丄 to 2, preferably η = 1. In another embodiment, the at least one formula (V I I) (Ar H a 1) is a halogenated C 9 aromatic or higher, more preferably a monofluorinated naphthyl group. Suitable non-limiting R ligands include: substituted or unsubstituted c ^ to c3o hydrocarbyl aliphatic or square radical. 'Substituted means that at least one hydrogen system on a carbon atom is replaced with a hydrocarbyl' halogen The 'halohydrocarbyl' is replaced by a hydrocarbyl or halohydrocarbyl group. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇 297 public love 1-TTfl-l · -----.---- ^ 丨 · installation ---- l ·! (Please read the precautions on the back before filling this page) Order --- # · 1245773 A7 B7 V. Invention Description f9) (Please read the precautions on the back before filling out this page) Organic Metal, dialkylamine, alkoxy, silyloxy, aryloxy, alkylthio, arylthio, alkylphosphoryl'arylphosphoryl or other anionic substituents; fluorine; bulky alkoxy, where Large volume means C 4 and higher carbon number hydrocarbon groups, for example, up to about c 2 Q, for example, third butoxy and 2,6-dimethylmonophenoxy, and 2,6-bis ( Third butyl) phenoxy; -SR; -NR2, and a PR'2, wherein each R is independently a substituted or unsubstituted hydrocarbon group, as defined above; and, via C i to C 3 Q Hydrocarbyl Organic metals such as trimethyl silicon group. Examples of Ar H a 1 include: US Patent No. 5,198,141, phenyl, naphthyl and anthracenyl, and halogenated biphenyl of W 0 7 7/2 9 8 5 4. The use of the term halogenated or halogenated, for the purpose of this application, means that at least one third of the hydrogen atoms on the carbon atom of the aryl-substituted aromatic ligand are replaced with a halogen atom, and more preferably Aromatic ligands are fully halogenated. Fluorine is the best halogen. In another embodiment, the molar ratio of the metal of the activator component to the metal containing the Group 15 catalyst compound is in the range of 0.3: 1 to 1000 ·· 1, preferably 20: 1 to 800: 1, and the best printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is between 50: 1 to 500: 1. When the activator is an ionizing activator, such as those based on anionic (pentafluorophenyl) boron, the mole of the metal of the activator component is better than that of the metal containing Group 15 catalyst catalyst. The range is from 0.3: 1 to 3: 1. It is also within the scope of the present invention that the Group 15 metal compound and / or bulky ligand metallocene metal catalyst compound described above may be combined with one or more of the catalyst compounds represented by formulae (III) to (VI) or One or more of the previous paper sizes are applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) < 32-1245773 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention Or a combination of activation methods. In another embodiment of the mixed catalyst composition, the modified aluminoxane is combined with the first and second metal compounds of the present invention to form a catalyst system. In another embodiment, M MAO3 A (modified methylaluminum oxide in heptane j: end, commercially available from Akzo Chemicals, In., Under the trade name Modified methylaluminum oxide Type 3 A, see, for example, methylaluminoxane discussed in U.S. Patent No. 5,0 4, 1, 5 84, which is incorporated herein by reference) combined with the first and second metal compounds to form A catalyst system. In a special embodiment, when the metal compounds represented by Formula 1 and Formula 2 are both activated with the same activator, the preferred weight percentage is based on the weight of the two metal compounds, rather than An activator or any support based on 10 to 95% by weight of a compound of formula 1 and 5 to 90% by weight of a compound of formula 2, preferably 50 to 90% by weight of a compound of formula 1 and 1 0 to 50% by weight of the compound of formula 2, more preferably 60 to 80% by weight of the compound of formula 1 and 40 to 20% by weight of the compound of formula 2. In a particularly preferred embodiment, the compound of formula 2 is activated with methylalumoxane, then combined with the compound of formula 2 and injected into the reactor. In a special embodiment, when using compound I and indenyl zirconium tris pivalate which are both activated with the same activator, the preferred weight percentage is based on the weight of the two metal compounds rather than The weight of the activator or any support is based on 10 to 95.5% by weight of compound I and 5 to 90% by weight of indenyl zirconium tri-valerate, preferably 50 and 90% by weight. Compound I and 10 to 50% by weight of indenyl zirconium tri-valerate, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -33-n 1 —ϋ ϋ · I n emaKm nnn ϋ · ann > ϋ nnnn ". 'Ann an nn an nt I (Please read the notes on the back before filling this page) 1245773

五、發明說明θ ) 更佳者6 0至8 0重量％的化合物I比4 0至2 0重量％ 的茚基鉻三-特戊酸鹽。在一特別較佳實施例中，茚基銷 三-特戊酸鹽係用甲基鋁氧烷活化，然後與化合物I結合 ’再注射入反應器中。 通常，合倂後的金屬化合物係與活化劑按約1 0 ◦ 0 :1到約0 · 5 : 1的比例組合，在一較佳實施例中，金 屬化合物與活化劑係按約3 0 0 : 1到約1 ·· 1，較佳者 約1 5 0 ·· 1至約1 ·· 1的比例組合，對於硼烷，硼酸鹽 ’鋁酸鹽等，該比例較佳者爲約1 : 1至約1 0 : 1，且 對於烷基鋁化合物（例如氯化二乙鋁與水組合）該比例較 佳者爲約〇 . 5 ·♦ 1至約1 0 : 1。 傳統類型的觸媒系統 本發明混合觸媒組成物可另外包括含第1 5族的金屬 化合物，如前面所述者，及一傳統類型的過度觸媒。 傳統類型的過渡金屬觸媒爲技藝中熟知的傳統戚格勒 一納塔（Ziegler-Natta )，釩及菲力普類型（Phillips-type )等觸媒。例如，戚格勒-納塔觸媒即在Ziegler-Natta Catalysts and Polymerization, John Boor, Academic Press, New York，1 979中有述及。傳統類型過渡金屬觸媒的例子也 在美國專利第4 ，1 15 ，639 ，4 ，077 ，9〇4 ，4，482，687，4，564’6〇5’ 4，721，763，4，879’359 及 4，960，741號中均有討論’所有這些都倂於本文 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-34- (請先閱讀背面之注意事項再填寫本頁) 裝 訂--- 經濟部智慧財產局員工消費合作社印製 1245773 A7 B7 五、發明說明02 ) 作爲參考。可用於本發明中的傳統類型過渡金屬觸媒化合 物包括來自元素週期表中的第3至1 7族，較佳者第4至 1 2族，更佳者第4至6族的過渡金屬化合物。 這些傳統類型的過渡金屬觸媒可用式M R X表之，其 中Μ爲一來自第3至1 7族的’較佳者第4至6族，更佳 者第4族金屬，最佳者爲鈦；R爲一鹵素或一烴氧基；且 X爲金屬Μ的氧化態。非限制性的R例子包括烷氧基，苯 氧基，溴，氯及氟。傳統類型過渡金屬觸媒的非限制性例 子於Μ爲鈦時包括T i C 1 4，T i B r 4， T i ( Ο C 2 Η 5 ) 3 C 1 ，丁 i ( 0 C 2 Η 5 ) CI3， Τ i (OC4H9) 3C 1 ，Ti (OC3H7) 2C Ι2 , Τ i (〇C2H5)2Br2， Τ i C 1 3 · 1/3A1C13 及 Τι ( Ο C i 2 Η 2 5 ) C 3 ο 經濟部智慧財產局員工消費合作社印製 可用於本發明中以鎂/鈦電子供體錯合物爲基礎的傳 統類型過渡金屬觸媒化合物在，例如，美國專利第 4 ，3〇2 ，565及4 ，3〇2 ，566號中有述及， 這兩專利皆倂於本文作爲參考。 M g Τ 1 C 1 6 (乙酸乙酯）4衍生物爲特別較佳者。 英國專利申請2，105，355及美國專利第 5，3 1 7，0 3 6號，彼等皆倂於本文作爲參考，述及 多種傳統類型的釩觸媒化合物。傳統類型釩觸媒化合物的 非限制性例子包括氧釩基三鹵化物，烷氧基鹵化物及烷氧 化物，例如V〇C 1 3，V〇C 1 2 (〇B u )，其中B u 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-35- 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（33 ) 二丁基及V〇（〇C 2 Η 5 ) 3 ;釩肆鹵化物及釩烷氧基鹵 化物例如V* C 1 4及V C 1 3 (〇B u ) ，·釩與氧釩基乙醯 丙酮酸鹽及氯乙醯基丙酮酸鹽例如V (A c A c ) 3及 V 0 C 1 2 ( A c A c )，其中（A cAc)爲一乙醯丙酮 酸根。較佳傳統類型釩觸媒化合物爲V〇C 1 3，V C 1 4 及VOC 12 — OR，其中R爲一烴基，較佳者爲C li至 C 1 i。脂族或芳族烴基，其例子爲乙基，苯基，異丙基， 丁基，丙基，正丁基，異丁基，第三丁基，己基，環己基 ，萘基，等，及釩乙醯丙酮酸鹽。 適合用於本發明中的傳統類型鉻觸媒化合物，常稱爲 菲力普型（Phillips-type )觸媒，包括C r〇3，茂合鉻， 鉻酸矽烷基酯，鉻醯氯化物（C r 0 2 C 1 2 )，鉻一 2 -乙基一己烷酸鹽，乙醯丙酮酸鉻（Cr (AcAc)3) ’ 等。非限制性例子載於美國專利第3，7 0 9，8 5 3， 3，709，954，3，231，5 5〇， 3 ，242 ，〇99 ，及 4，◦了 7 ’ 9 04 號中，彼等 以全文倂於本文作爲參考。 適合用於本發明的其他傳統類型過渡金屬觸媒化合物 及觸媒系統仍然也揭示於美國專利第4，1 2 4，5 3 2 ，4，3〇2，565，4，3〇2，566’ 4，376，062，4，379 ’758， 5，〇66，737，5，763，723， 5，849，655，5，852，144， 5，854，164，及 5，869，585 號以及已公 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公爱） -36 - ~ 裝-----：----訂·--' ------ (請先閱讀背面之注意事項再填寫本頁) 1245773 4 4 五、發明說明（34 ) 開的E P — A 2 〇 E p - A 1 〇 4 15 A 2 及 中，彼等全部倂於本文 作爲參考。 其他觸媒可包括陽離子觸媒例如A 1 C 1 3，及技藝熟 知的其他鈷，鐵，鎳與鈀觸媒。參看美國專利第 3’487，112，4，472，559， 4 ’ 182，814，及 4，689，437 號，彼等全 部倂於本文作爲參考。 典型地，除了某些傳統類型鉻觸媒化合物外，這些傳 統類型過渡金屬觸媒化合物都用一或多種上述傳統類型輔 觸媒于以活化。傳統類型的過渡金屬觸媒如諳於此技者所 瞭解者也可以用本專利說明書中上述的活化劑于以活化。 用於上述傳統類型過渡金屬觸媒化合物的傳統類型輔 觸媒化合物可用式M3M4vX2c：R3b-e表之其中M3爲來 自元素週期表第1至3族與第1 2至1 3族的金屬；M4爲 一來自元素週期表第1族的金屬；v爲一 〇至1的數；各 X2爲任何一種鹵素；c爲一 0至3的數；各R3爲一單價 烴基或氫；b爲一 1至4的數；且其中b減c至少等於1 。其他用於上述傳統類型過渡金屬觸媒的傳統類型有機金 屬輔觸媒化合物具有式M 3R3k，其中Μ 3爲一第I A， I I A，I I B或I I I A族金屬，例如鋰，鈉，鈹，鋇 ，硼，鋁，鋅，鎘，及鎵；k依Μ 3的價數而定，等於1， 2或3，而Μ 3的價數轉而依其所屬的特定族而定；且各 R 3可爲任何單價烴基。 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐）-37- (請先閱讀背面之注意事項^:填寫本頁) 裝 訂-丨丨”------#· 經濟部智慧財產局員工消費合作社印製 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（?5 ) 可與上述傳統類型的觸媒化合物一起使用的傳統類型 有機金屬輔觸媒化合物的非限制性例子包括甲基鋰，丁基 鋰’二己基汞，丁基鎂，二乙基鎘，苄鉀’二乙基鋅’三 一正丁基鋁，二異丁基乙基硼，二乙基鎘，二一正丁基鋅 及三正戊基硼，以及，特別者，烷基鋁，例如··三-己基 -鋁，三乙基鋁，三甲基鋁，與三-異丁基鋁。其他傳統 類型輔觸媒化合物包括單價有機鹵化物及第2族金屬氫化 物，與第3和1 3族金屬的單-或二-有機基鹵化物與氫 化物。這種傳統類型輔觸媒化合物的非限制性例子包括溴 化二-異丁基鋁，二氯化異丁基硼，氯化甲基鎂，氯化乙 基鈹，溴化乙基鈣，氫化二-異丁基鋁，氫化甲基鎘，氫 化二乙基硼，氫化己基鈹，氫化二丙基硼，氫化辛基鎂， 氫化丁基鋅，氫化二氯硼，氫化二-溴鋁及氫化溴鎘。傳 統類型有機金屬輔觸媒化合物係技藝中已知者且在美國專 利第3 ，221 ，0〇2與5 ，〇9 3 ，415號中對這 些化合物有更完整的討論，彼等全部倂於本文作爲參考。 擔體，載體與通用承載技術 上述含第1 5族觸媒及/或混合觸媒系統，包括含第 1 5族觸媒化合物和龐大配位子茂合金屬觸媒化合物，或 者傳統觸媒化合物，可與一或多種擔體材料或載體用技藝 中熟知的或下文所述的承載方法于以組合。在一實施例中 ，本發明含第1 5族觸媒或混合觸媒系統係呈經承載形式 ，例如沈積在一擔體或載體上，與彼等接觸，與彼等一起 P 裝-----^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -38- 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明π ) 蒸發，粘合彼等，或摻合在彼等之中，吸附或吸收在彼等 之中或之上。此外，在用於一混合系統中之時，也涵槪將 龐大配位子茂合金屬觸媒龐大配位子茂合金屬觸媒承載在 一與含第1 5族觸媒分開的載體上，特別是用在其中，一 反應器中用一經承載觸媒系統以產生高分子量成分而另一 反應器中用另一經承載觸媒系統以產生低分子量成分之反 應器系統中時。 '擔體（support) 〃或、、載體（carder) 〃兩詞可交 換使用且指任何承載材料，較佳者爲多孔擔體材料，包括 無機或有機擔體材料。無機擔體材料的非限制性例子包括 無機氧化物和無機氯化物。其他載體包括樹脂擔體材料例 如聚苯乙烯，官能化或交聯有機擔體，例如聚苯乙烯二乙 烯苯聚烯烴或聚合物型化合物或任何其他有機或無機擔體 材料等，或彼等的混合物。 較佳的載體爲無機氧化物，其包括第2，3，4，5 ’ 1 3或1 4族金屬氧化物。較佳擔體包括氧化矽，氧化 銘’氧化矽-氧化鋁和其混合物。其他有用擔體包括氧化 鎂，氧化鈦，氧化鉻，氯化鎂，蒙脫石（ EP — B1 〇 511 665)，葉矽酸鹽（ phyllosilicate )，沸石，滑石，粘土等等。也可以使用這 些擔體材料的組合，例如，氧化矽一鉻，氧化矽一鋁，氧 化砍-氧化鈦等。其他的擔體材料可包括 EP 〇 7 6 7 184 B1所述多孔丙烯酸聚合物 ，其倂於本文作爲參考。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -39- ------------· I---_--— 訂---I-----· (請先閱讀背面之注意事項再填寫本頁) 1245773 A7 B7 (請先閱讀背面之注意事項再填寫本頁> 裝----l·. 訂——·------· 經濟部智慧財產局員工消費合作社印製 五、發明說明（37 ) 較佳者該載體，最佳者 圍爲約1 0到約1 〇 0平方 〇.1到4.0立方釐米/ 到5 0 〇微米。更佳者，載 500平方米/克’孔洞體 立方釐米/克’且平均粒徑 。最佳者，載體表面積範圍 克，孔洞體積範圍爲約0 · 平均粒徑範圍爲約5到約1 孔洞大小範圍典型地爲1〇 約5 0 0 A，且最佳者7 5 本發明承載觸媒的例子 4，701，432，4, 4，912，075，4, 4，937，217，5, 5，238，892，5, 5，332，7〇6，5, 5，422，325，5, 5，466，766，5, 5，529，965，5, 5，629，253，5, 5，625，015，5, 5，665，665，5, 5，714，424，5, 爲一無機氧化物，其表面積範 米/克，孔洞體積範圍爲約 克，且其平均粒徑範圍爲約5 體表面積範圍爲約5 0到約 積範圍爲約0 . 5到約3 . 5 範圍爲約1 0到約2 0 0微米 爲約1 0 0到4 0 0平方米/ 8到約5 · 0立方釐米/克’ 0 0微米。本發明載體的平均 到1 0 0 0 A ;較佳從5 〇到 到約4 5 0 A。 載於下列之中：美國專利第 8 0 8，5 6 1， 9 2 5，8 2 1， 〇〇8 ， 2 2 8 ， 2 4 〇，8 9 4， 3 4 6，9 2 5， 4 6 6，6 4 9， 4 6 8，7 0 2， 5 5 4，7 〇 4， 6 3 9，8 3 5， 6 4 3，8 4 7， 6 9 8，4 8 7， 7 2 3 ，4 0 0 ， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -40 - 1245773 A7 五、發明說明⑺ ’723 ’759 ’770 4 0 2 9 4 0 6 6 4 7 3 17 6 78 4 6 〇8 25 和 經濟部智慧財產局員工消費合作社印製 ，939 ，348號；1994年7月7日提出申請的 美國申請序號27.1 , 598 , 1997年1月23日提 出申請的序號788,736;PCT公報 W 0 95/32995 ，W〇 95/14 0 44， W 0 96/〇6187和珂〇 97/02297;和 EP—Bl—〇 685 494。彼等都是以其全文倂 於本文作爲參考。 技藝中有許多其他方法可用來承載本發明聚合觸媒化 合物或混合觸媒系統。例如，含第1 5族觸媒化合物及/ 或包含龐大配位子茂合金屬觸媒化合物的混合觸媒系統， 可含有一美國專利第5，473，202和 5 ’ 7 7 0，7 5 5號中所述經聚合物結合配位子，彼等 以其全文其倂於本文作爲參•考；本發明含第1 5族觸媒化 合物及/或龐大配位子茂合金屬觸媒化合物可經噴霧乾燥 ’如美國專利第5，6 4 8，3 1 0號中所述者，其倂於 本文作爲參考；本發明含第i 5族金屬觸媒化合物及/或 龐大配位子茂合金屬觸媒化合物所用的擔體可經官能化， 如歐洲公報E P — A - 〇 8 0 2 2 0 3中所述者，其 倂於本文作爲參考；或至少一取代基或脫離基係依美國專 利第5 ’ 688，880號中所述者選出，其以其全文倂 於本文作爲參考。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-41 - • — ——hi— — « — — 111 — — — < (請先閱讀背面之注意事項再填寫本頁) 1245773 A7 B7 五、發明說明⑼） (請先閱讀背面之注意事項再填寫本頁) 在另一實施例中，本發明係提出包括龐大配位子茂合 金屬觸媒化合物的含第1 5族觸媒系統及/或混合系統， 其更包括一用於經承載觸媒系統製備中的表面改質劑，如 在PCT公報w〇 96/11960中所述者，其以其 全文倂於本文作爲參考。本發明觸媒系統可在烯烴，例如 己烯一 1 ，的存在中製備。 在另一實施例中，包括龐大配位子茂合金屬觸媒化合 物的含第1 5族給觸媒系統及/或混合系統可與羧酸金屬 鹽酯結合，例如鋁羧酸鹽酯如含鋁——，二一，和三一硬 脂酸鹽，鋁辛酸鹽，油酸鹽和環己基丁酸鹽，如1 9 9 8 年7月1 0日提出申請的美國申請序號 09/113，216中所述者。 經濟部智慧財產局員工消費合作社印製 製造經承載含第1 5族觸媒系統及/或龐大配位子茂 合金屬觸媒系統的方法要在下文說明且其載於1 9 9 4年 6月24日提出申請的美國申請序號265，533和 1994年6月24日提出申請的265，532;及兩 者皆於1 9 9 6年1月4日公開的P C T公報 W 0 9 6 / 0 0 245 和W〇 96/00243, 等之中，彼等皆以全文倂於本文作爲參考。此程式對含第 1 5族觸媒化合物與龐大配位子茂合金屬觸媒化合物可一 起使用或分開使用。於此方法中，係將一或多種觸媒化合 物攪和在液體內形成溶液，且另外形成含一活化劑和液體 的溶液。該液體可爲任何能與本發明一或多種觸媒化合物 及/或活化劑相容的溶劑或能形成溶液的其他液體等。在 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -42 - 1245773 經濟部智慧財產局員工消費合作社印製 A7 -—-----B7__ 五、發明說明（40 ) -較佳實施例中，該液體爲環狀脂族或芳族烴，最佳者爲 甲苯。將一或多種觸媒化合物與活化劑溶液混合在一起’ 並加到多孔單體上，使得一或多種觸媒化合物溶液與活化 劑溶液的總體積比多孔擔體孔洞體積的4倍較少，更佳者 少於其3倍，甚至更佳者少於2倍；較佳範圍從1 · 1倍 到3 · 5倍，最佳範圍從1 · 2倍到3倍。 測量多孔擔體總孔洞體積的程式係技藝中熟知者。這 些程式之一的細節在 Volume 1，Experimental Methods in Catalytic Research ( Academic Press，1968)中有討論（特 別可參看6 7 - 9 6頁）。此較佳程式包括使用傳統的用 於氮吸收的B E T儀器。另一技藝中熟知的方法載於I η n e s， Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration, Vol. 28, No. 3, Analytical Chemistry 332-334 ( March, 1 956 )之中。 承載本發明觸媒化合物的其他方法在1 9 9 9年5月 17日提出申請的美國申請序號09/312，878中 述及，其以其全文倂於本文作爲參考。 當用於混合觸媒系統之中時，本發明第1 5族觸媒化 合物和龐大配位子茂合金屬觸媒化合物係以1 : 1 0 〇 〇 到1 0 0 0 : 1，較佳者1 ·· 9 9到9 9 : 1，較佳者 1〇：9〇到9〇·· 1〇，更佳者？ 2〇：8 0到8〇： 20，更佳者30 : 70到70 : 3〇，更佳者40 : 6 0到6 0 : 4 0的莫耳比組合。 在本發明混合系統一實施例中，尤其在漿液聚合法φ I I馨裝·！卜ί訂- -------# (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention θ) More preferably, 60 to 80% by weight of Compound I is compared to 40 to 20% by weight of indenyl chromium tri-pivalate. In a particularly preferred embodiment, the indenyl pin tri-pivalate salt is activated with methylalumoxane, then combined with compound I 'and injected into the reactor. Generally, the combined metal compound and the activator are combined in a ratio of about 10 ◦ 0: 1 to about 0.5: 1. In a preferred embodiment, the metal compound and the activator are about 3 0 0 : 1 to about 1 ·· 1, preferably about 15 0 ·· 1 to about 1 ··· 1 ratio combination, for borane, borate 'aluminate, etc., the ratio is preferably about 1: 1 to about 10: 1, and for alkylaluminum compounds (such as a combination of diethylaluminum chloride and water), the ratio is preferably about 0.5 to about 1 to about 10: 1. Conventional type catalyst system The mixed catalyst composition of the present invention may further include a metal compound containing Group 15 as described above, and a conventional type of excessive catalyst. Traditional types of transition metal catalysts are traditional Ziegler-Natta, vanadium, and Phillips-type catalysts. For example, the Ziegler-Natta catalyst is described in Ziegler-Natta Catalysts and Polymerization, John Boor, Academic Press, New York, 1 979. Examples of traditional types of transition metal catalysts are also in U.S. Patent Nos. 4,11,639,4,077,904, 4,482,687, 4,564'6050 '4,721,763,4, 879'359 and No. 4,960,741 are discussed. 'All these are based on this paper. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -34- (Please read the note on the back first. Please fill in this page again for the matters) Binding --- printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1245773 A7 B7 V. Invention Description 02) for reference. Traditional types of transition metal catalyst compounds that can be used in the present invention include transition metal compounds from Groups 3 to 17 of the Periodic Table, preferably Groups 4 to 12, and more preferably Groups 4 to 6. These traditional types of transition metal catalysts can be represented by the MRX table, where M is a 'better group 4 to 6 from group 3 to 17 and more preferably a group 4 metal, the most preferred is titanium; R is a halogen or a alkoxy group; and X is an oxidation state of the metal M. Non-limiting examples of R include alkoxy, phenoxy, bromine, chlorine and fluorine. Non-limiting examples of traditional types of transition metal catalysts when M is titanium include T i C 1 4, T i B r 4, T i (Ο C 2 Η 5) 3 C 1, but i (0 C 2 Η 5 ) CI3, T i (OC4H9) 3C 1, Ti (OC3H7) 2C I2, T i (〇C2H5) 2Br2, T i C 1 3 · 1 / 3A1C13 and T (〇 C i 2 Η 2 5) C 3 ο Economy The Ministry of Intellectual Property Bureau employee consumer cooperatives printed traditional types of transition metal catalyst compounds based on magnesium / titanium electron donor complexes in the present invention. For example, U.S. Patent Nos. 4,302,565, and 4 As mentioned in No. 3, 566, both patents are incorporated herein by reference. The M g Τ 1 C 1 6 (ethyl acetate) 4 derivative is particularly preferred. British Patent Application No. 2,105,355 and U.S. Patent No. 5,3,17,306 are incorporated herein by reference, and describe various traditional types of vanadium catalyst compounds. Non-limiting examples of traditional types of vanadium catalyst compounds include vanadyl trihalides, alkoxy halides, and alkoxides, such as VOC 1 3, VOC 1 2 (〇B u), where B u This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -35-1245773 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (33) Dibutyl and V〇 (〇 C 2 Η 5) 3; vanadium halides and vanadium alkoxy halides such as V * C 1 4 and VC 1 3 (〇B u), vanadium and vanadyl acetamidine pyruvate and chloroethanyl Pyruvates are, for example, V (A c A c) 3 and V 0 C 1 2 (A c A c), where (A cAc) is monoacetam pyruvate. The preferred traditional vanadium catalyst compounds are Voc 1 3, V C 1 4 and VOC 12 —OR, where R is a hydrocarbon group, preferably C li to C 1 i. Aliphatic or aromatic hydrocarbon groups, examples of which are ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, isobutyl, third butyl, hexyl, cyclohexyl, naphthyl, etc., and Vanadium acetamidine pyruvate. Conventional types of chromium catalyst compounds suitable for use in the present invention, often referred to as Phillips-type catalysts, include CrO3, chromelocene, silyl chromate, and chromium chloride ( C r 0 2 C 1 2), chromium 2 -ethyl monohexane salt, chromium acetamate pyruvate (Cr (AcAc) 3) 'and the like. Non-limiting examples are contained in U.S. Patent Nos. 3,709,8 5 3, 3,709,954, 3,231,5 50, 3, 242, 099, and 4, 7 ′ 9 04 In the text, they take the full text for reference. Other traditional types of transition metal catalyst compounds and catalyst systems suitable for use in the present invention are also disclosed in U.S. Patent Nos. 4,12,5,3,2,4,302,565,4,302,566 '4,376,062,4,379' 758, 5, 〇66,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164, and 5,869,585 No. and official paper size are applicable to China National Standard (CNS) A4 (210 x 297 public love) -36-~ Pack -----: ---- Order ·-'------ ( Please read the notes on the back before filling out this page) 1245773 4 4 V. EP — A 2 〇E p-A 1 〇 4 15 A 2 and the description of the invention (34), all of them are hereby incorporated by reference . Other catalysts may include cationic catalysts such as A 1 C 1 3, and other cobalt, iron, nickel and palladium catalysts known in the art. See U.S. Patent Nos. 3'487,112,4,472,559, 4'182,814, and 4,689,437, all of which are incorporated herein by reference. Typically, with the exception of certain traditional types of chromium catalyst compounds, these traditional types of transition metal catalyst compounds are activated with one or more of the above-mentioned conventional types of secondary catalysts. As known to those skilled in the art, conventional types of transition metal catalysts can also be activated with the activators described in this patent specification. Conventional type auxiliary catalyst compounds for the above-mentioned conventional types of transition metal catalyst compounds can be used in the formula M3M4vX2c: R3b-e table where M3 is a metal from Groups 1 to 3 and Groups 1 to 1 of the Periodic Table; Is a metal from Group 1 of the periodic table; v is a number from 10 to 1; each X2 is any halogen; c is a number from 0 to 3; each R3 is a monovalent hydrocarbon group or hydrogen; b is a 1 To 4; and where b minus c is at least equal to 1. Other traditional types of organometallic auxiliary catalyst compounds for the above-mentioned traditional types of transition metal catalysts have formula M 3R3k, where M 3 is a Group IA, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium, barium, boron , Aluminum, zinc, cadmium, and gallium; k depends on the valence of M 3 and is equal to 1, 2, or 3, and the valence of M 3 in turn depends on the specific family to which it belongs; and each R 3 can be Any monovalent hydrocarbon group. This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) -37- (Please read the notes on the back ^: Fill this page first) Binding-丨 丨 "------ # · Economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau of the People's Republic of China 1245773 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy of China A7 B7 V. Description of the Invention (? 5) Traditional organic organometallic auxiliary catalyst compounds that can be used together with the traditional catalysts Non-limiting examples include methyl lithium, butyl lithium 'dihexylmercury, butyl magnesium, diethyl cadmium, benzyl potassium' diethyl zinc 'tri-n-butyl aluminum, diisobutyl ethyl boron, Diethyl cadmium, di-n-butyl zinc and tri-n-pentyl boron, and, in particular, alkyl aluminum, such as tri-hexyl-aluminum, triethyl aluminum, trimethyl aluminum, and tri-iso Butyl aluminum. Other traditional types of auxiliary catalyst compounds include monovalent organic halides and Group 2 metal hydrides, and mono- or di-organic halides and hydrides of Groups 3 and 13 metals. This traditional type Non-limiting examples of co-catalyst compounds include di-isobutylaluminum bromide, Boron, methylmagnesium chloride, ethyl beryllium chloride, ethyl calcium bromide, di-isobutyl aluminum hydride, methyl cadmium hydride, diethyl boron hydride, hexyl beryllium hydride, dipropyl boron hydride, Octylmagnesium hydride, butyl zinc hydride, dichloroboron hydride, di-bromoaluminum hydride, and cadmium bromide hydride. Conventional types of organometallic auxiliary catalyst compounds are known in the art and are described in U.S. Patent No. 3,221,00. These compounds are discussed more fully in Nos. 2 and 5, 0093, No. 415, all of which are incorporated herein by reference. Supports, Carriers, and General Carrier Technologies The above-mentioned Group 15 catalysts and / or mixed catalysts are included. Catalyst systems, including Group 15 catalyst compounds and bulky ligand metallocene catalyst compounds, or traditional catalyst compounds, can be used with one or more carrier materials or carriers known in the art or described below The loading methods are combined. In one embodiment, the system containing a Group 15 catalyst or a mixed catalyst according to the present invention is in a supported form, for example, deposited on a support or carrier, contacting them, and P together ----- ^ ---- Order --------- (Please read the note on the back first Please fill in this page for the matters needing attention) This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 public love) -38-1245773 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5. Inventive note π) Evaporation, Adhering them, or blending in them, adsorbing or absorbing in or on them. In addition, when used in a hybrid system, it also means that the bulky ligands are metallocated to the metal. The bulky ligand metallocene catalyst is supported on a carrier separate from the Group 15-containing catalyst, especially used therein. One reactor uses a catalyst system to generate high molecular weight components and another When another reactor is used in a reactor system that carries a catalyst system to produce low molecular weight components. The terms 'support' or 'carder' are used interchangeably and refer to any supporting material, preferably a porous support material, including inorganic or organic support materials. Non-limiting examples of inorganic support materials include inorganic oxides and inorganic chlorides. Other supports include resin support materials such as polystyrene, functionalized or crosslinked organic supports such as polystyrene divinylbenzene polyolefin or polymer compounds or any other organic or inorganic support materials, or the like mixture. Preferred supports are inorganic oxides, which include Group 2, 3, 4, 5 '1 3 or 14 metal oxides. Preferred supports include silica, oxide 'silica-alumina, and mixtures thereof. Other useful supports include magnesium oxide, titanium oxide, chromium oxide, magnesium chloride, montmorillonite (EP-B101 511 665), phyllosilicate, zeolite, talc, clay, and the like. Combinations of these support materials can also be used, for example, silicon oxide-chromium oxide, silicon oxide-aluminum oxide, oxide-titanium oxide, and the like. Other support materials may include the porous acrylic polymer described in EP 0 7 7 184 B1, which is incorporated herein by reference. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -39- ------------ · I ---_--- Order --- I-- --- · (Please read the precautions on the back before filling out this page) 1245773 A7 B7 (Please read the precautions on the back before filling out this page > Install ---- l ·. Order ---- · ---- -· Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (37) The carrier is better, and the best is around 10 to 1,000 square meters 0.1 to 4.0 cubic centimeters / to 5 0 μm. More preferably, the average particle size is 500 m2 / g 'pore cubic centimeters / gram'. The best is a carrier with a surface area in grams and a pore volume in the range of approximately 0. An average particle size in the range of approximately 5 The hole size range to about 1 is typically 10 to about 500 A, and the best is 7 5 Examples of catalysts supported by the present invention 4,701,432, 4, 4,912,075, 4, 4,937, 217, 5, 5, 238, 892, 5, 5, 332, 70, 5, 5, 422, 325, 5, 5, 466, 766, 5, 5, 529, 965, 5, 5, 629, 253,5,5,625,015,5,5,665,665,5,5,714,424,5, is an inorganic oxide, its surface Product range m / g, pore volume range is York, and its average particle size range is about 5 body surface area range is about 50 to about product range is about 0.5 to about 3.5 range is about 10 to about 2 0 micron is about 100 to 400 square meters / 8 to about 5.0 cubic centimeters per gram '0 micron. The average of the carrier of the present invention is 100 A; preferably from 50 to about 4 5 0 A. Contained in the following: U.S. Patent Nos. 8,08,5 6 1,9 2 5,8 2 1,008, 2 2 8, 2 4 0, 8 9 4, 3 4 6, 9 2 5, 4 6 6, 6 4 9, 9, 4 6 8, 7 0 2, 5, 5 4, 7 〇4, 6 3 9, 8, 8 3 5, 6, 4 3, 8 4 7, 6 9 8, 4 8 7, 7 2 3, 4 0 0, this paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -40-1245773 A7 V. Description of the invention ⑺ '723' 759 '770 4 0 2 9 4 0 6 6 4 7 3 17 6 78 4 6 0 8 25 Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs, No. 939, 348; U.S. Application No. 27.1, 598, filed on July 7, 1994 Application No. 788,736 filed on March 23; PCT Gazette W 0 95/32995, W 95/14 0 44, W 0 96 / 〇618 7 and Ke 97/02297; and EP-B1--0 685 494. They all take the full text for reference. There are many other methods in the art that can be used to carry the polymeric catalyst compound or hybrid catalyst system of the present invention. For example, a hybrid catalyst system containing a Group 15 catalyst compound and / or a bulky ligand metallocene metal catalyst compound may contain a U.S. Patent No. 5,473,202 and 5 '7 7 0, 7 5 The polymer-bound ligands described in No. 5 are incorporated herein by reference in their entirety; the present invention contains Group 15 catalyst compounds and / or bulky ligand-metallocene catalyst compounds Can be spray-dried 'as described in U.S. Patent No. 5,6,4,8,10, which is incorporated herein by reference; the present invention contains a group i 5 metal catalyst compound and / or bulky ligands The support used for the metal catalyst compound may be functionalized, as described in European Publication EP — A-0 0 2 2 0 3, which is incorporated herein by reference; or at least one substituent or leaving group is based on It was selected as described in US Patent No. 5'688,880, which is incorporated herein by reference in its entirety. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -41-• — — hi — — «— — 111 — — — (Please read the notes on the back before filling this page ) 1245773 A7 B7 V. Description of the invention ⑼) (Please read the notes on the back before filling this page) In another embodiment, the present invention proposes to include the first 5 Family catalyst systems and / or hybrid systems, which further include a surface modifier for use in the preparation of a supported catalyst system, as described in PCT Bulletin WO 96/11960, which is incorporated herein in its entirety. Reference. The catalyst system of the present invention can be prepared in the presence of an olefin, such as hexene-1. In another embodiment, a Group 15-containing catalyst system and / or a hybrid system comprising a bulky ligand metallocene catalyst compound may be combined with a metal carboxylate ester, such as an aluminum carboxylate ester such as Aluminium, dione, and tristearate, aluminocaprylate, oleate, and cyclohexylbutyrate, such as U.S. application serial number 09/113, filed July 10, 1998, As described in 216. The method for printing and manufacturing of the catalyst system containing the Group 15 catalyst and / or huge ligands of the metallocene catalyst system by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is described below and it was published in 1994. U.S. Application Serial Nos. 265,533 filed on May 24 and 265,532 filed on June 24, 1994; and both were published in PCT Gazette W 0 6 6/0, dated January 4, 1996 0 245 and WO 96/00243, etc., all of which are incorporated herein by reference in their entirety. This program can be used together or separately for Group 15 catalyst compounds and bulky ligand metallocene compounds. In this method, one or more catalyst compounds are stirred to form a solution in a liquid, and a solution containing an activator and a liquid is additionally formed. The liquid may be any solvent or other liquid capable of forming a solution compatible with one or more catalyst compounds and / or activators of the present invention. Applicable to China Paper Standard (CNS) A4 (210 X 297 mm) on this paper scale -42-1245773 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 ----------- B7__ 5. Description of the invention (40) -In a preferred embodiment, the liquid is a cyclic aliphatic or aromatic hydrocarbon, the best being toluene. Mix one or more catalyst compounds with the activator solution 'and add to the porous monomer, so that the total volume of the one or more catalyst compound solutions and the activator solution is less than 4 times the pore volume of the porous support, Better is less than 3 times, even better is less than 2 times; the preferred range is from 1.1 times to 3.5 times, and the best range is from 1.2 times to 3 times. Programs for measuring the total pore volume of porous supports are well known in the art. Details of one of these programs are discussed in Volume 1, Experimental Methods in Catalytic Research (Academic Press, 1968) (see especially pages 67-96). This preferred procedure involves the use of a conventional BET instrument for nitrogen absorption. Another method well known in the art is contained in I η ne s, Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1 956). Other methods of carrying the catalyst compounds of the present invention are described in U.S. Application Serial No. 09 / 312,878, filed on May 17, 1999, which is incorporated herein by reference in its entirety. When used in a mixed catalyst system, the Group 15 catalyst compound and the bulky ligand metallocene catalyst compound of the present invention are in the range of 1: 1 to 100: 1, preferably 1 ·· 9 9 to 9 9: 1, preferably 10:90 to 90 ·· 10, more preferably? 20:80 to 80:20, more preferably 30:70 to 70:30, more preferably 40:60 to 60:40 Morse ratio combination. In one embodiment of the mixing system of the present invention, especially in the slurry polymerization method φ I I Xinzhuang!卜 ί 定-------- # (Please read the notes on the back before filling this page)

12457731245773

五、發明說明（41 ) 經濟部智慧財產局員工消費合作社印製 以微鼋旲耳/克成品經承載觸媒（包括擔體材料，混合 觸媒和活化劑）計算時’含第丄5族化合物和龐大配位子 戊口金屬觸媒化合物的總裝載量爲約4 〇微毫莫耳每克， 較丨土爲約3 8微毫莫耳/克。 在另一實施例中，尤其是在利用本發明混合系統的氣 相聚合法中，以微毫莫耳/克成品經承載觸媒（包括擔體 材料，混合觸媒和活化劑）計算時，含第1 5族化合物和 龐大配位子茂合金屬觸媒化合物的總裝載量爲低於3 〇微 耄旲耳每克’較佳者低於2 5微毫莫耳/克，更佳者低於 2 0微毫莫耳/克。 在另一實施例中’上述式（V I I )中的r基，或配 位子’可以共價結合到擔體材料上，較佳者爲金屬/類金 屬氧化物或聚合物擔體。含路以士鹼基的擔體材料或基材 會與路以士酸活化劑反應，形成一經擔體結合型路以士酸 化合物，一經承載活化劑，其中， R n A 1 ( A r H a 1 ) 3 < u中的R基係經共價結合到擔體 材料上。例如，當擔體材料是氧化矽時，氧化矽的路以士 鹼羥基即爲此種在諸鋁配位部位之一進行鍵結的方法發生 之處。較佳者，在此實施例中，擔體材料是金屬或類金屬 氧化物，較佳者其表面羥基顯示出的P K a係等於或小於對 非晶態氧化矽觀察到者，亦即，P K a小於或等於1 1。 於不受限於任何特殊理論之餘，共價結合的陰離子活 化劑，路以士酸，經認爲係先形成一含有砂院醇基的配位 錯合物，例如氧化砂（作爲路以士驗），因而形成一鍵結 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） -44 - (請先閱讀背面之注意事項41填寫本頁) 1 · n n n n n n n^eJI n al· n n I n - • · 1245773 A7 B7 五、發明說明（42 ) 到金屬氧化物擔睦的金屬/類金屬上之形式上兩極（兩性 離子的）布忍斯特酸結構。然後，布忍斯特酸的質子將路 以士酸的R基質子化，將其摘取掉，此時路以士酸即共價 結合到氧原子上。路以士酸的取代R基則變成R - 一〇一 ，其中，R /是合適的擔體材料或基材，例如，氧化矽或 含羥基的聚合物擔體。任何含表面羥基的擔體材料都適合 用於此一特殊承載方法。其他擔體材料包括玻璃珠。 經濟部智慧財產局員工消費合作社印製 _裝----l·---訂 (請先閱讀背面之注意事項再填寫本頁) 於此實施例中，其中擔體材料是金屬氧化物組成物， 彼等組成物可以另外包含其他金屬的氧化物，例如鋁、鉀 、鎂、鈉、矽、鈦和鉻的氧化物且較佳者須用熱及/或化 學方法處理來淸除水分和游離氧氣。典型的這種處理方法 是在熱烘箱真空中，在熱流化床中或用脫水劑例如有機矽 烷、矽氧烷、烷基鋁化合物等。處理的程度應該是將儘可 能多的持留水分和氧去除，但保留一化學明顯量的羥基官 能性。因此，允許在，在高達8 0 0 °C或更高到擔體材料 分解前之點下鍛燒數小時，且如果想有更高裝載量的經承 載陰離子活化劑，則適宜採用較低的鍛燒溫度和較短的時 間。於金屬氧化物是氧化矽之情況中，達到少於〇 . 1毫 莫耳到3 · 0毫莫耳活化劑/克二氧化矽的裝載量典型地 係適當者且也爲能夠做到者，例如，經由將鍛燒溫度從 2 〇〇改變到 8 〇〇 + °C。參看 Zhuralev，et al., Langmuir， 1 9 87, Vol. 3, 316，其中述及鍛燒溫度和時間對表面積不同 的氧化矽所具羥基含量之間的關聯。 作爲接著部位的羥基之訂製可以透過在加入路以士酸 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -45 - 1245773 經濟部智慧財產局員工消費合作社印製 A7 ___B7______ 〜 五、發明說明（43 ) 前’用少於化學計算量的化學脫水劑預處理而完成。較佳 者所用者爲不足地使用且含有能與矽烷醇基起反應的單~ 配位子者（例如，（C Η 3 ) 3 S i C 1 )，或者爲可水解 者’以減小對過渡金屬觸媒化合物與經結合活化劑之間的 反應之干擾。如果採用低於4 0 0 t的鍛燒溫度，可以用 雙官能偶合劑（例如，（C Η 3 ) 3 S i C 1 2 )來覆蓋存 在于較不嚴厲的鍛燒條件下之經氫鍵結矽烷醇基配對。參 看例J 如、、Investigation of Quantitative SiOH Determination by the Silane Treatment of Disperse Silica ，Gorski，et al.， Journ. of Colloid and Interface Science, Vol. 126，No. 2, Dec 1 98 8，其中討論到矽烷偶合劑對氧化矽聚合物塡料的影響 ，其亦可有效地改質本發明觸媒擔體上的矽烷醇基。同樣 地，使用超過與過渡金屬化合物反應所需化學計算量的路 以士酸可用來中和多餘的矽烷醇基而不會對觸媒製備或隨 後的聚合反應產生不利的影響。 聚合物型擔體較佳的是含羥官能基聚合物型基材，但 該官能基可以是一級烷基胺，二級烷基胺和其他者之中任 何一者，其中該等基係經摻合進聚合物鏈結構中並能與路 以士酸進行酸鹼反應使得佔據鋁所具一配位部位的一配位 子質子化，並被經摻加官能性的聚合物所置換。參看，例 如，美國專利第5，288，677號中的含官能基聚合 物，其全文倂於本文作爲參考。 其他擔體包括氧化矽，氧化鋁，氧化矽一氧化鋁’氧 化鎂，氧化鈦，氧化锆，氯化鎂，蒙脫石，葉矽酸鹽，沸 裝-----r. ί琦先閱讀背面之注意事項再填寫本頁) 訂·丨丨------#· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公« ) - 46 - 1245773 A7V. Description of the invention (41) When printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs based on micro-ears per gram of finished product and bearing catalysts (including carrier materials, mixed catalysts and activators), the calculation includes 'Group 5' The total loading of the compound and the bulky ligand pentametal catalyst compound is about 40 millimolars per gram, compared to about 38 micrommoles per gram. In another embodiment, especially in the gas-phase polymerization method using the mixing system of the present invention, when the micro-mole / g finished product is supported by a supported catalyst (including a carrier material, a mixed catalyst and an activator), The total loading of the Group 15 compound and the bulky ligand metallocene catalyst compound is less than 30 micrometers per gram, preferably less than 25 micromoles per gram, and more preferably low At 20 micromolar / g. In another embodiment, the 'r group in the above formula (V I I), or a ligand' may be covalently bonded to a support material, preferably a metal / metal-like oxide or a polymer support. Supporting materials or substrates containing Leuze base will react with the Leuze acid activator to form a once-supported Leuze acid compound, and once bearing the activator, R n A 1 (A r H The R group in a 1) 3 < u is covalently bonded to the support material. For example, when the carrier material is silicon oxide, the leuco base hydroxyl group of silicon oxide is where this method of bonding at one of the aluminum coordination sites occurs. Preferably, in this embodiment, the support material is a metal or metal-like oxide, and more preferably, its surface hydroxyl group exhibits a PK a which is equal to or less than that observed for amorphous silicon oxide, that is, PK a is less than or equal to 1 1. Without being limited to any particular theory, the covalently bound anionic activator, leucoic acid, is thought to first form a coordination complex containing a sand alcohol group, such as oxidized sand (as (Inspection), thus forming a one-click paper size applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) -44-(Please read the precautions on the back 41 to complete this page) 1 · nnnnnnn ^ eJI n al · nn I n-• · 1245773 A7 B7 V. Description of the invention (42) The form of a bipolar (zwitterionic) Bronsted acid structure on a metal / metal-like metal supported by a metal oxide. Then, the proton of the Bronsted acid protonates the R matrix of the leucic acid and removes it. At this time, the leucic acid is covalently bound to the oxygen atom. The substituted R group of leucoic acid becomes R-101, where R / is a suitable support material or substrate, for example, silica or a polymer support containing a hydroxyl group. Any support material containing a surface hydroxyl group is suitable for this particular support method. Other carrier materials include glass beads. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _ installed ---- l · --- order (please read the notes on the back before filling this page) In this embodiment, the carrier material is composed of metal oxides The composition may further include oxides of other metals, such as oxides of aluminum, potassium, magnesium, sodium, silicon, titanium, and chromium and preferably must be treated with heat and / or chemical methods to remove moisture and Free oxygen. This treatment is typically carried out in a hot oven vacuum, in a hot fluidized bed or with a dehydrating agent such as an organosilane, a siloxane, an aluminum alkyl compound, and the like. The degree of treatment should be to remove as much retained water and oxygen as possible, but retain a chemically significant amount of hydroxyl functionality. Therefore, it is allowed to be calcined for several hours at a temperature up to 800 ° C or higher before the support material decomposes, and if a higher loading capacity of the supported anionic activator is desired, a lower Calcination temperature and shorter time. In the case where the metal oxide is silicon oxide, a loading of less than 0.1 millimolar to 3.0 millimolar activator per gram of silicon dioxide is typically appropriate and can also be achieved, For example, by changing the calcination temperature from 2000 to 800+ ° C. See Zhuralev, et al., Langmuir, 1 9 87, Vol. 3, 316, which deals with the relationship between calcination temperature and time versus the hydroxyl content of silica with different surface areas. Customization of the hydroxyl group as the bonding site can be achieved through the application of the Chinese National Standard (CNS) A4 specification (210 X 297 mm) to the standard of the paper added with Lexyl acid. ___B7______ ~ 5. Description of the invention (43) Before the pretreatment with less than the stoichiometric amount of chemical dehydrating agent is completed. The preferred ones are those that are insufficiently used and contain a mono-ligand that can react with a silanol group (for example, (C Η 3) 3 S i C 1), or are hydrolyzable 'to reduce the Interference of the reaction between the transition metal catalyst compound and the bound activator. If a calcination temperature below 400 t is used, a bifunctional coupling agent (for example, (C Η 3) 3 S i C 1 2) can be used to cover the hydrogen bonding existing in the less severe calcination conditions. Junction silanol groups. See Example J, Investigation of Quantitative SiOH Determination by the Silane Treatment of Disperse Silica, Gorski, et al., Journ. Of Colloid and Interface Science, Vol. 126, No. 2, Dec 1 98 8, in which silane is discussed The effect of the coupling agent on the silicon oxide polymer material can also effectively modify the silanol group on the catalyst support of the present invention. Likewise, the use of more than the stoichiometric amount of leurosic acid required to react with the transition metal compound can be used to neutralize excess silanol groups without adversely affecting catalyst preparation or subsequent polymerization reactions. The polymer-based support is preferably a polymer substrate containing a hydroxy-functional group, but the functional group may be any one of a primary alkylamine, a secondary alkylamine, and others. Blended into the polymer chain structure and capable of acid-base reaction with leucoic acid causes a coordinator that occupies a coordination site of aluminum to be protonated and replaced with a functional polymer. See, for example, U.S. Patent No. 5,288,677, the functional group-containing polymer, which is incorporated herein by reference in its entirety. Other supports include silica, alumina, silica-alumina, 'magnesium oxide, titanium oxide, zirconia, magnesium chloride, montmorillonite, phyllosilicate, boiling-loading ----- r. Ίqi first read the back Please pay attention to this page and fill in this page) Order 丨 丨 ------ # · This paper size applies to China National Standard (CNS) A4 (210 X 297) «-46-1245773 A7

五、發明說明) 經濟部智慧財產局員工消費合作社印製 石’滑石，粘土，氧化矽-鉻，氧化矽一氧化鋁，氧化砂 -氧化鈦，多孔丙烯酸系聚合物。 在本發明另一實施例中，係在進行主要聚合反應前， 於本發明經承載含第1 5族金屬觸媒及/或龐大配位子茂 合金屬觸媒的存在下，將烯烴，較佳者C 2到c 3 〇烯烴或 ^ -烯烴，較佳者乙烯或丙烯或其組合于以預聚合。該預 聚合可以在氣體，溶液或漿相中包括在高壓下批式地或連 續地進行。該預聚合可以用任何烯烴單體或組合及/或在 任何分子量控制劑如氫之存在下進行。預聚合程式的例子 ’可參看美國專利第4，748，22 1， 4，789，359，4，923，833， 4，921，825，5，283，278 和 5 ’ 7〇5 ，5 7 8 ，及歐洲公報 EP — B — 〇 2 7 9 863 及 PC 丁 公報 W 0 9 7/4 4 3 7 1彼等都以全文倂於本文作爲參考 含第1 5族金屬化合物的溶液進料 在另一實施例中，本發明含第1 5族金屬觸媒化合物 和活化劑係在液體載體，較佳者溶液之中，導入漿相或氣 相反應器內。該觸媒和活化劑可以分別給入或一起給入且 可以在即將進入反應器前組合後輸入，也可以在進入反應 器前接觸較長一段時間後再輸入。較佳的液體載體包括院 類，較佳者戊烷，己烷，異戊烷，甲苯，環己烷，異戊院 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -47 - ~裝-----^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 1245773 A7 B7 五、發明說明（45 ) ，庚烷，辛烷，異己烷等。特別較佳的液體載體包括己烷 ，戊烷，異戊烷和甲苯。 觸媒系統，金屬化合物及/或活化劑，最好透過一或 多種溶液導入反應器中。在一實施例中，係將經活化金屬 化合物在烷例如戊烷，己烷，甲苯，異戊烷等中的溶液導 入氣相或漿相反應器內。在另一實施例中，觸媒系統或其 成分可以透過懸浮液或乳液導入反應器中。在一實施例中 ，過渡金屬化合物係與活化劑如經改質甲基鋁氧烷在溶劑 中接觸，然後立即將溶液輸入氣相或漿相反應器內。在另 一實施例中，係將金屬化合物溶液和活化劑溶液組合，使 其反應一段時間後，導入反應器內。在一較佳實施例中， 係使觸媒和活化劑在導入反應器前，反應至少1秒，較佳 者至少5分鐘，甚至更佳者反應5〜6 0分鐘。觸媒和活 化劑在溶液中的典型濃度爲0 . 0 0 0 1到0 . 2 0 0莫 耳/升，較佳者0·001到0·05莫耳/升，更佳者 0·005到0·025莫耳/升。通常，金屬化合物和 活化劑的組合比例爲約1 0 0 0 : 1到約0 . 5 ·· 1。在 一較佳實施例中，金屬化合物和活化劑的組合比例爲約 3〇〇·· 1到約1 : 1 ;較佳者約1 0 : 1到1 : 1 ，對 硼烷而言，較佳比例爲約1 : 1到約1 0 : 1且對烷基鋁 化合物（例如組合水的氯化二乙基鋁）而言，較佳比例爲 約 0 · 5 ·· 1 到 1 0 : 1。 在另一實施例中，觸媒系統係由過渡金屬化合物（觸 媒）及/或活化劑（輔觸媒）構成，彼等最好係在溶液中 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-48 - (請先閱讀背面之注意事項再填寫本頁) · n n H· ϋ n n n 一OJ0 i n ·_1 n n n ·# 經濟部智慧財產局員工消費合作社印製 1245773 Α7 Β7 五、發明說明π ) (請先閱讀背面之注意事項再填寫本頁> 給到反應器內內。金屬化合物溶液典型地係經由將觸媒溶 解在任何溶劑例如烷，甲苯，二甲苯等中而製備成。可以 先純化溶劑以去除可影響催化活性的任何毒物，包括任何 微量水及/或經氧化的化合物。溶劑純化可以透過，例如 ，使用經活化氧化鋁和經承體活化銅觸媒。觸媒較佳者爲 完全溶解在溶液中形成均勻溶液。如果需要，觸媒和活化 劑兩者都可以溶解在相同溶劑中。觸媒一旦溶解，可以儲 存起來直到使用爲止。 對於聚合作用而言，較佳者在注入反應器前即將觸媒 與活化劑組合。另外，可以將其他溶劑和反應物加到觸媒 溶液中（線上或離線），加到活化劑中（線上或離線）， 或加到經活化的一或多種觸媒中。 在較佳實施例中，本發明觸媒系統的產率爲每小時每 克觸媒產生10，0 0 0克的聚合物或更多。 經濟部智慧財產局員工消費合作社印製 上述經溶液給入的本發明觸媒系統，在廣泛的反應器 條件和樹脂品級從流動指數0 . 2 d g /m i η到溶融指 數3 dg/m i η及密度從〇 · 9 5 0克/立方釐米到 0·916克/立方釐米下有極佳操作性。在1〇多天連 續的領試規模操作中，觸媒系統沒有發生任何樹脂黏聚或 成片現象。本發明也有很少或沒有產生污垢的優點。在聚 合過程之中或之後，看不到任何片，厚塊或碎粒。在反應 器壁內側或循環氣體管內，也沒有聚合物蓄積。而且，在 整個運轉中，沒有發生跨熱交換器，循環氣體壓縮機或氣 體發散板的壓力降增加現象。 本紙張尺度適用中國國家標準（CNS— (210 X 297公爱)Γ49Τ ' 1245773 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明67 ) 混合觸媒系統的溶液淮料 在另一實施例中，本發明混合觸媒系統及/或活化劑 (輔觸媒）係以溶液狀態給到反應器內內。金屬化合物溶 液可以透過將觸媒溶解在任何合適溶劑例如烷，甲苯，二 甲苯等之中而製備。可以先純化溶劑以去除可影響催化活 性的任何毒物，包括任何微量水及/或經氧化的化合物。 溶劑純化可以透過使用經活化氧化鋁和經承載體活化銅觸 媒。觸媒較佳者要完全溶解在溶液中，形成均勻溶液。如 果需要，可以將兩種觸媒溶解在同種溶劑中。一旦觸媒溶 解，可以無限期儲存起來直到使用。 對於聚合作用，較佳者在給到反應器內前將觸媒和一 活化劑組合。另外，可以將其他溶劑和反應物加到觸媒溶 液中（線上或離線），加到活化劑中（線上或離線），或 加到經活化一或多種觸媒中。參看美國專利第 5，317，036 和 5，693，727 號， EP-A - 0 5 9 3 083 和 W 0 97/46599，彼等都全文倂於本文作爲參考 ，彼等皆述及反應器溶液進料系統。有許多不同的組態可 用來組合觸媒和活化劑。 觸媒系統，金屬化合物及/或活化劑可以在一或多種 溶液中給到反應器內。金屬化合物可以分別活化，按順序 地或一起地。在一實施例中，係將兩種經活化金屬化合物 的烷例如戊烷，己烷，甲苯，異戊烷等中溶液輸入氣相或 漿相反應器。在另一實施例中，觸媒系統或其成分可以透 (請先閱讀背面之注意事項再填寫本頁) .· 裝----l· — 訂-丨-1-----#· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-50 - 經濟部智慧財產局員工消費合作社印製 1245773 A7 ____B7__ 五、發明說明β ) 過懸浮液或乳液給到反應器內。在另一實施例中，係將第 二種金屬化合物在溶劑中與活化劑例如改質甲基鋁氧烷接 觸，然後立即將溶液輸入氣體、漿或溶液相反應器內。含 第1 5族金屬化合物溶液係和第二種化合物與活化劑的溶 液組合，然後給到反應器內。 在以下的闡述例中，A指一種觸媒或觸媒混合物，且 B指不同的觸媒或觸媒混合物。A和B中的觸媒混合物可 以是相同觸媒，只是比例不同。而且，値得注意的是加添 溶劑或惰性氣體可以在許多位置上加入。 闡述例1 : A和B加上活化劑離線混合，然後給到反 應器內。闡述例1由圖1圖式表出。 P述例2 : A和B離線混合。線內（in-line )加入活 化劑，然後給到反應器內。闡述例2由圖2圖式表出。 闉述例3 : A或B與活化劑接觸離線），然後在給 到反應器內前線內加入A或B。闡述例3由圖形3圖式表 出。 闡述例4 : A或B與活化劑接觸（線上），然後在給 到反應器內前線內加入A或B。闡述例4由圖4圖式表出 〇 闡述例5 : A和B分別與活化劑離線接觸，然後在進 入反應器前將A和活化劑與將B和活化劑線內接觸。闡述 例5由圖5圖式表出。 閫述例6 : A和B各自與活化劑線內接觸，然後在進 入反應器前將A和活化劑與將B和活化劑線內接觸。（由 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -51 - - ' < · n ϋ— ·ϋ ·ϋ n n n I— m i i ΙΙΜ,Ν v 0 tmeme n n n < (請先閱讀背面之注意事項再填寫本頁) 訂——'---- 1245773 A7 B7 五、發明說明θ9 ) (請先閱讀背面之注意事項再填寫本頁) 於A對B的比例祖:活化劑對A的比例担J舌化劑對B的比例 能夠分別控制，因此這是較佳的組態。）闡述例6由圖6 圖式表出。 闡述例7 :在此例中，係將A或B與活化劑（線上） 接觸，同時A或B的另一溶液與活化劑離線接觸，然後在 給到反應器內前將A或B與活化劑的兩種溶液流線內接觸 。闡述例7由圖7圖式表出。 闡述例8 : A與B線上接觸，然後線內將活化劑給到 A與B的混合液中。闡述例8由圖8圖式表出。 闡述例9 :將A用活化劑離線活化。然後將A和活化 劑線上與B接觸。然後線內將活化劑給到A和B和活化劑 的混合物中。闡述例9由圖9圖式表出。 在以上的任一闡述例中，可以採用用於混合及/或造 成某一滯留時間的工具。例如，可以使用一混合葉片或螺 絲來混合組成分，或使用某一長度的管件來獲得組成分間 合意的接觸或滯留時間。v'線上〃指所述物質係在直接或 間接與反應器系統相連的管件，試管或容器中。''離線〃 經濟部智慧財產局員工消費合作社印製 指所述物質在不與反應器系統相連的管件，試管或容器中 〇 在另一實施例中，本發明係有關在氣相反應器中聚合 烯烴的方法，其中係將至少2種觸媒和至少1種活化劑在 液體載體中給到聚合反應器內。在一較佳實施例中，係將 觸媒和活化劑在給到反應器內前係在液體載體中組合。 在另一實施例中，諸觸媒係在液體載體中組合，然後 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-52 - 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明⑼） 輸入與反應器相連的引導裝置中且其後，在與觸媒相同或 不同點將活化劑給到引導裝置內。在另一實施例中，係將 諸觸媒在液體載體中組合後，將活化劑導到該液體載體內 0 在另一實施例中，係將含觸媒和活化劑的液體載體放 在引導液體載體進入反應器的裝置中。在另一實施例中， 係將觸媒和液體載體導入該裝置中，再加入活化劑。 在另一較佳實施例中，包含液體載體的組合物更包含 一液體流，該液體流係流入或噴入反應器。 在另一較佳實施例中，將至少一種觸媒，至少一種活 化劑和液體載體放入一裝置內，以便導到反應器內，其中 ，在第一種觸媒和活化劑經導入裝置後，才加入其他一或 多種觸媒。 聚合方法 上述本發明觸媒組成物，觸媒系統，混合觸媒系統， 經承載觸媒系統或溶液進料觸媒系統適合用於任何聚合方 法’包括溶液，氣體或漿相法，或以上方法的結合。較佳 的聚合法是氣相或漿相法且更佳者爲採用單一反應器，而 最佳者是採用單一氣相反應器者。 在一實施例中，本發明係有關聚合反應或共聚反應， 其包括1或多含有2至3 0碳原子，較佳者2至1 2碳原 子，且更佳者2至8碳原子的單體之聚合反應。本發明尤 其適合共聚反應，其包括1或多種烯烴單體的聚合反應， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -53- • L---------^丨 裝-----^----訂·-------- (請先閱讀背面之注意事項再填寫本頁) 1245773 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明θ ) 包括乙烯’丙烯’丁烯—1 ，戊烯一 1 ，4 一甲基—戊烯 —1 ’己烯一 1 ，辛烯一 1 ，癸烯一 1 ，3 —甲基—戊烯 —1 ’ 3，5，5 —三甲基一己烯一 1和環狀烯烴或上述 的組合。其他單體可包括乙烯基單體，二烯烴例如二烯， 多嫌，原冰片烯，原冰片二烯單體。較佳者係製成乙烯共 聚物’其中的共單體爲至少一種含有4至15個碳原子， 較佳者含4至1 2個碳原子，更佳者含4至8個碳原子且 最佳者含4至7碳原子的α -燃烴。在另一實例中，可將 W〇9 8/3 7 1 0 9中揭示的墣暖孿二取代烯烴用本文 所述本發明于以聚合或共聚合。 在另一實施例中，係將乙烯或丙烯和至少兩種不同的 共單體聚合形成一參聚物。較佳的共單體是含4至1 0個 碳原子，更佳者含4至8個碳原子的α -烯烴單體視需要 與至少一種二烯單體的組合。較佳的參聚物包括乙烯/丁 烯一 1/己烯一 1，乙烯/丙烯/丁烯一 1，丙烯/乙烯 /己烯一 1 ，乙烯/丙烯/原冰片烯等的組合。 在一特別較佳實施例中，本發明方法係有關乙烯和至 少一種含3至8個碳原子，較佳者含4至7個碳原子的共 單體之聚合。特別者，該共單體爲丁烯一 1，4 -甲基-戊烯一 1，己烯一 1和辛烷一 1，最佳的共單體是己烯一 1及/或丁烯一 1。 在氣相聚合法中，典型情況是使用一連續循環，其中 ，在反應器系統循環的一部分，係在反應器中用聚合熱來 加熱一循環氣體流，也叫再循環流或流化質。而在循環的 ------------111^ 裝-----^----訂--------- (靖先閱讀背面之注音？事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -54 - 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7_ 五、發明說明戶2 ) 另一部分係用反應器外部冷卻系統從再循環組成物取出該 熱量。通常’在製造聚合物所用的氣體流化床法中，係將 含有一或多種單體的氣體流在反應條件下觸媒存在中，連 續循環通過流化床。氣流從流化床中流出並再循環流進反 應器。同時’將聚合產生物從反應器中取出並加入新的單 體以補充經聚合單體。（參看例如美國專利第 4，543，399，4，588，79〇， 5，〇28，670，5，317，036， 5，352，749，5，405，922， 5，436，304，5，453，471 ，5，462，999，5，616，661 和 5 ’ 668，228，以上都以其全文倂於本文作爲參考 )° 氣相法中反應器壓力的變易範圍係約1 0 p s i g ( 69kPa)到約5〇〇psig(3448kPa)， 較佳的變化範圍爲約1 〇 〇 p s i g ( 6 9 0 k P a )到 約4 0 0 p s i g ( 2 7 5 9 k P a )，或從約2〇〇 PS ig (i379kPa)到約 400ps ig ( 2 7 5 9 k P a )，更佳的變化範圍爲約25 Ops ig (1724kPa)到約35〇psig(2414 k P a ) 〇 氣相法中反應器溫度的變易範圍爲約3 0 °C到約 1 2 0 °C，較佳的變化範圍爲約6 0 t到約1 1 5 °C，更 佳的變化範圍爲約7 5 °C到1 1 0 °C，且最佳的變化範圍 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-55 - | 裝-----^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1245773 Λ7 --—___ B7 i、發明說明户） 爲約8 5 °C到約1 1 0 °c。改變聚合溫度也可用來作爲改 變最終聚合產物性質的工具。 觸媒或觸媒系統的產率係受到主要單體的分壓所影響 。主要單體’乙烯或丙烯，較佳者乙烯，的較佳莫耳比爲 約2 5到9 0莫耳比且單體分壓範圍爲約7 5 p s 1 g ( 5l7kPa)到約30〇psig (2〇69kPa) ’其爲氣相聚合法中的典型條件。在一實施例中，乙烯分 壓爲約 220 到 24 Ops ig (1517 到 1653 a)。在另一實施例中，反應器中己烯對乙烯的莫耳 比爲0 · 0 3 : 1到〇，〇 8 : 1 。 在另一實施例中，本發明所用的反應器及本發明方法 產生的聚合物大於5 0 0磅每小時（2 2 7公斤/時）到 大於約200，000磅/時（90，900公斤/每小 時）或更多，較佳者大於1 0 0 0磅/每小時（4 5 5公 斤/ ·時），更佳者大於10，000磅/時（4540公 斤/時），甚至更佳者大於25，000磅/時（ 11，300公斤/時），仍然更佳者大於35，0〇〇 磅/時（1 5，9 0 0公斤/時）；依然甚至更佳者大於 50，000磅/時（22，70〇公斤/時）且最佳者 大於65，000磅/時（29，000公斤/時）到大 於100 ，000磅/時（45 ，5〇〇公斤/時）。 本發明方法所涵蓋的其他氣相法包括在美國專利第 5，627，242，5，665，818 和 5，6 7 7，3 7 5號，及歐洲公報 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-56 - l·----------裝-----r . (請先閱讀背面之注意事項再填寫本頁) 訂--------- 1245773 A7 五、發明說明0 ) EP — a—〇 7 9 4 2〇〇，V. Description of the invention) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Stone talc, clay, silica-chromium oxide, silica-alumina, sand oxide-titanium oxide, porous acrylic polymer. In another embodiment of the present invention, before the main polymerization reaction is performed, the olefin is compared in the presence of a supported Group 15 metal catalyst and / or bulky ligand-metallocene metal catalyst in the present invention. Preferred are C 2 to c 3 0 olefins or ^ -olefins, more preferred is ethylene or propylene or a combination thereof for prepolymerization. This prepolymerization can be carried out batchwise or continuously in the gas, solution or slurry phase, including under high pressure. This prepolymerization can be performed with any olefin monomer or combination and / or in the presence of any molecular weight control agent such as hydrogen. Examples of pre-polymerization programs' can be found in U.S. Patent Nos. 4,748,22 1, 4,789,359, 4,923,833, 4,921,825, 5,283,278, and 5'705, 5 7 8, and European Gazette EP — B — 〇 2 7 9 863 and PC Ding Gong W 0 9 7/4 4 3 7 1 They are all incorporated herein by reference in their entirety. In another embodiment, the Group 15 metal-containing catalyst compound and activator of the present invention are introduced into a slurry carrier or a gas phase reactor in a liquid carrier, preferably a solution. The catalyst and the activator may be fed separately or together and may be input after being combined immediately before entering the reactor, or may be input after being contacted for a long period of time before entering the reactor. The preferred liquid carriers include hospitals, preferably pentane, hexane, isopentane, toluene, cyclohexane, and isopentane. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). -47-~ Pack ----- ^ ---- Order --------- (Please read the notes on the back before filling this page) 1245773 A7 B7 V. Description of the invention (45), Geng Alkane, octane, isohexane, etc. Particularly preferred liquid carriers include hexane, pentane, isopentane and toluene. The catalyst system, metal compound and / or activator is preferably introduced into the reactor through one or more solutions. In one embodiment, a solution of an activated metal compound in an alkane such as pentane, hexane, toluene, isopentane, etc. is introduced into a gas phase or slurry phase reactor. In another embodiment, the catalyst system or its components can be introduced into the reactor through a suspension or emulsion. In one embodiment, the transition metal compound is contacted with an activator such as modified methylaluminoxane in a solvent, and the solution is immediately introduced into a gas phase or slurry phase reactor. In another embodiment, the metal compound solution and the activator solution are combined and reacted for a period of time before being introduced into the reactor. In a preferred embodiment, the catalyst and activator are allowed to react for at least 1 second, preferably for at least 5 minutes, and even more preferably for 5 to 60 minutes before being introduced into the reactor. The typical concentration of the catalyst and activator in the solution is from 0. 0 0 0 1 to 0. 2 0 0 mol / L, preferably 0. 001 to 0. 05 mol / L, and more preferably 0. 005. To 0.025 mol / liter. Generally, the combined ratio of the metal compound and the activator is from about 100 0: 1 to about 0.5 ·· 1. In a preferred embodiment, the combined ratio of the metal compound and the activator is from about 300 ·· 1 to about 1: 1; preferably about 10: 1 to 1: 1. For borane, The preferred ratio is about 1: 1 to about 10: 1 and for alkylaluminum compounds (such as diethylaluminum chloride in combination with water), the preferred ratio is about 0. 5 ·· 1 to 1 0: 1 . In another embodiment, the catalyst system is composed of a transition metal compound (catalyst) and / or an activator (auxiliary catalyst), and they are preferably in solution. The paper size applies Chinese National Standard (CNS) A4. Specifications (210 X 297 mm) -48-(Please read the precautions on the back before filling out this page) · nn H · ϋ nnn-OJ0 in · _1 nnn · # Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1245773 Α7 Β7 V. Description of the invention π) (Please read the precautions on the back before filling out this page> Give it to the reactor. The metal compound solution is typically dissolved by dissolving the catalyst in any solvent such as alkane, toluene, xylene, etc. It can be prepared by purification. The solvent can be purified first to remove any poisons that can affect the catalytic activity, including any trace amount of water and / or oxidized compounds. The solvent purification can be through, for example, the use of activated alumina and support-activated copper contacts The catalyst is preferably completely dissolved in the solution to form a homogeneous solution. If necessary, both the catalyst and the activator can be dissolved in the same solvent. Once the catalyst is dissolved, it can be stored Get up until use. For polymerization, it is better to combine the catalyst and activator before injection into the reactor. In addition, other solvents and reactants can be added to the catalyst solution (online or offline), and added to Activator (online or offline), or added to one or more activated catalysts. In a preferred embodiment, the catalyst system of the present invention has a yield of 10,000 per gram of catalyst per hour. Grams of polymer or more. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the above-mentioned catalyst system of the present invention fed by solution, under a wide range of reactor conditions and resin grades from a flow index of 0.2 dg / mi η It has excellent operability under the melting index of 3 dg / mi η and density from 0.950 g / cm3 to 0.916 g / cm3. In more than 10 days of continuous pilot scale operation, the catalyst The system does not have any resin cohesion or sheeting. The invention also has the advantage of little or no fouling. During or after the polymerization process, no sheets, lumps or particles can be seen. Inside the reactor wall or Inside the circulating gas pipe Polymer accumulation. In addition, during the entire operation, no increase in pressure drop across the heat exchanger, circulating gas compressor or gas diffusion plate occurred. This paper size applies to the Chinese national standard (CNS- (210 X 297 公 爱) Γ49Τ '' 1245773 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description 67) Solution solution of mixed catalyst system In another embodiment, the mixed catalyst system and / or activator (auxiliary catalyst of the present invention) ) Is supplied into the reactor in the form of a solution. The metal compound solution can be prepared by dissolving the catalyst in any suitable solvent such as alkane, toluene, xylene and the like. The solvent may be purified first to remove any toxicants that can affect catalytic activity, including any trace amounts of water and / or oxidized compounds. Solvent purification can be accomplished by using activated alumina and carrier-activated copper catalysts. The catalyst should be completely dissolved in the solution to form a homogeneous solution. If desired, both catalysts can be dissolved in the same solvent. Once the catalyst is dissolved, it can be stored indefinitely until use. For polymerization, it is preferred to combine the catalyst with an activator before feeding into the reactor. In addition, other solvents and reactants can be added to the catalyst solution (online or offline), to the activator (online or offline), or to one or more activated catalysts. See U.S. Patent Nos. 5,317,036 and 5,693,727, EP-A-0 5 9 3 083 and WO 97/46599, all of which are incorporated herein by reference in their entirety, and they all refer to the reactor Solution feeding system. There are many different configurations for combining catalysts and activators. Catalyst systems, metal compounds and / or activators can be fed into the reactor in one or more solutions. The metal compounds can be activated separately, sequentially or together. In one embodiment, a solution of two activated metal compound alkane such as pentane, hexane, toluene, isopentane, etc. is input into a gas phase or slurry phase reactor. In another embodiment, the catalyst system or its components can be transparent (please read the precautions on the back before filling out this page). · Equipment ---- l ·-order-丨 -1 ----- # · This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -50-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1245773 A7 ____B7__ V. Description of the invention β) Super suspension or emulsion is given to the reactor Inside. In another embodiment, the second metal compound is contacted with an activator, such as modified methylaluminoxane, in a solvent, and the solution is immediately introduced into the gas, slurry, or solution phase reactor. A solution containing a Group 15 metal compound and a solution of the second compound and an activator are combined and fed to the reactor. In the following illustrative examples, A refers to a catalyst or a catalyst mixture, and B refers to a different catalyst or a catalyst mixture. The catalyst mixtures in A and B can be the same catalyst, but the ratios are different. Furthermore, it is important to note that the addition of solvents or inert gases can be added at many locations. Illustrative Example 1: A and B are mixed offline with the activator and then fed to the reactor. Explanatory example 1 is schematically illustrated in FIG. 1. Example 2: A and B are mixed off-line. The activator was added in-line and fed into the reactor. Explanatory example 2 is schematically shown in FIG. 2. Example 3: A or B is in contact with the activator offline), and then A or B is added to the front line of the reactor. Explanatory example 3 is shown diagrammatically in Figure 3. Elaboration Example 4: A or B is in contact with the activator (on-line), and then A or B is added to the front line to the reactor. Explanatory Example 4 is graphically shown in Figure 4 〇 Explanatory Example 5: A and B were in offline contact with the activator, respectively, and then A and activator were brought into contact with B and the activator in line before entering the reactor. Elaboration Example 5 is schematically illustrated in FIG. 5. Description Example 6: A and B are each brought into contact with the activator line, and then A and activator are brought into contact with B and the activator line before entering the reactor. (From this paper size, Chinese National Standard (CNS) A4 specifications (210 X 297 mm) apply -51--'< · n ϋ— · ϋ · ϋ nnn I— mii ΙΙΜ, Ν v 0 tmeme nnn < (Please First read the notes on the back before filling this page) Order --'---- 1245773 A7 B7 V. Description of the invention θ9) (Please read the notes on the back before filling this page) The ratio of A to B: Activator The ratio of agent to A can be controlled separately, so this is a better configuration. ) Explanatory example 6 is schematically shown in FIG. 6. Elaboration Example 7: In this example, A or B is brought into contact with an activator (online), while another solution of A or B is brought into offline contact with the activator, and then A or B is activated with the activator before being fed into the reactor. The two solutions of the agent are in streamline contact. Explanatory example 7 is schematically illustrated in FIG. 7. Elaboration Example 8: A and B are in contact with each other, and then the activator is given to the mixed solution of A and B in the line. Explanatory example 8 is schematically shown in FIG. 8. Elaboration Example 9: A was activated off-line with an activator. A and the activator are then brought into contact with B. The activator was then given to the mixture of A and B and the activator in-line. Explanatory example 9 is schematically illustrated in FIG. 9. In any of the above examples, tools for mixing and / or creating a certain residence time may be used. For example, a mixing blade or screw can be used to mix the components, or a certain length of pipe can be used to obtain the desired contact or residence time between the components. The v 'line means that the substance is in a pipe, test tube or container directly or indirectly connected to the reactor system. '' Offline〃 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs means that the substance is in a tube, test tube or container that is not connected to the reactor system. In another embodiment, the present invention relates to a gas phase reactor A method for polymerizing olefins, wherein at least two catalysts and at least one activator are fed into a polymerization reactor in a liquid carrier. In a preferred embodiment, the catalyst and activator are combined in a liquid carrier before being fed into the reactor. In another embodiment, the catalysts are combined in a liquid carrier, and then this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -52-1245773 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation A7 B7 V. Description of the Invention ⑼) Enter the guide device connected to the reactor and thereafter, give the activator to the guide device at the same or different point from the catalyst. In another embodiment, after the catalysts are combined in a liquid carrier, the activator is introduced into the liquid carrier. In another embodiment, the catalyst and the activator-containing liquid carrier are placed in the guide The liquid carrier enters the device of the reactor. In another embodiment, the catalyst and the liquid carrier are introduced into the device, and then an activator is added. In another preferred embodiment, the composition comprising a liquid carrier further comprises a liquid stream which flows into or is sprayed into the reactor. In another preferred embodiment, at least one catalyst, at least one activator and a liquid carrier are placed in a device to be introduced into the reactor, wherein after the first catalyst and activator are introduced into the device Before adding one or more other catalysts. Polymerization method The above-mentioned catalyst composition, catalyst system, mixed catalyst system of the present invention, the supported catalyst system or the solution feed catalyst system are suitable for any polymerization method, including the solution, gas or slurry phase method, or the above methods Combination. The preferred polymerization method is a gas phase or slurry phase method, and a more preferred one is a single reactor, and a more preferred one is a single gas phase reactor. In one embodiment, the present invention relates to a polymerization reaction or a copolymerization reaction, which includes 1 or more monomers containing 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Body polymerization. The present invention is particularly suitable for copolymerization, which includes the polymerization of one or more olefin monomers. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -53- • L ------- -^ 丨 Installation ----- ^ ---- Order · -------- (Please read the precautions on the back before filling out this page) 1245773 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs V. Description of the invention θ) Including ethylene 'propylene' butene-1, pentene-1, 4-methyl-pentene-1 'hexene-1, octene-1, decene-1, 3-methyl —Pentene-1 ′ 3,5,5-trimethyl-hexene-1 and a cyclic olefin or a combination thereof. Other monomers may include vinyl monomers, diolefins such as diene, polyphosphine, orthobornadiene, orthobornadiene monomers. The preferred one is made of an ethylene copolymer. The comonomer is at least one containing 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Preferred are alpha-burning hydrocarbons having 4 to 7 carbon atoms. In another example, the warm twin disubstituted olefins disclosed in W09 8/3 7 10 9 can be polymerized or copolymerized with the invention described herein. In another embodiment, ethylene or propylene and at least two different comonomers are polymerized to form a parapolymer. The preferred comonomer is a combination of an α-olefin monomer having 4 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms, if necessary, with at least one diene monomer. Preferred reference polymers include a combination of ethylene / butene-1 / hexene-1, ethylene / propylene / butene-1, propylene / ethylene / hexene-1, ethylene / propylene / orbornene and the like. In a particularly preferred embodiment, the process of the present invention relates to the polymerization of ethylene and at least one comonomer containing 3 to 8 carbon atoms, preferably 4 to 7 carbon atoms. In particular, the comonomers are butene-1,4-methyl-pentene-1, hexene-1 and octane-1, the best comonomers are hexene-1 and / or butene-1 1. In the gas-phase polymerization method, a continuous cycle is typically used, in which, in a part of the reactor system cycle, the polymerization heat is used in the reactor to heat a circulating gas stream, also called a recycle stream or a fluidized substance. And in the cycle of ------------ 111 ^ equipment ----- ^ ---- order --------- (Jing first read the phonetic on the back? Matters before filling in (This page) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -54-1245773 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Inventor 2) The other part is the reaction The external cooling system removes this heat from the recycled composition. Generally, in a gas fluidized bed process for producing polymers, a gas stream containing one or more monomers is continuously circulated through the fluidized bed in the presence of a catalyst under reaction conditions. The gas flow exits the fluidized bed and recirculates into the reactor. At the same time 'the polymerization product is taken out of the reactor and a new monomer is added to replenish the polymerized monomer. (See, for example, U.S. Patent Nos. 4,543,399, 4,588,79, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661, and 5'668,228, all of which are incorporated herein by reference in their entirety) ° The range of change in reactor pressure in the gas phase process is about 10 psig (69 kPa) to about 500 psig (3448 kPa), with a preferred variation ranging from about 1000 psig (690 kPa) to about 400 psig (2.775 kPa), or From about 2000 PS ig (i379kPa) to about 400ps ig (2 759 kPa), a better variation range is about 25 Ops ig (1724kPa) to about 35psig (2414 kPa). In the phase method, the temperature range of the reactor is about 30 ° C to about 120 ° C. The preferred range is about 60 ° to about 115 ° C. The more preferred range is about 7 5 ° C to 1 10 ° C, and the best range of variation This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -55-| Packing ----- ^ ---- Order --------- (Please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Consumer cooperative work printed 1245773 Λ7 ---___ B7 i, the invention described households) of about 8 5 ° C to about 1 1 0 ° c. Changing the polymerization temperature can also be used as a tool to change the properties of the final polymerization product. The yield of a catalyst or catalyst system is affected by the partial pressure of the main monomer. The main monomer 'ethylene or propylene, preferably ethylene, has a preferred molar ratio of about 25 to 90 molar ratios and a monomer partial pressure range of about 7 5 ps 1 g (511.7 kPa) to about 30 psig (2069 kPa) 'It is a typical condition in a gas phase polymerization method. In one embodiment, the ethylene partial pressure is about 220 to 24 Ops ig (1517 to 1653 a). In another embodiment, the molar ratio of hexene to ethylene in the reactor is from 0.03: 1 to 0.08: 1. In another embodiment, the reactor used in the present invention and the process of the present invention produce a polymer of greater than 500 pounds per hour (2 27 kg / hr) to greater than about 200,000 pounds per hour (90,900 kg) Per hour) or more, preferably greater than 1,000 pounds per hour (4.55 kg / hour), more preferably greater than 10,000 pounds per hour (4540 kg / hour), or even better More than 25,000 lbs / hour (11,300 kg / h), still better than 35,000 lbs / hour (15,900 kg / h); still even better than 50, 000 lbs / hour (22,70 kg / h) and the best is greater than 65,000 lbs / hour (29,000 kg / h) to more than 100,000 lbs / hour (45,500 kg / h) . Other gas-phase methods covered by the method of the present invention include U.S. Patent Nos. 5,627,242, 5,665,818 and 5,6 7,7,3 7 5 and European Gazette. The paper standards are applicable to Chinese national standards (CNS ) A4 size (210 X 297 mm) -56-l · ---------- install ----- r. (Please read the precautions on the back before filling this page) Order --- ------ 1245773 A7 V. Description of the invention 0) EP — a—〇7 9 4 2〇〇,

E PE P

A 0 8 0A 0 8 0

2〇2和E (請先閱讀背面之注意事項再填寫本頁) p — B — 6 34 42 1中所述者，彼等都以全文倂於本 文作爲參考。 @液聚合法通常使用的壓力範圍爲約1到5 0大氣壓 &甚g更高者，溫度範圍爲從〇 t；到約1 2 〇 °C。在漿液 聚合中’係形成固體，尤其是粒狀聚合物在加入乙烯和共 胃體’還常加入氫及觸媒的液體聚合稀釋劑介質中的懸浮 '液°將包括稀釋劑在內的懸浮液從反應器間歇或連續取出 ’其中’從聚合物分離出揮發性成分，視需要經蒸餾後再 循環回反應器。聚合介質中使用的液體稀釋劑典型地是含 3至7個碳原子的烷類，較佳者爲支鏈烷。使用的介質應 是在聚合作用條件下爲液體者，且相對鈍性者。當使用丙 烷介質時，此方法必須在反應稀釋劑臨界溫度和壓力之上 進行。較佳者係使用己烷或異丁烷介質。 經 濟 部 智 慧 財 產 局 員 X 消 費 合 社 印 製 在一實施例中，本發明較佳聚合技術係稱爲粒子形成 聚合法或漿液法，其中，溫度係保持在聚合物溶解時的溫 度之下。這種技術係技藝中熟知者，且載於，例如，美國 專利第3，2 4 8，1 7 9號中，其以全文倂於本文作爲 參考。粒子形成法的較佳溫度係處於約1 8 5 °F ( 8 5 °C )到2 3 0 °F ( 1 1 〇 °c )之間。漿液法的兩較佳聚合方 法爲一種使用環圈反應器者及一種使用許多經串聯，倂列 或其組合的攪拌反應器者。漿液法的不受限制例子包括連 續的環圈或攪拌槽法。此外，漿液法的其他例子在美國專 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） .57 - 1245773 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明戶5 ) 利第4，6 1 3 ，4 8 4號中也有說明，其以全文倂於本 文作爲參考。 在另一實施例中，係在一環圈反應器中連續進行漿液 法。將呈溶液，呈懸浮液，呈乳液，呈異丁烷漿液或呈乾 自由流動性粉末的觸媒，定期注入反應器線圈，反應器線 圈本身塡充著成長聚合物粒子在含單體和共單體的異丁烷 稀釋劑中之循環漿液。氫可視需要作爲分子量控制物加入 。依據所欲聚合物密度而定，反應器壓力係保持在約 5 2 5ps ig 到 625ps ig (362〇kPa 到 4 3 Ο 9 k P a )之間，且溫度係保持在約1 4 0 °F到約 2 2 0 °F (約6 0 °C到約1 Ο 4 t )之間。由於大多數反 應器爲雙套層管，因此反應熱係透過環圏壁散發。使漿液 定期或連續排出反應器按順序流到經加熱的低壓閃蒸容器 ，旋轉乾燥器和氮氣沖滌管柱以取出異丁烷稀釋劑和所有 未反應單體和共單體。然後，將所得烴自由粉調配用於各 種應用。 在一實施例中，本發明漿液法中使用的反應器能產生 大於2000磅聚合物/時（907公斤/時）’更佳者 大於5，000磅/時（2268公斤/時）’且最佳者 大於10，000磅/時（4540公斤/時）°在另一 實施例中，本發明使用的漿液反應器每小時產生的聚合物 大於1 5，0 0 0磅（6 8 0 4公斤/時）’較佳者大於 2 5，0 0 0磅/時（1 1 ，3 4 0公斤/時）到大於約 1〇〇，〇0〇磅/時（4 5 ，5 0 〇公斤/時）° 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-58 - ----------------..---- 訂·-----11« (請先閱讀背面之注意事項再填寫本頁) 1245773 A7 ____B7____ 五、發明說明⑼） 在另一實施例中本發明漿液法的反應器總壓力範圆係 在 4〇〇ps ig (2758kPa)到 8〇〇ps ig (請先閱讀背面之注意事項再填寫本頁) (5 5 1 6 k P a ) ’較佳範圍爲從45 Ops lg( 31〇3kPa)到約 7〇〇ps ig (4827kPa )，更佳範圍爲從50〇？3 1茗（34481^?3)到 約650psig(4482kPa)，最佳範圍爲約 5 2 5 P s i g (362〇kPa)到 62 5 psig ( 4 3 0 9 k P a )。 在另一實施例中本發明漿液法的反應器液體介質中之 乙烯濃度範圍爲約1到1 0重量百分比，較佳者約2到約 7重量百分比，更佳者約約2 · 5到約6重量百分比，最 佳者約3到約6重量百分比。 本發明較佳方法是該方法，較佳者漿液法或氣相法， 係在沒有或基本上沒有任何淸除劑例如三乙基鋁，三甲基 鋁，三異丁基鋁，三-正己基鋁，氯化二乙基鋁和二丁基 鋅等的狀態下進行。在P C T公報 W 0 96/08 520和美國專利第 經濟部智慧財產局員工消費合作社印製 5，7 1 2，3 5 2號中有說明此較佳方法，彼等皆以全 文倂於本文作爲參考。 於本發明一較佳實施例中，係將鋁二硬脂酸鹽在礦油 中的漿液導到反應器內，分開地或與第一及/或第二種金 屬錯合物及/或一種活化劑一起地，與金屬化合物及/或 活化劑分開地。使用硬脂酸鋁型添加劑的更多資訊可以在 1 9 9 8年7月1 〇日提出申請的美國申請序號 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-59 - 1245773 A7 _ B7__ 五、發明說明θ7 ) 〇9 / 1 1 3 ’ 2 6 1中找到’其倂於本文作爲參| (請先閱讀背面之注意事頊再填寫本頁) 在另一實施例中’如果將觸媒系統的第二種金_ (匕合 物和含第1 5族金屬化合物按順序給到反應器內，_ @ # 爲加入及/或活化第二種金屬化合物，再加入及/ $丨舌化 含第1 5族金屬化合物。 在另一實施例中，觸媒組成物的滯留時間爲約3 g，約 6小時之間，且較佳者約3 · 5至約5小時之間。 在一實施例中，共單體對乙烯的莫耳比例C x/ c 2爲 約〇· 0 0 1到〇.0 1 0〇，且較佳莫耳比例爲約 0 · 002到0 · 008，其中，Cx爲共單體量，（：2爲 乙烯量。 產生的聚合物的熔融指數（和其他性質）可以透過下 列控制聚合系統中的氫濃度來改變： 1 )改變聚合系統中第一種觸媒的量，及/或 2 )改變聚合系統中第二種觸媒的量，及/或 3 )聚合作用過程中加入氫，及/或 經濟部智慧財產局員工消費合作社印製 4 )改變從聚合過程中取出及/或沖滌出的液體及/ 或氣體之量，及/或 5 )改變返回到聚合過程中的回收液體及/或氣體的 量及/或組成，該回收的液體或氣體是從聚合過程中排出 的聚合物回收的，及/或 6 )在聚合過程中使用氫化觸媒，及/或 7 )改變聚合溫度，及/或 8 )改變聚合過程中的乙烯分壓’及/或 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-60 - 1245773 A7 B7 五、發明說明㈣ ） 9 )改變聚合過程中乙烯對己烯的比例，及/或 1 0 )改變活化序列中活化劑對過渡金屬的比例。 反應器中氫濃度爲約1 0 0到5 0 0 0 P p m，較佳 者200到2〇〇〇Ppm;更佳者250到19〇〇 P pm，更佳者3〇〇到1 8〇〇ppm ，且更佳者 35〇到17 0 Oppm，更佳者400到1600 ppm，更佳者5〇〇到1 50〇ppm，更佳者500 到14〇0ppm，更佳者500到1 20〇ppm，更 佳者600到1200ppm;較佳者7〇◦到11〇〇 P pm，且更佳者8〇〇到1 0 0〇P pm。反應器中氫 濃度係與聚合物的重量平均分子量（M w )成反比。 本發明聚合物 本發明方法製出的新聚合物可用於廣多種產品和終端 用途應用中。較佳者該新聚合物包括聚乙烯和在本發明混 合觸媒系統的作用下，在單一反應器中產生的雙峰型聚乙 烯。除了雙峰型聚合物外，混合系統產生單峰或多峰聚合 物，並未超出本申請案的範圍。 若單獨使用時，含第1 5族金屬化合物會產生高重量 平均分子量的聚合物（例如，咼於1 0 0，0 0 0，較佳 者高於15〇，〇〇0，較佳者高於20〇，〇〇〇，較 佳者高於25〇，〇〇〇，更佳者高於3〇〇，〇〇〇。 )。若單獨使用第二種金屬化合物’其產生的聚合物分子 量較低（例如低於8 0，0 0 〇 ;較佳者低於 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -61 - ▼裝---- (請先閱讀背面之注意事項再填寫本頁> 訂--- •禮丨 經濟部智慧財產局員工消費合作社印製 1245773 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明押） 7〇，〇〇〇，較佳者低於6〇，0〇〇；更佳者低於 5〇，0 〇 〇 ，較佳者低於4 0，0 0 0 ，較佳者低於 3 0 ，〇〇〇，較佳者低於2〇，〇〇〇但高於 5 ，0〇0 ，較佳者低於2 0 ，0 0〇但高於 1 0 , 0 0 0 )。 本發明產生的聚烯烴，尤其是聚乙烯，密度爲 〇· 88到0 . 97克/立方釐米（據ASTM 2 8 3 9測量所得）。較佳者產生的聚乙烯密度爲 0 . 910到0 · 965克/立方釐米；更佳者爲 0 · 9 1 5到0 · 960克/立方釐米且甚至更佳者爲 0 · 920到0 · 955克/立方釐米。在某些實施例中 ，密度0·915到0.940克/立方釐米爲較佳者； 在另一些實施例中，密度0.930到0.970克/立 方釐米爲較佳者。 在一較佳實施例中，回收的聚烯烴典型地具約 0 · 0 1到1〇0 0 d g /m i η，或更小的熔融指數I 2 (據A S T M D - 1 2 3 8，條件Ε，溫度1 9 0 °C測量 所得）。在一較佳實施例中，聚烯烴是乙烯均聚物或共聚 物。在對某些應用例如膜管，模製品等爲較佳的一實例中 ，較佳熔融指數爲1 0 d g /m i η或更小。對某些膜和 模製品的應用中，較佳熔融指數爲1 d g /m i η或更小 。熔融指數I 2爲〇 . 〇 1到1 〇 d g / m i η的聚乙烯爲 較佳者。 於一較佳實施例中，其所製聚合物所具I 2 1 (據 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-62 - -裝---- (請先閱讀背面之注意事項再填寫本頁) 訂——------禮！ 1245773 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明) A S T M D — 1 2 3 8 — F ，溫度爲1 9〇測量所得） 爲〇· 1到1〇d g / m 1 η ，較佳者爲〇 · 2到了 · 5 dg/mi η，較佳者2 · Odg/rni η或更少，較佳 者1 . 5dg/min或更少，較佳者1 · 2dg/ mi η或更少；更佳者在〇 · 5到1 · 〇dg/mi η之 間，更佳者0 · 6到0 · 8 d g /m i η之間。 在另一實施例中，本發明聚合物的熔融流動指數'' MIR〃 ， I21/I2爲80或更大；較佳者爲9〇或更 大，較佳者1 0 0或更大，較佳者1 2 5或更大。 在另一實施例中，聚合物的I 21 (據ASTMD -1 2 3 8，條件F，溫度爲1 9 0 °C測量所得）（有時也 稱爲流動指數）爲2 · 0 d g/m i η或更小；較佳者 1 · 5dg/min 或更小，較佳者 1 · 2dg/min 或更小；更佳者在0 · 5到1 · 0 d g /m i n之間，更 佳者0 . 6到〇 · 8dg/mi n之間及80或更大，較 佳者9 0或更大，較佳者1 〇 〇或更大，較佳者1 2 5或 更大的I 2 i / I 2且另外，還具有以下一或多種性質： (a ) M w /Μ η位於1 5到8 〇之間，較佳是位於 2〇到6 0之間，較佳者2 0到4 0之間。分子量（M w 和Μ η )係按下文實施例中所述測量； (b)Mw爲180，000或更大，較佳者 2〇〇，〇〇〇或更大，較佳者250 ，000或更大， 較佳者3〇〇 ，〇 〇 〇或更大； (c )密度（據A S T Μ 2 8 3 9測量所得）爲 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉_ 63 - —裝----Κ----訂------ (請先閱讀背面之注意事項再填寫本頁) •禮· 1245773 A7 五、發明說明（61 ) 0 · 94到0 · 970克/立方釐米，較佳者〇 · 945 0 · 9 6 5克/立方釐米；較佳者〇 . 9 5 0到 (請先閱讀背面之注意事項再填寫本頁) 〇· 960克/立方釐米； (d)殘餘金屬含量爲5 · 0 p pm過渡金屬或更少 ;較佳者2 · Oppm過渡金屬或更少，較佳者1 · 8 PPm過渡金屬或更少，較佳者1.6ppm過渡金屬或 更少’較佳者1 · 5 p p m過渡金屬或更少，較佳者 2 · Oppm或更少的第4族金屬，較佳者1 · 8ppm 或更少的第4族金屬，較佳者1 · 6 p pm或更少的第4 族金屬，較佳者1 · 5ppm或更少的第4族金屬，較佳 者2 · 〇ppm或更少的鉻，較佳者1 · 8ppm或更少 的鉻’較佳者1·6ppm或更少的鉻，較佳者1·5 P P m或更少的鉻（這些資料由 ''誘導耦合電漿光學發散 光譜學〃 （I C P A E S )相對於商業可得標準品測量所 得）其中，樣品受熱以完全分解所有有機物和溶劑包含硝 酸’且若有任何擔體存在，則還包含分解任何擔體的另一 酸（例如分解矽石擔體用的氫氟酸）； 經濟部智慧財產局員工消費合作社印製 (e )依粒度排斥層析術測量所得有3 5重量百分比 或更高，較佳者4 0%或更高的高重量平均分子量成分。 在一特別較佳實施例中，較高分子量部份係在3 5到7 〇 重量百分比之間，更佳者在4 0到6 0重量百分比之間。 在一較佳實施例中，係用上述觸媒組成物來製造密度 在0·94到0·970克/立方釐米之間（據 A S T M D 2 8 3 9測量所得）且I 2爲0 · 5克/分或 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 64 1245773 A7 B7 五、發明說明（62 ) 少於1 0克/分或更少的聚乙烯。 在另一實施例中，係用上述觸媒組成物來製造I 2 i少 於10，且密度約0 . 940到0 · 950克/立方釐米 之間；或者I 2 i少於2 0，且密度爲約0 . 9 4 5克/立 方釐米或更小的聚乙烯。 在另一實施例中，係用技藝中已知的方法將本發明聚 合物製成管件。在管件的應用中，本發明聚合物的I 2 i約 2到約1 〇 d g /m i η，且較佳者約2到約8 d g / m i η。在另一實施例中，本發明管件符合I S〇規格。 在另一實施例中，本發明觸媒組成物係用來製造在周 溫爲2 0 °C，水爲內部測試介質且以水或空氣爲外界環境 的條件下，至少能用5 0年。（ISO T R 9 0 8 0 測得之水力靜態（周）應力（Hydro static (hoop) stress ) 之聚乙烯管件。 在另一實施例中，聚合物具有在3 · OmP a下，超 過150小時，較佳者在3 · OmPa下，超過500小 時且更佳者在3·OmPa下，超過600小時的缺口張 力試驗（對裂縫緩慢增長的抗性）之結果 F 1 4 7 3測量所得）。 在另一實施例中，係用本發明觸媒組成物來製造聚乙 烯管件，其對1 1 〇毫米管件預期有低於- 5 °C，較佳者 低於一 1 5 °C且更佳者低於一 4 0 °C的S — 4 T c： ( I S〇 DIS 13477/ASTM F 1589)。 在另一實施例中，該聚合物的擠壓速率大於約1 7 1 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公f 「65 - (請先閱讀背面之注意事項再填寫本頁) 訂- -------^91. 經濟部智慧財產局員工消費合作社印製 1245773 經濟部智慧財產局員工消費合作社印製 A7 _ B7 _ 五、發明說明科） 磅/小時/英寸模頭周長’較佳者大於約2 0磅/小時/ 英寸模頭周長，且更佳者大於約2 2 1磅/小時/英寸模 頭周長。 本發明聚烯烴可製成膜，模製品（包括管件），片材 ，金屬線和電纜塗料等。膜可以用技藝中已知的任何習用 技術製得，包括擠壓，共擠壓，層壓，吹膜和澆鑄。膜可 經由扁平膜或管狀程序，其後接著在膜平面上的單軸方向 或兩互相垂直的方向上以相同或不同的程度定向而製得。 在雨方向上的定向程度可以相同，也可以不相同。將聚合 物形成膜的特別較佳方法包括在吹膜或澆鑄膠線上擠壓或 共擠壓。 在另一實施例中，係將本發明聚合物用技藝中已知的 方法製成膜。本發明聚合物應用到膜時，其I 2 1約2到約 5 0 d g /m i η之間，較佳者約2到約3 0 d g / m i η之間，甚至更佳者約2到約2 0 d g /m i η之間 ’仍然更佳者約5到約1 5 d g /m i n之間，且還更佳 者約5到約1 0 d g /m i η之間。 在另一實施例中，聚合物的· 5密爾（m i 1 )( 1 3微米）膜所具MD抗撕強度爲約5克/密爾和2 5克 /密爾之間，較佳者約1 5克/密爾到2 5克/密爾之間 ’且更佳者約2 0克/密爾和2 5克/密爾之間。 所製膜還可含有以下添加劑，例如：滑劑，抗阻劑， 抗氧化劑，顏料，塡料，抗霧劑，U V穩定劑，抗靜電劑 ，聚合物加工助劑，中和劑，潤滑劑，表面活性劑，顏料 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -66- -----------裝·—..—訂·-------- (請先閱讀背面之注意事項再填寫本頁) 1245773 砍，合成氧 硬脂酸金屬 ，5夕藻土，獵 A7 五、發明說明（64 ’染料’和成核劑。較佳添加劑包括：二氧 化矽，一氧化鈦，聚二甲基矽氧烷，碳酸鈣 鹽’硬脂酸鈣，硬脂酸鋅，滑石，B a S〇 ，碳黑，滯燃劑，低分子量樹脂，烴樹脂，玻璃珠等。添 加劑的量可以是技藝中熟知的典型有效量，例如 0.〇01重量％到1〇重量％。 在另一實施例中，本發明聚合物可以用技藝.中已知方 法製成模製品’例如，透過吹模和注射拉伸模製。應用到 模製品時’本發明聚合物的I 2 1爲約2 〇 d g /m i η到 約5 0 d g /m i η ，且較佳者約3 5 d g /m i η到 4 5 d g / m i n。 在另一實施例中，所製本發明聚合物，包括上述者， 其含灰量少於1 0 0 ppm，更佳者少於7 5 ppm，且 甚至更佳者少於5 0 p pm。在另一實施例中，據技藝中 熟知的《誘導耦合電漿光學發散光譜學》（ICPAES )測量所得，灰中含有可以忽略的少量鈦。 在另一實施例中，本發明聚合物含有用技藝中熟知的 《高解析率質譜學》（H R M S )可以測得之含氮配位子 實施例 爲了對本發明，包括其代表性優點，提供更佳的理解 ，乃提出以下實施例。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -67 - ----------------^----訂·-------- (請先閱讀背面之注意事項再填寫本頁) 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明P5 ) 定義 ： Μ η和M w是在水溫爲1 5 0 °C的配備差示折射率探 測器的G P C儀器上運用膠透層析術測量的。透過一系列 分子量標準品的流通分析校準G P C管柱且用標的聚合物 的M a r k Η 〇 u w i n k係數計算分子量。 MWD=Mw/Mn 根據A S T M D 1 5 Ο 5測量密度。 根據1993年2月18日出版的 W〇9 3 / 0 3 0 9 3中的程序來測量C D Β I (組成分 佈寬度指數），不同處在於忽略不計分子量低於 1 〇 ，Ο Ο〇 Μ η的部份。2〇2 and E (please read the notes on the back before filling this page) p — B — 6 34 42 1. They are all incorporated by reference in their entirety. The @liquid polymerization method usually uses a pressure ranging from about 1 to 50 atmospheres and even higher, and a temperature ranging from 0 ° to about 120 ° C. In slurry polymerization, 'forms solids, especially granular polymers when added to ethylene and gastrointestinal bodies.' Suspension of liquid polymerization diluent medium with hydrogen and catalyst is often added. 'The liquid suspension will include the diluent. The liquid is taken out of the reactor intermittently or continuously 'wherein', the volatile components are separated from the polymer, and if necessary, it is recycled back to the reactor after distillation. The liquid diluent used in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The media used should be those that are liquid under polymerization conditions and relatively inert. When using a propane medium, this method must be performed above the critical temperature and pressure of the reaction diluent. Preferably, a hexane or isobutane medium is used. Printed by Intellectual Property Bureau of the Ministry of Economic Affairs, X Consumer Products Co., Ltd. In one embodiment, the preferred polymerization technique of the present invention is referred to as a particle formation polymerization method or a slurry method, wherein the temperature is maintained below the temperature at which the polymer dissolves. This technique is well known in the art and is contained, for example, in U.S. Patent No. 3, 24.8, 179, which is incorporated herein by reference in its entirety. The preferred temperature for the particle formation method is between about 185 ° F (85 ° C) and 230 ° F (110 ° C). The two preferred polymerization methods of the slurry method are one using a loop reactor and one using a plurality of stirred reactors in series, queuing, or a combination thereof. Non-limiting examples of the slurry method include a continuous loop or stirred tank method. In addition, other examples of the slurry method apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) in the US special paper size. 57-1245773 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economics B7 V. Invention Description 5 ) It is also described in Li No. 4, 6 1 3, 4 8 4 which is hereby incorporated by reference in its entirety. In another embodiment, the slurry process is performed continuously in a loop reactor. The catalyst, which is a solution, a suspension, an emulsion, an isobutane slurry, or a dry free-flowing powder, is periodically injected into the reactor coil. The reactor coil itself is filled with growing polymer particles. Circulating slurry in monomeric isobutane diluent. Hydrogen can be added as a molecular weight control if necessary. Depending on the desired polymer density, the reactor pressure is maintained between about 5 2 5 ps ig to 625 ps ig (362 0 kPa to 4 3 0 9 k P a) and the temperature is maintained at about 1 40 ° F To about 2 2 0 ° F (about 60 ° C to about 1 0 4 t). Since most reactors are double-layered tubes, the reaction heat is emitted through the ring wall. The slurry was discharged from the reactor periodically or continuously to a heated low-pressure flash vessel, a spin dryer and a nitrogen purging column to remove the isobutane diluent and all unreacted monomers and co-monomers. The resulting hydrocarbon free powder is then formulated for various applications. In one embodiment, the reactor used in the slurry process of the present invention is capable of producing greater than 2000 pounds of polymer per hour (907 kg / hour) 'more preferably greater than 5,000 pounds per hour (2268 kg / hour)' and most Preferably, it is greater than 10,000 pounds per hour (4540 kg / hr). In another embodiment, the slurry reactor used in the present invention produces more than 15,000 pounds per hour (6.84 kg / H) 'is preferably greater than 25,000 pounds per hour (1,340 kg / hour) to greater than about 10,000 pounds per hour (45,500 kg / hour) Hours) ° This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -58-----------------..---- Order ·- ---- 11 «(Please read the notes on the back before filling this page) 1245773 A7 ____B7____ V. Description of the invention ⑼) In another embodiment, the total pressure range of the reactor of the slurry method of the present invention is in the range of 400. ps ig (2758kPa) to 800〇ps ig (please read the notes on the back before filling in this page) (5 5 1 6 k P a) 'The preferred range is from 45 Ops lg (31〇3kPa) to about 7 〇〇ps ig (4827kPa), more preferably from 50? 3 1 茗 (34481 ^? 3) to about 650 psig (4482 kPa), and the optimal range is about 525 P sig (362 0 kPa) to 625 5 psig (4 3 0 9 k Pa). In another embodiment, the ethylene concentration in the reactor liquid medium of the slurry method of the present invention ranges from about 1 to 10 weight percent, preferably about 2 to about 7 weight percent, and more preferably about 2.5 to about 5 6 weight percent, the best being about 3 to about 6 weight percent. The preferred method of the present invention is this method, and the slurry method or the gas phase method is preferred, in the absence or substantial absence of any scavenger such as triethylaluminum, trimethylaluminum, triisobutylaluminum, tri-n-hexane Alkali, diethylaluminum chloride, dibutylzinc, and the like. This preferred method is described in PCT Bulletin W 0 96/08 520 and USP Patent No. 5, Intellectual Property Office Employee Consumer Cooperatives Printing No. 5,7 1 2, 3 5 2 and they are all included in the full text of this article as reference. In a preferred embodiment of the present invention, the slurry of aluminum distearate in mineral oil is introduced into the reactor, separately or with the first and / or second metal complex and / or one Together with the activator, separately from the metal compound and / or activator. More information on the use of aluminum stearate type additives can be filed on July 10, 1998. US Application Serial Number This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -59 -1245773 A7 _ B7__ V. Description of the invention θ7) 〇9 / 1 1 3 '2 6 1' found in this article as a reference | (Please read the notes on the back first and then fill out this page) In another embodiment "If the second gold of the catalyst system (a compound and a group 15 metal compound is given to the reactor in order, _ @ # is to add and / or activate the second metal compound, then add And / $ 丨 tongue containing a Group 15 metal compound. In another embodiment, the residence time of the catalyst composition is about 3 g, between about 6 hours, and preferably about 3.5 to about 5 In one embodiment, the molar ratio Cx / c 2 of the comonomer to ethylene is from about 0.001 to 0.001, and the preferred molar ratio is about 0.002 To 0. 008, where Cx is the amount of comonomer, (: 2 is the amount of ethylene. The melt index (and other properties) of the polymer produced can be controlled by the following To change the hydrogen concentration in the system: 1) change the amount of the first catalyst in the polymerization system, and / or 2) change the amount of the second catalyst in the polymerization system, and / or 3) add during the polymerization Hydrogen, and / or printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4) Change the amount of liquid and / or gas taken out and / or washed out from the polymerization process, and / or 5) Change the return to the polymerization process The amount and / or composition of the recovered liquid and / or gas, the recovered liquid or gas being recovered from the polymer discharged from the polymerization process, and / or 6) using a hydrogenation catalyst in the polymerization process, and / or 7) Change the polymerization temperature, and / or 8) Change the partial pressure of ethylene during the polymerization process and / or the size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -60-1245773 A7 B7 V. Description of the invention Ii) 9) change the ratio of ethylene to hexene during the polymerization process, and / or 10) change the ratio of activator to transition metal in the activation sequence. The hydrogen concentration in the reactor is about 1000 to 5000 P pm, preferably 200 to 2000 Ppm; more preferably 250 to 1900 P pm, and more preferably 300 to 180. 〇ppm, and more preferably 350 to 170 Oppm, more preferably 400 to 1600 ppm, more preferably 500 to 150 ppm, more preferably 500 to 140,000 ppm, and more preferably 500 to 120 〇ppm, more preferably 600 to 1200ppm; more preferably 70◦ to 11000P pm, and more preferably 800 to 1000P pm. The hydrogen concentration in the reactor is inversely proportional to the weight average molecular weight (Mw) of the polymer. Polymers of the Invention The new polymers produced by the method of the invention can be used in a wide variety of products and end-use applications. Preferably, the new polymer includes polyethylene and a bimodal polyethylene produced in a single reactor under the action of the hybrid catalyst system of the present invention. Except for bimodal polymers, hybrid systems produce unimodal or multimodal polymers without exceeding the scope of this application. When used alone, Group 15-containing metal compounds will produce polymers with a high weight average molecular weight (for example, less than 10,00, preferably more than 150,000, more preferably At 20,000, preferably more than 250,000, more preferably more than 30,000.). If the second metal compound is used alone, the polymer produced will have a lower molecular weight (for example, less than 80,000; the better is lower than this paper size. Chinese National Standard (CNS) A4 specification (210 X 297) -61-▼ Loading ---- (Please read the precautions on the back before filling out this page> Order --- • Gifts Printed by the Intellectual Property Bureau Employee Consumption Cooperative of the Ministry of Economic Affairs 1245773 Employee Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed A7 B7 V. Description of the invention) 70,000, preferably less than 60,000; more preferably less than 50,000, more preferably less than 40, 0 0 0, preferably less than 30, 00, more preferably less than 20,000, but more than 5, 000, more preferably less than 20, 0, but higher than 1 0, 0 0 0). The polyolefins, especially polyethylenes, produced by the present invention have a density of 0.88 to 0.97 g / cm3 (measured according to ASTM 2 8 39). The better produced polyethylene with a density of 0.910 to 0. 965 g / cm3; more preferably 0. 9 1 5 to 0. 960 g / cm3 and even more preferably 0. 920 to 0. 955 g / cm3. In some embodiments, a density of 0.915 to 0.940 g / cm3 is preferred; in other embodiments, a density of 0.930 to 0.970 g / cm3 is preferred. In a preferred embodiment, the recovered polyolefin typically has a melt index I 2 of about 0.01 to 1000 dg / mi η or less (according to ASTM D-1 2 3 8, condition E, Measured at a temperature of 190 ° C). In a preferred embodiment, the polyolefin is an ethylene homopolymer or copolymer. In a preferred embodiment for certain applications such as film tubes, molded articles, etc., the preferred melt index is 10 dg / m i η or less. For certain films and molding applications, a preferred melt index is 1 d g / m i η or less. Polyethylenes having a melt index I 2 of 0.01 to 10 d g / m i η are preferred. In a preferred embodiment, the polymer produced by it has I 2 1 (according to this paper size, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -62--packed-(Please Read the precautions on the back before filling this page) Order ---------- Gift! 1245773 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention) ASTMD — 1 2 3 8 — F, temperature Measured at 190) is from 0.1 to 10 dg / m 1 η, preferably from 0.2 to 5 dg / mi η, more preferably from 2 · Odg / rni η or less, more preferably 1.5 dg / min or less, more preferably 1.2 dg / mi η or less; more preferably 0.5 to 1 · dg / mi η, and more preferably 0 6 to 0 · 8 dg / mi η. In another embodiment, the polymer of the present invention has a melt flow index "MIR", I21 / I2 of 80 or more; preferably 90 or more, more preferably 100 or more, and The best is 1 2 5 or more. In another embodiment, the polymer's I 21 (measured according to ASTMD -1 2 38, condition F, temperature 1 900 ° C) (sometimes referred to as flow index) is 2 · 0 dg / mi η or less; preferably 1 · 5dg / min or less, more preferably 1 · 2dg / min or less; more preferably between 0 · 5 and 1 · 0 dg / min, more preferably 0 6 to 0.8 dg / min and 80 or more, preferably 90 or more, more preferably 100 or more, more preferably 1 2 5 or more I 2 i / I 2 and also have one or more of the following properties: (a) M w / M η is between 15 and 80, preferably between 20 and 60, and more preferably between 20 and 40 between. The molecular weights (M w and M η) are measured as described in the examples below; (b) Mw is 180,000 or more, preferably 20,000 or more, more preferably 250,000 Or greater, preferably 300,000 or greater; (c) Density (measured according to AST M 2 8 39) is the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297) Mm> _ 63-—install ---- Κ ---- order ------ (Please read the notes on the back before filling out this page) • Li · 1245773 A7 V. Description of the invention (61) 0 · 94 to 0 · 970 g / cm3, preferably 0.945 0 · 9 65 g / cm3; preferably 0.95 0 to (please read the precautions on the back before filling this page) 〇 · 960 grams / cubic centimeter; (d) residual metal content of 5 · 0 p pm transition metal or less; preferably 2 · Oppm transition metal or less, more preferably 1 · 8 PPm transition metal or less, 1.6 ppm transition metal or less is preferred '1.5 ppm transition metal or less is preferred, a Group 4 metal is 2 · 0 ppm or less, and 1 · 8 ppm or less is preferred Group 4 metals, preferably 1 · 6 p pm Or less Group 4 metals, preferably 1.5 ppm or less Group 4 metals, more preferably 2.0 ppm or less chromium, more preferably 1.8 ppm or less chromium The best chromium is 1.6 ppm or less, and the better is 1.5 PP m or less. (These data are measured by "ICPAES" compared to commercially available standards. (Results) where the sample is heated to completely decompose all organic matter and the solvent contains nitric acid 'and if any support is present, it also contains another acid that decomposes any support (for example, hydrofluoric acid used to decompose silica support) (E) printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives, measured by particle size exclusion chromatography, has a high weight average molecular weight component of 35 weight percent or higher, preferably 40% or higher. In the embodiment, the higher molecular weight portion is between 35 and 70 weight percent, and more preferably between 40 and 60 weight percent. In a preferred embodiment, the catalyst composition described above is used. To produce densities between 0.94 and 0.970 g / cm3 (according to ASTMD 2 8 3 9 Measured) and I 2 is 0.5 g / min or this paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 64 1245773 A7 B7 V. Description of the invention (62) less than 10 G / min or less polyethylene. In another embodiment, the catalyst composition is used to make I 2 i less than 10, and the density is about 0.940 to 0.950 g / cm 3; or I 2 i is less than 20, and Polyethylene having a density of about 0.945 g / cm3 or less. In another embodiment, the polymer of the present invention is made into a pipe by a method known in the art. In the application of pipe fittings, the polymer of the present invention has an I 2 i of about 2 to about 10 d g / m i η, and more preferably about 2 to about 8 d g / m i η. In another embodiment, the pipe fitting of the present invention conforms to the ISO standard. In another embodiment, the catalyst composition of the present invention can be used for at least 50 years under the conditions that the ambient temperature is 20 ° C, water is the internal test medium, and water or air is the external environment. (ISO TR 9 0 8 0 Hydrostatic (hoop) stress measured for polyethylene pipe fittings. In another embodiment, the polymer has a temperature of more than 150 hours at 3 · OmP a, The results are preferably measured at a notch tension test (resistance to slow crack growth) of more than 500 hours at 3 · OmPa and more than 600 hours at 3 · OmPa). In another embodiment, the catalyst composition of the present invention is used to manufacture polyethylene pipe fittings, which are expected to be less than -5 ° C for 110 mm pipe fittings, more preferably less than -15 ° C and more preferably The S-4 T c below 40 ° C: (ISODIS 13477 / ASTM F 1589). In another embodiment, the extrusion rate of the polymer is greater than about 1 7 1 This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 male f "65-(Please read the precautions on the back before filling (This page) Order-------- ^ 91. Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1245773 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7 _ V. Inventory Section) lbs / hour / An inch die circumference is preferably greater than about 20 pounds per hour per inch die circumference, and more preferably greater than about 21 pounds per hour per inch die circumference. The polyolefin of the present invention can be made into a film , Molded products (including pipe fittings), sheets, wire and cable coatings, etc. Films can be made using any conventional technique known in the art, including extrusion, coextrusion, lamination, blown film and casting. Films can be It is produced through a flat membrane or tubular procedure, and then oriented in the uniaxial direction or two mutually perpendicular directions on the plane of the membrane to the same or different degrees. The degree of orientation in the rain direction can be the same or different A particularly preferred method of forming polymers into films includes Extrusion or co-extrusion on casting line. In another embodiment, the polymer of the present invention is made into a film by a method known in the art. When the polymer of the present invention is applied to a film, its I 2 1 is about 2 Between about 50 dg / mi η, preferably between about 2 and about 30 dg / mi η, even more preferably between about 2 and about 20 dg / mi η ', still more preferably about 5 Between about 15 dg / min, and even more preferably between about 5 and about 10 dg / mi η. In another embodiment, the polymer's .5 mil (mi 1) (13 micron ) The MD tear strength of the film is between about 5 g / mil and 25 g / mil, preferably about 15 g / mil to 25 g / mil 'and more preferably about Between 20 g / mil and 25 g / mil. The film can also contain the following additives, for example: lubricants, anti-blocking agents, antioxidants, pigments, additives, anti-fog agents, UV stabilizers, Antistatic agents, polymer processing aids, neutralizers, lubricants, surfactants, pigments This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) -66- ------ ----- Equipped · —..— Order · -------- (Please read the back first Please pay attention to this page and fill in this page again) 1245773 Chopping, synthesizing metal oxystearate, celestial soil, hunting A7 V. Description of the invention (64 'dye' and nucleating agent. Preferred additives include: silicon dioxide, monoxide Titanium, polydimethylsiloxane, calcium carbonate 'calcium stearate, zinc stearate, talc, B a S0, carbon black, flame retarder, low molecular weight resin, hydrocarbon resin, glass beads, etc. Additives The amount may be a typical effective amount well known in the art, for example, from 0.01 to 10% by weight. In another embodiment, the polymer of the present invention can be formed into a molded article by a method known in the art ', for example, by blow molding and injection stretch molding. When applied to a molded article, the I 2 1 of the polymer of the present invention is about 20 d g / m i η to about 50 d g / m i η, and more preferably about 35 d g / m i η to 4 5 d g / m i n. In another embodiment, the polymers of the present invention, including those described above, have an ash content of less than 100 ppm, more preferably less than 75 ppm, and even more preferably less than 50 ppm. In another embodiment, as measured by "Inductively Coupled Plasma Optical Divergence Spectroscopy" (ICPAES), which is well known in the art, ash contains a negligible amount of titanium. In another embodiment, the polymer of the present invention contains nitrogen-containing ligands that can be measured using "high-resolution mass spectrometry" (HRMS), which is well known in the art. In order to provide the present invention, including its representative advantages, with more For better understanding, the following examples are proposed. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -67----------------- ^ ---- Order · ----- --- (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 1245773 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics, printed A7 B7 V. Invention Description P5 M w was measured using gel permeation chromatography on a GPC instrument equipped with a differential refractive index detector at a water temperature of 150 ° C. GPC columns were calibrated by flow-through analysis of a series of molecular weight standards and the molecular weights were calculated using the M a r k u u w i n k coefficient of the target polymer. MWD = Mw / Mn The density is measured according to A S T M D 1 5 Ο 5. CD Β I (Composition Distribution Width Index) was measured according to the procedure in WO 903/0 3 0 93, published on February 18, 1993, except that the molecular weight was less than 1.0, 〇〇〇〇Μ η The part.

根據ASTMD — 1238 ，條件Ε，溫度19〇°C ，測量熔融指數（Μ I ) I 2。 根據A S T M D — 1 2 3 8，條件F，溫度1 9 0 °C ，測量I 2 1。 熔融指數比例（Μ I R )爲I 2 i 對I 2比，其由 A S T M D — 1 2 3 8 測定。 共單體的重量％由質子NMR測量。 根據A S T M D 1 7 Ο 9測量抗落錘衝擊強度。 根據A S T M D 1 9 2 2測量M D和丁 D的The melt index (M I) I 2 was measured according to ASTM D-1238, condition E, and a temperature of 19 ° C. Measure I 2 1 according to A S T M D — 1 2 3 8, condition F, temperature 190 ° C. The melt index ratio (M I R) is the I 2 i to I 2 ratio, which is determined from A S T M D — 1 2 3 8. The co-monomer weight% is measured by proton NMR. The resistance to drop weight impact was measured according to A S T M D 1 7 〇 9. Measured according to A S T M D 1 9 2 2

Elmendorf抗撕強度。 根據八3丁“0 882測量&10和丁0的1%的正割模數。 根據A S T M D 8 8 2測量M D和T D的伸長率和極限 張力強度。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-68 - _裝----l· (請先閱讀背面之注意事項再填寫本頁) 訂--------^9. 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（66 ) 根據A S T M D 4 1 2測量M D和丁 D的伸長率及 極限伸長率。 根據A S T M D 8 8 2 — 9 1 ’測量M D和T D的 模數。 根據A S T M D 1 〇〇3 — 9 5 ，狀態A，測量濁 度。 根據A S T M D 2 4 5 7，測量4 5 °光澤度。 BUR 爲吹爆比（blowupratio)。根據 A S TM D 1 7 0 9 ’方法A ’測量2 6英寸抗落錘衝擊強度 E S C〇R E T M L L· 3 Ο Ο 2 · 3 2爲線性低密度乙 嫌—己燃共聚物，係使用得自Exxon Chemical Company， Houston, Texas的戚格勒一納塔觸媒在單一氣相反應器內製 得者，其密度爲0.918克/立方釐米，12爲2dg/ m i η且其C D B I (組成分佈寬度指數）小於6 5。 EXCEED™ECD 1 2 5爲線性低密度乙烯一 己燒共聚物，係使用得自Exxon Chemical Company,Elmendorf tear resistance. 1% secant modulus measured according to "8 882" 0 & 882 & 1 0. Measured elongation and ultimate tensile strength of MD and TD according to ASTM D 8 8 2. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -68-_ equipment ---- l · (Please read the precautions on the back before filling this page) Order -------- ^ 9. 1245773 Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of the invention (66) Measure the elongation and ultimate elongation of MD and D according to ASTM D 4 1 2. Measure the modulus of MD and TD according to ASTM D 8 8 2 — 9 1 '. Turbidity was measured according to ASTMD 1 000-95, state A. Gloss was measured at 45 ° according to ASTMD 2 4 5 7. BUR is blowup ratio. According to AS TM D 1 7 0 9 'method A 'Measures the impact strength of 26 inch drop hammer ESC0RETMLL · 3 〇 〇 2 · 3 2 is a linear low-density ethylene-hexamethylene copolymer, which is used from Exxon Chemical Company, Houston, Texas. Nata catalysts were prepared in a single gas phase reactor with a density of 0.918 g / cm3 and 12 2dg / m i η and its C D B I (composition distribution width index) is less than 6 5. EXCEED ™ ECD 1 2 5 is a linear low density ethylene-hexane copolymer, which is obtained from Exxon Chemical Company,

Houston, Texas的茂合金屬觸媒，在單一氣相反應器內製得 者，其密度爲約0 · 9 1克/立方釐米，MI爲1 · 5克 / 1 0 分。 E S C〇R E N E T M L L 3〇〇1 · 6 3爲一線性低 密度乙烯—己烯共聚物，係使用得自Exxon Chemical C o m p a n y，Η o u s t ο η，T e x a s的戚格勒—納塔觸媒’在單一*氣相 反應器內製得者，其密度爲約約0 · 9 1 8克/立方釐米 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -69 - _裝---- (請先閱讀背面之注意事項再填寫本頁) tr-i —------Λ0, 1245773 A7 ---------B7__ 五、發明說明（67 ) ’ Μ I爲1 ·〇克/ 1〇分。 (請先閱讀背面之注意事項再填寫本頁) Ε X C E E D τ M 3 5〇D δ〇爲一線性低密度乙烯一 己嫌共聚物’係使用得自Exx〇n Chenucal Company， Houston，Texas的茂合金屬觸媒，在單—氣相反應器內製得 者’其密度爲約〇 · 9 18克/立方釐米，MI爲1 ·〇 克/ 1 0分。 '' P P Η "爲膀·每小時。、、m ρ ρ η 〃爲毫磅每小時 ° p pmw〃爲重量p pm。MD爲機械方向，TD爲 橫向。 以下實施例節I中的實施例使用混合觸媒系統，其包 括含第1 5族金屬觸媒和龐大配位子茂合金屬觸媒。 RJUI節I。混合觸媒系統，包括含第1 5族金 龐大配位子茂合金屬觸媒。 茚基锆tris特戊酸鹽之製備 經濟部智慧財產局員工消費合作社印製 茚基鉻tris特戊酸鹽爲一龐大配位子茂合金屬化合物 ，也由式V I表之，可透過以下一般反應製備：The metallocene catalyst of Houston, Texas, was produced in a single gas phase reactor with a density of about 0.91 g / cm3 and an MI of 1.5 g / 10 min. ESCORENETMLL 3001 · 63 is a linear low-density ethylene-hexene copolymer, which is based on the use of the "Qigler-Natta catalyst" from Exxon Chemical Copany, ousoust ο η, Texas. * Produced in a gas-phase reactor with a density of about 0.98 g / cm3. This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) -69-_pack- -(Please read the precautions on the back before filling this page) tr-i ------- Λ0, 1245773 A7 --------- B7__ V. Description of the invention (67) 'Μ I is 1.0 g / 10 minutes. (Please read the precautions on the back before filling in this page) Ε XCEED τ M 3 5〇D δ〇 is a linear low-density ethylene-copolymer, which is obtained from Exxon Chenucal Company, Houston, Texas. The metal catalyst was produced in a single-gas phase reactor with a density of about 0.918 g / cm3 and a MI of 1.0 g / 10 minutes. '' P P Η " For the bladder every hour. , M ρ ρ η 毫 is milli-pounds per hour ° p pmw〃 is weight p pm. MD is the mechanical direction and TD is the horizontal direction. The examples in the following Example Section I use a hybrid catalyst system, which includes a Group 15 metal catalyst and a bulky ligand metallocene catalyst. RJUI Section I. Hybrid catalyst systems, including metallocene catalysts with bulky ligands from Group 15 gold. Preparation of indenyl zirconium tris pivalate is printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Indenyl chromium tris pivalate is a large ligand metallocene compound, which is also represented by formula VI. Reaction Preparation:

1) Zr(NEu)4 + IndH— IndZr(NEt〇3 +EhNH1) Zr (NEu) 4 + IndH— IndZr (NEt〇3 + EhNH

2) IndZr(NEt2)3 + 3(CH3)3CC〇2H — IndZr[〇2CCl(CH3)]3 + Et2NH 其中，Ind=茚基，Et是乙基。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -70 - 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（68 ) 〔（2 ’ 4，6 — iM e C 6 Η 2 ) N H C Η 2 C Η 2〕2 N Η 配 位子（配位子1) 之製備 於一兩公升單臂Schlenk燒瓶內於無氧無水氮氣下給入 一磁攪棒’二伸乙三胺（23 · 450克，0 · 227莫 耳），2 —溴三甲基苯（9 0.51克，0.455莫耳 )，三（二伸苄基丙酮）二鈀（1 /041克，1 : 14 毫莫耳），外消旋一 2，2 / -二（苯膦）一 1，1 / 一 聯萘（外消旋B I N A P ) ( 2 . 1 2 3克，3 . 4 1毫 莫耳），第三丁氧化鈉（65.535克，0.682莫 耳）和甲苯（8 0 0毫升）。攪拌反應混合液並加熱到 1 0 0 °C。1 8小時後，根據質子N M R光譜學判斷反應 完全。所有餘下步驟可在空氣中進行。真空脫除所有溶劑 並將剩餘物溶解在1升的***中。先用水將醚淸洗（ 2 5 0毫升3次），然後用飽和氯化鈉水溶液（1 8 0克 于5 0 0毫升水中）淸洗，再用3 0克硫酸鎂脫水。真空 脫除***生成紅油狀物，將其在7 0 °C真空乾燥1 2小時 後（產率 71 · 1〇克，92%) QiHNMR (C6D6 )586.83(s，4) ，3.39(brs，2)， 2.86(t，4)，2.49(t，4)，2.27( s，12)，2.21(s，6)，0.68(br s ，1 ) o 觸媒A (用於此實施例節I者） 之製備 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -71 - ▼裝----l·. (請先閱讀背面之注意事項再填寫本頁) 訂| 1245773 經濟部智慧財產局員工消費合作社印製 Λ7 ______B7_ 五、發明說明（69 ) 1 . 5重量％觸媒甲苯溶液 注：以下的所有程式都在手套箱中進行。 1 ·稱出1 0 0克純化甲苯，倒入1升配備塗有 Teflon的攪棒之錐瓶中。 2·加入7·28克四苄基鉻。 3 ·將溶液置於攪動器上並攪拌5分鐘。所有固體都 溶解。 4·加入5·42克上製配位子I 。 5 ·加入另一份5 5 1克純化甲苯並使混合物攪拌 1 5分鐘。溶液中沒有殘留固體。 6 ·將觸媒溶液倒入一乾淨的沖滌過的1升WhUey樣 本筒中，于以標記，從手套箱中取出，並置於持置處供操 作用。 化合物 I{ [ ( 2,4,6-Me3C6H2 ) NCH2CH2]2NH}Zr ( CH2Ph ) 2 的另一製備法 於一 5 0 0毫升圓底燒瓶中在乾燥無氧氮氣下裝入一 磁攪拌棒，四苄基鉻（Boulder Scientific )( 41 · 729克，91 · 56毫莫耳）和甲苯300毫升 。加入上製固體配位子I (32 · 773克，96 · 52 毫莫耳），並攪拌1分鍾（合意化合物沈澱）。將漿液體 積縮減到1 0 0毫升，並攪拌加入3 0 0毫升的戊烷。過 濾收集黃橘色固體產物並真空乾燥（4 4 · 8 1 1克， 80% 產率）°lH NMR (CbDb) (57 . 22- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -72 - L-------I------l·--丨IT--------I (請先閱讀背面之注意事項再填寫本頁) 1245773 A7 B7 五、發明說明（70 ) (請先閱讀背面之注意事項再填寫本頁) 6.8l(m，12)，5.9〇（d，2)，3·38 (m，2)，3.11( m，2)，3.〇l(m，i) ，2.49(m，4) ，2.43(s，6) ，2·41 (s，6) ，2.18(s，6) ，1.89(s，2) ，〇· 9 6 ( s，2 ) ° 觸媒B (用於此實施例節I ) 之製備 1重量％觸媒B己烷溶液 所有程式都在手套箱內進行。 1 ·將1升純化己烷倒入1升錐瓶中，該錐瓶配備塗 有Teflon的攪棒。 2 ·加6 · 67克茚基鉻tns特戊酸鹽乾粉。 3 .將溶液置於磁攪動器上並攪拌1 5分鐘。所有固 體溶解。 4 ·將溶液倒入一乾淨沖滌過的1升Whitey樣品筒內 ，于以標記，從手套箱中移出並置置於持置處供操作用。 經濟部智慧財產局員工消費合作社印製 實施例節I 一比較例1 : 在溫度爲85°C，總反應器壓力爲350ps ig ( 2 · 4 m P a )下操作，配有水冷卻型熱交換器的1 4英 寸（3 5 · 6釐米）領試工廠規模氣相反應器中製造乙烯 -己烯共聚物。將乙烯以每小時約4 0磅的速率（ 1 8 · 1公斤/小時）給到反應器內’將己烯以每小時約 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-73- 1245773 A7 B7 五、發明說明) (請先閱讀背面之注意事項再填寫本頁) 〇 · 6磅的速率（〇 · 27公斤/小時）給到反應器內並 將氫以5毫磅/小時的速率給到反應器內。氮係以約5 -8磅/小時的速率給到反應器內作爲補充氣體。製造速率 爲約2 7膀/小時。反應器配備一通氣器（plenum) ’該 通氣器含有約1 9 0 0磅/小時的循環氣流。（通氣器爲 一裝置，用來在流化床氣相反應器中造成無粒子區，如在 美國專利第5，6 9 3，7 2 7號中詳述者’該專利倂於 本文作爲參考）。在通氣器氣流中配置一管口大小爲 〇 · 0 4 1英寸（0 · 1 0釐米）錐形觸媒注射噴嘴。將 1重量％的觸媒A甲苯溶液與輔觸媒（MMAO — 3 A ’ 1重量％鋁）線內混合，再透過注射噴嘴輸入流化床。（ ΜMAO - 3 A是庚烷中的改質甲基鋁氧烷，其在商業上 可得自AK20Chemicals, Inc.購得，商標名爲改質甲基鋁氧烷 型3 A ) 。Μ Μ A〇與觸媒的比係經控制以使A 1 : Z r 經濟部智慧財產局員工消費合作社印製 莫耳比爲4 0 0 ·· 1。視需要也將氮和異庚烷給入注射噴 嘴以用來保持穩定的平均粒度。獲得的單峰型聚合物，其 標稱121爲0 · 28dg/mi η且其密度爲0 · 935 克/立方釐米。以反應器質量平衡爲基礎計算出1 · 6 3 p p m w的殘餘鉻含量。 竇施例節I 一比較例2 : 在溫度爲8 5 °C，總反應器壓力爲3 2 0 P s i g ( 2 . 2 m P a )下操作，配有水冷卻型熱交換器的1 4英 寸（3 5 · 6釐米）領試工廠規模氣相反應器中製造乙烯 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -74 - 1245773 A7 B7 五、發明說明) -己烯共聚物。將乙烯以每小時約3 7磅的速率（ 1 9 . 8公斤/小時）給到反應器內，將己烯以每小時約 Γ%先閱讀背面之注音？事項再填寫本頁) 0 . 4磅的速率（0 . 1 8公斤/小時）給到反應器內逝 將氫以1 2毫磅/小時的速率給到反應器內。給入乙烯來 保持反應器中1 8 0磅（1 · 2 m P a )的乙烯分壓。製 造速率爲約2 5磅/小時。反應器配備一通氣器，該通氣 器具有約1 ，〇 3 0磅/小時的循環氣流。（通氣器爲〜 裝置，用來在流化床氣相反應器中生成無粒子區）。在通 氣器氣流中配置一管口大小爲0 · 055英寸（0 · 14 釐米）錐形觸媒注射噴嘴。在一 3 / 1 6英寸（0 . 4 8 釐米）不銹鋼管中，將1重量％的觸媒B己烷溶液與 〇.2磅/小時（0 · 0 9公斤/小時）的己烯混合約 1 5分鐘。將觸媒B和己烯混合物與輔觸媒（Μ Μ A〇一 3 A，1重量％鋁）線內混合約4 0分鐘。除溶劑外，也 加入異戊烷和氮以控制粒子大小。將整個系統從注射噴嘴 穿過進入流化床。控制Μ Μ A〇與觸媒的比例，以使A 1 :Z r莫耳比爲3 0 0 : 1。產生的雙峰型聚合物熔融指 經濟部智慧財產局員工消費合作社印製 數爲797克/10分，密度爲0·9678克/立方釐 米。在反應器質量平衡的基礎上計算殘餘鉻，爲0 . 7 p p m w。完成S E C分析並用4粉狀分佈消捲積，且將 結果顯示在表I中。 實施例節I 一實施例3 ; 在溫度爲8 5 t，總反應器壓力爲3 2 0 p s i g ( 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -75 - 1245773 經濟部智慧財產局員工消費合作社印製 Λ7 B7 五、發明說明C3 ) 2 · 2 m P a )下操作，配有水冷卻型熱交換器的1 4英 寸（3 5 · 6釐米）領試工廠規模氣相反應器中製造乙烯 -己烯共聚物。將乙烯以每小時約5 3磅的速率（2 4公 斤/小時）給到反應器內，將己烯以每小時約〇 . 5磅（ 〇· 2 2公斤/小時）的速率給到反應器內，且將氫以9 毫磅/小時的速率給到反應器內。給入乙烯來保持反應器 中22〇ps ig (1 · 52mPa)的乙烯分壓。製造 速率爲約2 5磅/小時。反應器配備一通氣器，該通氣器 具有約9 9 0榜/小時的循環氣流（通氣器爲一裝置，用 來在流化床氣相反應器中生成無粒子區）。在通氣器氣流 中放置一錐形觸媒注射噴嘴，該噴嘴的管口大小爲 〇· 055英寸（〇· 12釐米）。在一 3/16英寸（ 〇·48釐米）不銹鋼管中，1重量％的觸媒B己烷溶液 與0 · 2榜/小時（0 · 0 9公斤/小時）己稀混合約 1 5分鐘。將觸媒B和己嫌混合液與輔觸媒（ΜMA〇-3A ’ 1重量％銘）線內混合約2 0 — 2 5分鐘。在一分 開的活化不銹鋼管中，用輔觸媒（Μ Μ A〇一 3 A，1重 量比鋁）將1重量％觸媒A甲苯溶液活化約5 0 - 5 5分 鐘。將兩分別活化的溶液組合進一單一程序線內約4分鐘 。觸媒A觸媒量爲總給入溶液的約4 0 - 4 5莫耳％。除 溶液外，也加入異戊烷和氮以控制粒子大小。將整個系統 從注射噴嘴通過進入流化床。控制Μ Μ A 0與觸媒的比例 以使A 1 : Z r的莫耳比爲3 0 0 : 1。產生的雙峰型聚 合物熔融指數爲0 · 0 4 5克/ 1 0分且其流動指數爲 紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐) =76 - "" (請先閲讀背面之注意事項再填寫本頁) 訂——'------, 1245773 ___B7______ 五、發明說明) 7 . 48克/10分。其密度爲0 · 9496克/立方鐘 米。在反應器質量平衡的基礎上計算殘餘锆，爲1 . 7 ρ p m w。完成S E C分析且用7 - 8粉狀分佈消捲積， 結果顯示在表I中。 實施例節I 一實施例4 ; 在溫度爲8 5 °C，總反應器壓力爲3 2 0 p s i g ( 2.2mPa)下操作，配有水冷卻型熱交換器的14英 寸（3 5 · 6釐米）領試工廠規模氣相反應器中製造乙烯 一己烯共聚物。乙烯以每小時約5 0磅的速率（2 2 · 7 公斤/小時）給到反應器內，將一些己烯以每小時約 〇· 7磅（0 · 3 2公斤/小時）的速率給到反應器內’ 並將氫以1 1毫磅/小時的速率給到反應器內。給入乙烯 以保持反應器中22〇psig (1·52mPa)的乙 烯分壓。製造速率爲約2 9磅/小時。反應器配備一通氣 器，該通氣器具有約9 7 0磅/小時的循環氣流。（通氣 器爲一裝置，用來在流化床氣相反應器中創造一無粒子區 )。在通氣器氣流中放置一錐形觸媒注射噴嘴’該噴嘴的 管口大小爲〇 · 055英寸（0 · 14釐米）°在一 3/ 1 6英寸（0 · 48釐米）不銹鋼管中’ 1重量％的觸媒 B己烷觸媒溶液與0 . 2磅/小時（〇 · 〇 9公斤/小時 )的己烯混合約1 5分鐘。將觸媒B和己燃混合液與_觸 媒（Μ Μ A〇一 3 A，1重量％鋁）線內混合約2 〇 一 2 5分鐘。在一分開的活化不銹鋼管中’用铺觸媒、活彳匕1 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -77 - ------------>---裝--- (請先閱讀背面之注意事項寫本頁) 訂： 線， 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作钍印焚 1245773 Α7 _ Β7 五、發明說明（75 ) 重量％觸媒A甲苯溶液（Μ Μ A〇—3 A ， L逍m %鋁） 約5 0 - 5 5分鐘。將兩分別活化的溶液組合進一單一程 序線約4分鐘。觸媒Α觸媒量爲給入總溶液的約4 〇 -4 5莫耳％。除溶液外，加入異戊烷和氮以控制粒子大小 。將整個系統從注射噴嘴通過進入流化床。控制Μ Μ A〇 與觸媒的比例以使A 1 : Z r莫耳比爲3 0 0 : 1。產生 的雙峰型聚合物熔融指數爲0 · 0 5 4克/ 1 0分，流動 指數爲7·94克/10分，密度爲0.948克/立方 鐘米。在反應器質量平衡的基礎上計算殘餘結，爲1 · 1 p pmw。完成S E C分析並用7 - 8粉狀分佈消捲積， 結果顯示在表I中。 實施例節I 一實施例5 ; 在溫度爲8 5 °C，總反應器壓力爲3 2 0 P s g ( 2 . 2 m P a )下操作，配有水冷卻型熱交換器的1 4英 寸（3 5 . 6釐米）領試工廠規模氣相反應器中製造乙烯 〜己烯共聚物。將乙烯以每小時約6 0磅（2 7 · 2公斤 /小時）的速率給到反應器內，己烯以每小時約0 · 8磅 (〇· 3 6公斤/小時）的速率給到反應器內及將氫以 1 3毫磅/小時的速率給到反應器內。給入乙丨希以保持反 應器中2 2 Ο P s i g ( 1 · 5 2 m P a )的乙燃分壓。 製造速率爲約3 4磅/小時。反應器配備一通氣器’該通 氣器含有約9 6 0磅/小時的循環氣流° (通氣器爲一裝 置，用來在流化床氣相反應器中創造一無粒子區）υ在通 (請先閱讀背面之注意事項寫本頁) 一-J. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -78 - 1245773 A7 B7 五、發明說明《6 ) 氣器氣流中放置一錐形觸媒注射噴嘴，該噴嘴的管口大小 爲〇·〇5 5英寸（0 · 1 4釐米）。在一 3 / 1 6英寸 • J------·<----:丨裝--- (請先閒讀背面之注意事項寫本頁) (〇.4 8釐米）不銹鋼管中，將1重量％觸媒B己烷觸 媒溶液與〇 . 2膀/小時（0 · 〇 9公斤/小時）己烯混 合約1 5分鐘。將觸媒B和己烯混合液與輔觸媒（ 經濟部智慧財產局員工消費合作社印製 Μ Μ A〇一 3 A，1重量％鋁）線內混合約2 〇 — 2 5分 鐘。在一分開的活化不銹鋼管中’用輔觸媒（Μ Μ A〇一 3 A，1重量％鋁）活化1重量％觸媒A甲苯溶液約5 Ο - 5 5分鐘。將兩分別活化的溶液組合進一單一程序線約 4分鐘。觸媒Α觸媒量爲約輸入的總溶液量的4 0 - 4 5 莫耳％。除溶液外，加入異戊烷和氮以控制粒子大小。將 整個系統從注射噴嘴通過進入流化床。控制Μ Μ A 0與觸 媒的比例以使A 1 : Z r莫耳比爲3 Ο Ο : 1。爲生的雙 峰型聚合物熔融指數爲0 . 0 7 7克/ 1 0分，流動指數 爲12.7克/10分，密度爲0·9487克/立方釐 米。在反應器質量平衡的基礎上計算殘餘鉻，爲0 . 9 p pmw。完成S E C分析，用7 - 8粉狀分佈消捲積， 結果顯示在表I中。 實施例節I —例6 : 在溫度爲8 5 °C，總反應器壓力爲3 2 0 P s l g ( 2 · 2 m P a )下操作，配有水冷卻型熱交換器的1 4英 寸（3 5 · 6釐米）領試工廠規模氣相反應器中製造乙烯 -己烯共聚物。將乙烯以每小時約6 0磅（即2 7 · 2公 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-79 - 1245773 A7 B7 經濟部智慧財產局員工消費合作社印¾ 五、發明說明<77 ) 斤/小時）的速率給到反應器內，己烯以每小時約〇 . 8 磅（即0 · 3 6公斤/小時）的速率給到反應器內並將氫 以1 3毫磅/小時的速度給到反應器內。給入乙烯以保持 反應器中22〇psig (1.52mpa)的乙烯分壓 。製造速率爲約3 4磅/小時。反應器配備一通氣器，該 通氣器含有約1 ，1 0 0磅/小時的循環氣流。（通氣器 爲一裝置，用來在流化床氣相反應器中創造一無粒子區） 。在通氣器氣流中放置一錐形觸媒注射噴嘴，該噴嘴的管 口大小爲0 · 055英寸（0 · 14釐米）。在一 3/ 16英寸（0 · 48釐米）不銹鋼管中，將1重量％觸媒 B己烷觸媒溶液與0 · 2磅/小時（0 · 〇 9公斤/小時 )己烯混合約1 5分鐘。觸媒B和己烯混合液與輔觸媒（ iM Μ A〇一 3 A，1重量％鋁）線內混合約1 〇 — 1 5分 鐘。將1重量％觸媒A甲苯溶液加到經活化觸媒B溶液中 約5分鐘後噴入反應器。觸媒A觸媒量爲給入總溶液量的 約4 0 - 4 5莫耳％。除溶液外，加入異戊烷和氮以控制 粒子大小。將整個系統從注射噴嘴通過進入流化床。控制 Μ Μ A〇與觸媒的比例以使A 1 : Z r莫耳比爲3 0 0 : 1。產生的雙峰型聚合物熔融指數爲0 . 1 3 6克/1 0 分，流動指數爲3 8 . 1克/ 1 0分，密度爲 〇.9 4 8 8克/立方釐米。在反應器質量平衡的基礎上 計算殘餘鉻，爲〇 · 5ppmw。完成SEC分析，用7 - 8粉狀分佈消捲積，結果顯示在表I中。 (請先閱讀背面之注意事項寫本頁) --α 裝 · 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-80 - 經濟部智慧財產局員工消費合作社印製 1245773 Λ7 B7 五、發明說明（78 ) 窗施例節[—例^-2) IndZr (NEt2) 3 + 3 (CH3) 3CC〇2H — IndZr [〇2CCl (CH3)] 3 + Et2NH where Ind = indenyl and Et is ethyl. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -70-1245773 Printed by the Consumers 'Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (68) [(2' 4, 6 — iM e C 6 Η 2) NHC Η 2 C Η 2] 2 N 位 Coordination (coordinator 1) was prepared in a two-liter one-arm Schlenk flask and fed into a magnetic stirrer in the absence of oxygen and anhydrous nitrogen. Diethylenetriamine (23.450 g, 0.2227 mol), 2-bromotrimethylbenzene (9 0.51 g, 0.455 mol), tris (dibenzylacetone) dipalladium (1/041 g , 1: 14 millimoles), racemic one 2, 2 /-bis (phenylphosphine)-1, 1 / one naphthalene (racemic BINAP) (2. 1 2 3 g, 3. 4 1 milli Mol), tertiary sodium butoxide (65.535 g, 0.682 mole) and toluene (800 ml). The reaction mixture was stirred and heated to 100 ° C. After 18 hours, the reaction was judged to be complete by proton N M R spectroscopy. All remaining steps can be performed in air. All solvents were removed in vacuo and the residue was dissolved in 1 liter of ether. The ether was first rinsed with water (3 times in 250 ml), then rinsed with saturated aqueous sodium chloride solution (180 g in 500 ml of water), and then dehydrated with 30 g of magnesium sulfate. The ether was removed in vacuo to produce a red oil, which was dried under vacuum at 70 ° C for 12 hours (yield 71.10 g, 92%). QiHNMR (C6D6) 586.83 (s, 4), 3.39 (brs, 2), 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1) o Catalyst A (used in Section I of this embodiment The size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -71-▼ Packing ---- l ·. (Please read the precautions on the back before filling this page) Order | 1245773 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Λ7 ______B7_ V. Description of the Invention (69) 1.5% by weight catalyst toluene solution Note: All the following procedures are performed in the glove box. 1. Weigh out 100 grams of purified toluene and pour into a 1 liter conical flask equipped with a Teflon-coated stir bar. 2. Add 7.28 grams of tetrabenzyl chromium. 3 • Place the solution on a stirrer and stir for 5 minutes. All solids are dissolved. 4. Add 5.42 grams of upper ligand I. 5. Add another 5 1 g of purified toluene and stir the mixture for 15 minutes. No solids remained in the solution. 6 · Pour the catalyst solution into a clean washed 1 liter WhUey sample tube, mark it, remove it from the glove box, and place it in the holder for manipulation. Another method for preparing compound I {[((2,4,6-Me3C6H2) NCH2CH2] 2NH} Zr (CH2Ph) 2) was put in a 500 ml round bottom flask under a dry oxygen-free nitrogen into a magnetic stir bar, Tetrabenzyl chromium (Boulder Scientific) (41.729 g, 91.56 mmol) and 300 ml of toluene. The solid ligand I (32.773 g, 96.52 mmol) was added and stirred for 1 minute (the desired compound precipitated). The slurry volume was reduced to 100 ml, and 300 ml of pentane was added with stirring. The yellow-orange solid product was collected by filtration and dried under vacuum (4 4 · 8 11 1 g, 80% yield) ° lH NMR (CbDb) (57. 22- This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -72-L ------- I ------ l ·-丨 IT -------- I (Please read the precautions on the back before filling this page) 1245773 A7 B7 V. Description of the invention (70) (Please read the precautions on the back before filling this page) 6.8l (m, 12), 5.90 (d, 2), 3.38 (m, 2), 3.11 ( m, 2), 3.01 (m, i), 2.49 (m, 4), 2.43 (s, 6), 2.41 (s, 6), 2.18 (s, 6), 1.89 (s, 2 ), 0.96 (s, 2) ° Catalyst B (used in Section I of this example) Preparation of 1% by weight Catalyst B hexane solution All procedures were performed in a glove box. 1 · Purify 1 liter Hexane was poured into a 1 liter Erlenmeyer flask equipped with a Teflon-coated stir bar. 2. Add 6.67 grams of indyl chromium tns pivalate dry powder. 3. Place the solution on a magnetic stirrer and stir. 15 minutes. All solids dissolve. 4 • Pour the solution into a clean, washed 1 liter Whitey sample tube, mark it, remove it from the glove box and place it in the holder For operation. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Example I-Comparative Example 1: Operating at a temperature of 85 ° C and a total reactor pressure of 350 ps ig (2 · 4 m P a). An ethylene-hexene copolymer was produced in a 14-inch (3 5 · 6 cm) pilot plant-scale gas phase reactor in a water-cooled heat exchanger. Ethylene was produced at a rate of approximately 40 pounds per hour (1 8 · 1 Kg / hour) to the reactor 'apply hexene to the paper standard per hour at the standard of China National Standards (CNS) A4 (210 X 297 mm) -73-1245773 A7 B7 V. Description of the invention (please first Read the notes on the back and fill in this page again.) A rate of 0.6 pounds (27 kg / hour) was fed into the reactor and hydrogen was fed into the reactor at a rate of 5 milli pounds / hour. Nitrogen is fed into the reactor as a make-up gas at a rate of about 5-8 pounds per hour. The manufacturing rate is about 27 bpm. The reactor was equipped with a plenum 'which contained a circulating air flow of about 19,000 pounds per hour. (Aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor, as detailed in US Patent No. 5,6 9 3, 7 2 7 'this patent is incorporated herein by reference ). A cone-shaped catalyst injection nozzle with a nozzle size of 0 · 0 4 1 inch (0 · 10 cm) is arranged in the air flow of the ventilator. A toluene solution of 1% by weight of Catalyst A was mixed with an auxiliary catalyst (MMAO — 3 A ′ 1% by weight of aluminum) in a wire, and then fed into a fluidized bed through an injection nozzle. (MMA-3A is a modified methylalumoxane in heptane, which is commercially available from AK20 Chemicals, Inc. under the trade name Modified Methylalumoxane Type 3A). The ratio of M M A0 to the catalyst is controlled so that A 1: Z r is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the Morse ratio is 4 0 ·· 1. Nitrogen and isoheptane are also fed into the injection nozzle as needed to maintain a stable average particle size. The obtained unimodal polymer had a nominal 121 of 0. 28 dg / mi η and a density of 0. 935 g / cm 3. Based on the mass balance of the reactor, the residual chromium content of 1.63 p p m w was calculated. Sinus Section I-Comparative Example 2: Operating at a temperature of 85 ° C and a total reactor pressure of 3 2 0 P sig (2.2 m P a), 1 4 with a water-cooled heat exchanger Inch (3 5 · 6 cm) Leadership pilot plant scale gas phase reactor for manufacturing ethylene Paper size Applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -74-1245773 A7 B7 V. Description of the invention-- Hexene copolymer. Feed ethylene into the reactor at a rate of about 37 pounds per hour (19.8 kg / hour), and read hexene first at about Γ% per hour? Please fill in this page again.) The rate of 0.4 pounds (0.18 kg / hour) was fed into the reactor. Hydrogen was fed into the reactor at a rate of 12 milli pounds / hour. Ethylene was fed to maintain a 180-pound (1.2 mPa) ethylene partial pressure in the reactor. The manufacturing rate is about 25 pounds per hour. The reactor was equipped with a ventilator having a circulating gas flow of about 1.00 lb / hr. (The aerator is a ~ device used to generate a particle-free zone in a fluidized bed gas phase reactor). A 0. 055 inch (0 · 14 cm) conical catalyst injection nozzle is configured in the ventilator airflow. In a 3/16 inch (0.48 cm) stainless steel tube, a 1% by weight catalyst B hexane solution was mixed with 0.2 lb / hr (0.99 kg / hr) of hexene for about 15 minutes. The catalyst B and hexene mixture were mixed in the wire with the auxiliary catalyst (MM A03-3 A, 1% by weight of aluminum) for about 40 minutes. In addition to the solvent, isopentane and nitrogen were added to control particle size. Pass the entire system from the injection nozzle into the fluidized bed. The ratio of M M A0 to the catalyst is controlled so that the A 1: Z r mole ratio is 3 0 0: 1. The resulting bimodal polymer melt refers to the number printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at 797 g / 10 min and a density of 0.99678 g / cm3. The residual chromium was calculated on the basis of the mass balance of the reactor and was 0.7 p p m w. The S EC analysis was completed and deconvolved with a 4 powder distribution, and the results are shown in Table I. Example Section I Example 3; at a temperature of 8 5 t and a total reactor pressure of 3 2 0 psig (this paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) -75-1245773 economic Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau Λ7 B7 V. Description of the invention C3) 2 · 2 m P a), a 14-inch (3 5 · 6 cm) pilot plant scale equipped with a water-cooled heat exchanger An ethylene-hexene copolymer is produced in a gas phase reactor. Ethylene was fed into the reactor at a rate of about 53 pounds per hour (24 kg / hour), and hexene was fed to the reactor at a rate of about 0.5 pounds (0.22 kg / hour) per hour. And hydrogen was fed into the reactor at a rate of 9 lb / hr. Ethylene was fed to maintain a partial pressure of ethylene of 22 psig (1.52 mPa) in the reactor. The manufacturing rate is about 25 pounds per hour. The reactor was equipped with a ventilator with a circulating air flow of about 990 per hour (the ventilator is a device used to generate a particle-free zone in a fluidized bed gas phase reactor). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator, and the nozzle size was 0.055 inches (0.12 cm). In a 3/16 inch (0.48 cm) stainless steel tube, 1% by weight of Catalyst B in hexane solution was diluted with 0.2 b / h (0.9 kg / h) for about 15 minutes. The catalyst B and the mixed solution were mixed with the auxiliary catalyst (MMA-3A '1% by weight) in the line for about 20 to 25 minutes. In a split activated stainless steel tube, a 1% by weight catalyst A toluene solution was activated with a secondary catalyst (MM A03-3 A, 1 weight ratio aluminum) for about 50 to 55 minutes. Combine the two separately activated solutions into a single program line for about 4 minutes. Catalyst A The catalyst amount is about 40-45% by mole of the total feeding solution. In addition to the solution, isopentane and nitrogen were also added to control particle size. Pass the entire system from the injection nozzle into the fluidized bed. The ratio of M M A 0 to the catalyst is controlled so that the molar ratio of A 1: Z r is 3 0 0: 1. The bimodal polymer produced has a melt index of 0 · 0 4 5 g / 10 minutes and its flow index is the paper size. Applicable to China National Standard (CNS) A4 (210 X 297 mm) = 76-" " (Please read the notes on the back before filling out this page) Order --'------, 1245773 ___B7______ V. Description of the invention) 7. 48g / 10min. Its density is 0.9496 grams per cubic meter. The residual zirconium was calculated on the basis of the mass balance of the reactor to be 1.7 p p m w. The S EC analysis was completed and deconvolved with a 7-8 powder distribution. The results are shown in Table I. Example Section I Example 4; Operating at a temperature of 85 ° C and a total reactor pressure of 320 psig (2.2 mPa), a 14-inch (3 5 · 6 cm) water-cooled heat exchanger ) Production of ethylene-hexene copolymer in pilot plant scale gas phase reactor. Ethylene was fed into the reactor at a rate of about 50 pounds per hour (22.7 kg / hour), and some hexene was fed at a rate of about 0.7 pounds per hour (0.32 kg / hour). Into the reactor 'and hydrogen was fed into the reactor at a rate of 1 1 lb / hr. Ethylene was fed to maintain a partial pressure of ethylene of 22 psig (1.52 mPa) in the reactor. The manufacturing rate was about 29 lbs / hour. The reactor was equipped with a ventilator with a circulating air flow of about 970 pounds per hour. (Aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor). A cone-shaped catalyst injection nozzle is placed in the air flow of the ventilator. The nozzle size of the nozzle is 0. 055 inches (0. 14 cm) in a 3/16 inch (0. 48 cm) stainless steel tube. 1 The wt% Catalyst B Hexane catalyst solution was mixed with 0.2 lb / hr (0.09 kg / hr) of hexene for about 15 minutes. The catalyst B and the ignited mixed liquid were mixed with the catalyst (MM A 03 A, 1% by weight aluminum) in the wire for about 205 to 25 minutes. In a separate activated stainless steel tube, 'Use catalyst, active dagger 1' This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -77----------- -> --- install --- (Please read the notes on the back to write this page first) Order: Online, printed by the Consumers ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the employee ’s consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1257773 Α7 _ B7 V. Description of the invention (75) The toluene solution of catalyst A (M MW A-3 A, L% m aluminum) is about 50 to 5 minutes. The two separately activated solutions were combined into a single program line for about 4 minutes. The amount of catalyst A was about 40 to 45 mole% of the total solution fed. In addition to the solution, isopentane and nitrogen were added to control the particle size. Pass the entire system from the injection nozzle into the fluidized bed. The ratio of M M A0 to the catalyst was controlled so that the A 1: Z r mole ratio was 3 0 0: 1. The resulting bimodal polymer had a melt index of 0.054 g / 10 min, a flow index of 7.94 g / 10 min, and a density of 0.948 g / m3. The residual junction was calculated on the basis of the mass balance of the reactor and was 1 · 1 p pmw. The S EC analysis was completed and deconvolved with a 7-8 powder distribution. The results are shown in Table I. Example Section I Example 5; operating at a temperature of 85 ° C and a total reactor pressure of 3 2 0 P sg (2.2 m P a), 14 inches with a water-cooled heat exchanger (35.6 cm) A pilot plant-scale gas phase reactor was used to produce ethylene ~ hexene copolymers. Ethylene was fed into the reactor at a rate of about 60 pounds per hour (27. 2 kg / hour), and hexene was given to the reaction at a rate of about 0.8 pounds per hour (0.36 kg / hour). Hydrogen was fed into the reactor and into the reactor at a rate of 13 milli-pounds per hour. B is introduced to maintain the partial pressure of ethane at 2 2 0 P s i g (1.52 m P a) in the reactor. The manufacturing rate is about 34 pounds per hour. The reactor is equipped with a ventilator 'which contains a circulating air flow of about 960 lbs / hour (the ventilator is a device used to create a particle-free zone in a fluidized bed gas phase reactor). Please read the notes on the back first to write this page) I-J. This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -78-1245773 A7 B7 V. Description of the invention "6" Air flow A cone-shaped catalyst injection nozzle was placed in the nozzle, and the nozzle size of the nozzle was 0.05 mm (0.14 cm). In a 3/1 6 inch • J ------ · < ----: --- (Please read the precautions on the back to write this page) (0.48 cm) stainless steel tube In the process, a 1% by weight catalyst B hexane catalyst solution was mixed with 0.2 b / h (0.09 kg / h) hexene for about 15 minutes. Mix catalyst B and hexene with auxiliary catalyst (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by MM A03-3A, 1% by weight of aluminum) in the line for about 20-25 minutes. In a separate activated stainless steel tube ', a 1% by weight catalyst A toluene solution was activated with a secondary catalyst (MM A03-3 A, 1% by weight aluminum) for about 50 to 55 minutes. The two separately activated solutions were combined into a single program line for about 4 minutes. The amount of the catalyst A was about 40-4 5 mol% of the total amount of the input solution. In addition to the solution, isopentane and nitrogen were added to control the particle size. Pass the entire system from the injection nozzle into the fluidized bed. The ratio of M M A 0 to the catalyst was controlled so that the A 1: Z r Molar ratio was 3 OO: 1. The bimodal polymer has a melting index of 0.077 g / 10 min, a flow index of 12.7 g / 10 min, and a density of 0.94887 g / cm3. The residual chromium was calculated on the basis of the mass balance of the reactor and was 0.9 p pmw. The S EC analysis was completed and the deconvolution was performed with a 7-8 powder distribution. The results are shown in Table I. Example Section I—Example 6: Operate at a temperature of 85 ° C and a total reactor pressure of 3 2 0 P slg (2 · 2 m P a), with a 14 inch ( 3 5 6 cm) The ethylene-hexene copolymer was produced in a pilot plant-scale gas phase reactor. Ethylene is printed at about 60 pounds per hour (that is, 2 7 · 2 liters of paper. Applicable to China National Standard (CNS) A4 (210 X 297 mm)) -79-1245773 A7 B7 Ⅴ. Description of the invention < 77) kg / hour) into the reactor, hexene was fed into the reactor at a rate of about 0.8 pounds per hour (ie, 0.36 kg / hour) and Hydrogen was fed into the reactor at a rate of 13 millilbs / hour. Ethylene was fed to maintain a ethylene partial pressure of 22 psig (1.52 mpa) in the reactor. The manufacturing rate is about 34 pounds per hour. The reactor was equipped with a ventilator, which contained a circulating air flow of about 1,100 pounds per hour. (Aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor). A cone-shaped catalyst injection nozzle was placed in the ventilator airflow and the nozzle size was 0 · 055 inches (0 · 14 cm). In a 3/16 inch (0. 48 cm) stainless steel tube, mix 1% by weight of Catalyst B in hexane catalyst solution with 0.2 lb / hr (0. 09 kg / hr) hexene for about 15 minute. The mixed solution of catalyst B and hexene was mixed with auxiliary catalyst (iM M A03-3A, 1% by weight aluminum) in the wire for about 10-15 minutes. A 1% by weight toluene solution of catalyst A was added to the activated catalyst B solution for about 5 minutes, and then sprayed into the reactor. The amount of catalyst A was about 40-45% by mole of the total solution fed. In addition to the solution, isopentane and nitrogen were added to control the particle size. Pass the entire system from the injection nozzle into the fluidized bed. The ratio of M M A0 to the catalyst was controlled so that the A 1: Z r mole ratio was 3 0 0: 1. The resulting bimodal polymer had a melt index of 0.136 g / 10 minutes, a flow index of 38.1 g / 10 minutes, and a density of 0.948 g / cm3. The residual chromium was calculated based on the mass balance of the reactor and was 0.5 ppmw. Complete the SEC analysis and deconvolve with a 7-8 powder distribution. The results are shown in Table I. (Please read the precautions on the back first to write this page) --α Packing · This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -80-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1245773 Λ7 B7 V. Description of the invention (78) Window example section [—example ^-

在溫度爲8 5 °C ’反應器總壓力爲3 5 0 p s l g C 2 . 4 m P a )的條件下’在1 4英寸（3 5 · 6釐米） 的領試工廠規模氣相反應器中製造乙烯—己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙烯以每小時約4 2磅 (1 9 · 1公斤/小時）的速率給到反應器內，己烯以每 小時約0 · 8磅（〇 · 3 6公斤/小時）的速率給到反應 器內並將氫以1 3毫磅/小時的速率給到反應器內。給入 乙烯以保持反應器中2 2 0 p s i g ( 1 · 5 2 m P a ) 的乙烯分壓。製造速率爲約3 2磅/小時。反應器配備一 通氣器，該通氣器含有約2，0 10PPH的循環氣流。 (通氣器爲一裝置’用來在流化床氣相反應器中創造一無 粒子區）。在通氣器氣流中放置一錐形觸媒注射噴嘴，該 噴嘴的管口大小爲0 · 055英寸（0 · 14釐米）。在 一 3/1 6英寸（〇 · 48釐米）不銹鋼管中，將 〇· 2 5重量％觸媒B己烷觸媒溶液與〇 · 1磅/小時（ 〇· 0 5公斤/小時）己烯混合約1 5分鐘。觸媒B和己 烯混合液與輔觸媒（Μ Μ A〇—3 A，1重量％鋁）線內 混合約1 5分鐘。將〇 · 5重量％觸媒A甲苯溶液加到經 活化觸媒B溶液中約1 5分鐘後噴入反應器。觸媒A觸媒 量爲給入總溶液量的約6 5 — 7 0莫耳％。除溶液外，加 入異戊烷和氮以控制粒子大小。將整個系統從注射噴嘴通 過進入流化床。控制Μ Μ A〇與觸媒的比例以使最後A 1 :Z r·莫耳比爲3 0 0 : 1。產生的雙峰型聚合物熔融指 .I-----------I 裝--- (請先閱讀背面之注意事項Hi寫本頁) 訂. 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） .81 - 1245773 A7 _B7_ 五、發明說明（79 ) 数爲0 . 0 6克/ 1 0分，流動指數爲6 · 2 6克/ 1〇 分，密度爲0 . 9 5 0 1克/立方釐米。在反應器質量平 衡的基礎上計算殘餘锆，爲0 · 6 5 p p m w。完成 S E C分析，用7 - 8粉狀分佈消捲積，結果顯示在表I 中 〇 I.------r---一------ (請先閱讀背面之注意事項H寫本頁> .. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -82 - 1245773 Λ7 B7 五、發明說明（8Q ) 經濟部智慧財產局員工消費合作社印製 表[ 實施例 1(比較例） 2(比較例） o J 4 5 6 7 [：! ( dg/min ) ^ J.28 n/a 7.5 7.94 12.6 38.1 5.26 I：：/ I： 165.3 147 164.6 280.4 104 I：(dg/mm) 不流動 797 0.045 0.054 0.077 0.136 0.06 SEC實驗數據 Μη針算値） 80,600 2,952 7,908 10,896 10,778 10,282 8,700 Mw(計算値） 407,375 13,398 340,011 263,839 259,389 261,138 287,961 Mw/Mn(計算値） 5.05 4.54 43 24.2 24.1 25.4 33.1 Μη(計算値） 7,645 10,552 10,673 10,105 8,523 Mw(計算値） 339,752 258,282 248,215 252,310 284,814 iV[w/Mn(計算値） 44.44 24.48 23.26 24.97 33.42 LMWMn (計算値 ) 2,988 3,741 5,548 5J31 6,382 4,165 LMW Mw(計算値） 13,214 13,259 16,388 15,214 18,333 11,771 LMW Mw/Mn(計算 値） 4.42 3.54 2.95 2.65 2.87 2.83 HMW Μη(計算値） 73,979 122,758 111,256 85,461 88,374 115,954 HMW Mw(計算値） 407,513 633,154 501,013 484,657 607,625 526,630 HMW Mw/Mn(計算 値） 5.51 5.16 4.5 5.67 6.88 4.54 ***物(HMW/總量) 100 0 52.67 49.92 49.64 39.7 53.03 反應器條件 反應器溫度(°C) 85 80 80 5 !5 85 85 85 C：psi/mPa 220/1.52 180/1.24 220/1.52 ' Ώ0/1.52 220/1.52 220/1.52 220/1.52 H:/G莫耳比 0.0016 0.0018 0.0013 C ).0014 0.0014 0.001 0.0019 C6/ G莫耳比 0.00488 0.00153 0.0074 C ).0073 0.0077 0.0075 0.005 滯留時間（小時） 3.6 7.5 5.3 ^ L74 3.87 3.87 3.4 莫耳比HMW/LMW 0.71 〔 ).73 0.76 0.76 2.16 莫耳％觸媒A 100 41 ^ β 43 43 68 Zrppm，實驗 1.33 1 ί·61 1.33 0.8 0.97 Z卬pm,進料 1.63 1.46 1 [.06 0.9 0.54 0.62 平均 1.63 1.4 i ί·34 1.12 0.67 0.8 鋁/锆莫耳比 400 330 ： 380 320 307 500 觸媒B作用克PE/ 毫莫耳觸媒-小時 9,965 12,515 18,754 37,288 50,142 觸媒A活性克PE/ 毫莫觸媒-小時 15,559 15,730 17,042 24,323 32,465 26,203 • I------r---„---裝--- (請先閱讀背面之注意事項1^11寫本頁〕 訂-· 本紙張尺度適用中國a家標準（CNS)A4规格（210 X 297公釐） -83 - 1245773 A7 B7 五、發明說明（81 ) 節I -比較例1和2給出關於單一成分的觸媒系統是 如何反應的實驗數據。實施例3和4證實在相同的反應條 件及觸媒送料系統下溫度的影響。注意溫度越高，M w/ Μ η就越低，正如M F R —般。實施例5與6比較出對於 大體相同的反應器條件及觸媒送料系統下活化程序的影響 。注意在實施例6中，觸媒的整體活性較良好。實施例6 與7表明在大體相同的反應器條件下控制所製高分子物質 的量之能力。實施例7給入一更高比例的觸媒A，由此就 產生一更高量的更M w物質。 貫施例節 I —實施例8 ·· 根據上面實施例4產生的3 5 0磅（1 5 9公斤）聚 乙烯（以下簡稱聚合物A )在一 Werner-Fleidei*er ZSK-30的 雙螺桿擠壓機中，用1 0 0 0 p p m的IrganoxTM 1 067及 1 5 0 0 ??111的1以以〇5^ 1 068在220°(：熔融溫度下混 練形成九粒，然後將這些九粒在一 Alpine吹膜擠壓線上吹 成0 · 5密爾（1 3微米）的膜。擠壓條件爲：模頭 —1 6 0毫米的三層體，1 . 5毫米的模隙，4 0 0 °C的 模溫，4 8英寸（1 2 2釐米）的平鋪寬度，標的熔化溫 度一 4〇〇°F(21〇°C)，擠壓速率爲一 31〇磅/小 時（1 4 4公斤/小時），4 2 0磅/小時（1 9 1公斤 /小時）及4 6 0磅/小時（2 0 9公斤/小時）。將 ESCORENE™ HD7 7 5 5. 1 0 ( Exxon Chemical Company, Houston, Texas的一種傳統系列反應器產品）在相同的條件 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -84 - I------r---,---裝--- (請先閒讀背面之注意事項βι寫本頁> 訂· -線. 經濟部智慧財產局員工消費合作社印裂 1245773 Λ7 _B7_五、發明說明（82 )下運轉以作比較。所有的膜皆經2 3 °C ’ 5 0 %濕度’調 理4 0小時。這些數據列於I A表中。 (請先閒讀背面之注意事項寫本頁) . 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -85 - 1245773 Λ7 B7 r— 表I A __—— 比冽膀/小時 (公斤/小時)_- 日苗塌格 a 317(144) HD7755.10 ------- 317(144) 聚合物A HD7755.10 緊合物A HD7755.10 421(191) 421(191) 460(209) 460(209) 密爾/ 13微米 0.502密爾/ 13微米 0.532密爾/ 14微米 0.519密爾/ 13微米 0.543密爾 /14微米 0.528密爾/ 13微米 tizKWm ____- 密度克/立方麗 乎 0.9489 0.949 0.9502 0.949 0.9468 0.9489 26英寸(66釐米)孜: 擲1天 ___ 26英寸(66釐米)投: 擲7天 355克 308克 327克 .325 克 Nm nm 351克 308克 314克 344克 301克 360克 MD抗撕強度克 /密爾（mPa) . 22 (0.87) 16(0.63) 25(0.98) 15(0.59) 22(0.87) 15(0.59) TD抗撕強度克/ 密爾(mPa) 97 ( 3.82) 102(4.02) 77(3.03) 84(3.31) 100(3.94) 81(3.19) 1%正割MD psig(mPa) 161,000 (1110) 200,200 (1380) 159,000 (1096) 183,800 (1267) 156,200 (1077) 178,700 (1232) 1%正割TD psig(mPa) 184,500 (1272) 212,500 (1465) 163,500 (1127) 206,600 (1425) 161,400 (1113) 212,500 (1465) MD極限張力 psig(mPa) 14445 (100) 14347(99) 12574(87) 15110(104) 12934(89) 15609(108) TD極限張力 psig(mPa) 13369 (92) 12124(84) 10785(74) 12278(85) 11727(81) 11482(79) 極限伸長率％ 285 293 246 296 253 299 極限伸長率％ 317 393 305 377 340 377 濁度％ 59.6 64 57.8 62.0 56.9 60.9 45度光澤度 13.6 10.8 13.4 12.0 14.9 11.9 、發明説明θ3 (請先閱讀背面之注意事項fSR寫本頁)At a temperature of 8 5 ° C 'with a total reactor pressure of 350 pslg C 2.4 mP a)' in a pilot plant-scale gas phase reactor of 14 inches (3 5 · 6 cm) Manufacture of ethylene-hexene copolymer. The reactor was equipped with a water-cooled heat exchanger. Ethylene was fed into the reactor at a rate of about 42 pounds (19. 1 kg / hour) per hour, and hexene was given to the reaction at a rate of about 0.8 pounds (0.36 kg / hour) per hour. The reactor was fed with hydrogen at a rate of 13 milli-pounds per hour. Ethylene was fed to maintain a ethylene partial pressure of 220 p s i g (1.52 m P a) in the reactor. The manufacturing rate was about 32 lbs / hour. The reactor was equipped with a ventilator containing a circulating gas flow of about 2.00 PPH. (Aerator is a device 'used to create a particle-free zone in a fluidized bed gas phase reactor). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator, and the nozzle size was 0. 055 inches (0. 14 cm). In a 3/1 6 inch (0.48 cm) stainless steel tube, 0.25% by weight of Catalyst B Hexane catalyst solution and 0.1 lb / hour (0.05 kg / hour) hexene Mix for about 15 minutes. The mixed solution of catalyst B and hexene was mixed with auxiliary catalyst (MM A0-3 A, 1% by weight aluminum) in the wire for about 15 minutes. A 0.5% by weight catalyst A toluene solution was added to the activated catalyst B solution for about 15 minutes and sprayed into the reactor. The amount of the catalyst A was about 65 to 70 mole% of the total solution amount. In addition to the solution, isopentane and nitrogen were added to control the particle size. Pass the entire system from the injection nozzle into the fluidized bed. The ratio of M M A0 to the catalyst was controlled so that the final A 1: Z r · Mole ratio was 300: 1. The produced bimodal polymer melt index. I ----------- I Pack --- (Please read the note on the back first to write this page) Order. This paper size applies Chinese national standards ( CNS) A4 specification (210 x 297 mm) .81-1245773 A7 _B7_ V. Description of the invention (79) The number is 0.06 g / 10 minutes, the flow index is 6.26 g / 10 minutes, density 0.99 g / cm3. Residual zirconium was calculated on the basis of the mass balance of the reactor to be 0.65 p p m w. Complete SEC analysis, deconvolution with 7-8 powder distribution, and the results are shown in Table I. I .------ r ---------- (Please read the note H on the back first Write this page & .. .. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperatives. This paper is printed in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -82-1245773 Λ7 B7 V. Description of Invention (8Q) Printed by the Consumers' Cooperative of the Ministry of Intellectual Property Bureau [Example 1 (comparative example) 2 (comparative example) o J 4 5 6 7 [:! (Dg / min) ^ J.28 n / a 7.5 7.94 12.6 38.1 5.26 I :: / I: 165.3 147 164.6 280.4 104 I: (dg / mm) non-flowing 797 0.045 0.054 0.077 0.136 0.06 SEC experimental data μn calculation 80) 600 2,952 7,908 10,896 10,778 10,282 8,700 Mw (calculation) 407,375 13,398 340,011 263,839 259,389 261,138 287,961 Mw / Mn (calculated 値) 5.05 4.54 43 24.2 24.1 25.4 33.1 Mn (calculated 値) 7,645 10,552 10,673 10,105 8,523 Mw (calculated 値) 339,752 258,282 248,215 252,310 284,814 iV [w / Mn (calculated 値) 44.44 24.48 23.26 24.97 33.97 LMWMn (calculated) 2,988 3,741 5 , 548 5J31 6,382 4,165 LMW Mw (calculated) 13,214 13,259 16,388 15,214 18,333 11,771 LMW Mw / Mn (calculated) 4.42 3.54 2.95 2.65 2.87 2.83 HMW Mn (calculated) 73,979 122,758 111,256 85,461 88,374 115,954 HMW Mw (calculated) 407,513 633,154 501,013 484,657 607,625 526,630 HMW Mw / Mn (calculated 値) 5.51 5.16 4.5 5.67 6.88 4.54 split (HMW / total) 100 0 52.67 49.92 49.64 39.7 53.03 reactor conditions reactor temperature (° C) 85 80 80 5! 5 85 85 85 C: psi / mPa 220 / 1.52 180 / 1.24 220 / 1.52 'Ώ0 / 1.52 220 / 1.52 220 / 1.52 220 / 1.52 H: / G Molar ratio 0.0016 0.0018 0.0013 C) .0014 0.0014 0.001 0.0019 C6 / G Morse ratio 0.00488 0.00153 0.0074 C) .0073 0.0077 0.0075 0.005 Dwell time (hours) 3.6 7.5 5.3 ^ L74 3.87 3.87 3.4 Morse ratio HMW / LMW 0.71 []. 73 0.76 0.76 2.16 Mole% catalyst A 100 41 ^ β 43 43 68 Zrppm, experiment 1.33 1 ί · 61 1.33 0.8 0.97 Z 卬 pm, feed 1.63 1.46 1 [.06 0.9 0.54 0.62 average 1.63 1.4 i ί · 34 1.12 0.67 0.8 aluminum / zircon molar ratio 400 330: 380 320 307 500 touches B action gram PE / millimolar catalyst-hour 9,965 12,515 18,754 37,288 50,142 Catalyst A active gram PE / millimolar catalyst-hour 15,559 15,730 17,042 24,323 32,465 26,203 • I ------ r --- „- --Install --- (Please read the precautions on the back 1 ^ 11 first to write this page) Order-· This paper size is applicable to China A Standard (CNS) A4 (210 X 297 mm) -83-1245773 A7 B7 V. Description of the Invention (81) Section I-Comparative Examples 1 and 2 give experimental data on how a single-component catalyst system reacts. Examples 3 and 4 demonstrate the effect of temperature under the same reaction conditions and catalyst feed system. Note that the higher the temperature, the lower the M w / M η, just as M F R —. Examples 5 and 6 compare the effects on substantially the same reactor conditions and activation procedures under the catalyst feed system. Note that in Example 6, the overall activity of the catalyst is good. Examples 6 and 7 demonstrate the ability to control the amount of polymer material produced under substantially the same reactor conditions. Example 7 feeds a higher proportion of Catalyst A, thereby producing a higher amount of more Mw material. Throughout Example Section I—Example 8 · The 350 screw (159 kg) polyethylene (hereinafter referred to as polymer A) produced in Example 4 above was a twin screw of a Werner-Fleidei * er ZSK-30 In an extruder, knead with 1000 ppm of IrganoxTM 1 067 and 1 50 0 ?? 111 to 0 5 ^ 1 068 at 220 ° (: melting temperature to form nine pellets, then these nine pellets A 0.5 mil (13 micron) film is blown on an Alpine blown film extrusion line. The extrusion conditions are: die head-a three-layer body of 160 mm, a die gap of 1.5 mm, and 40 0 ° C die temperature, 48 inch (122 cm) tile width, target melting temperature-400 ° F (21 ° C), extrusion rate of-31 pounds per hour (1 4 4 kg / h), 420 lbs / hr (191 kg / h) and 460 lbs / hr (209 kg / h). ESCORENE ™ HD7 7 5 5. 1 0 (Exxon Chemical Company , Houston, Texas, a traditional series of reactor products) Under the same conditions, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -84-I ------ r ---, --- install --- (please read the note on the back first) Item βι write this page ℴ-line. Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1245773 Λ7 _B7_ V. Description of Invention (82) for comparison. All films are subjected to 2 3 ° C '5 0% humidity 'conditioning for 40 hours. These data are listed in the IA table. (Please read the precautions on the back to write this page). Printed on paper standards applicable to the Chinese National Standard (CNS) ) A4 size (210 X 297 mm) -85-1245773 Λ7 B7 r— Table IA __—— Than the upper arm / hour (kg / hour) _- Rimiao Grid a 317 (144) HD7755.10 --- ---- 317 (144) polymer A HD7755.10 compact A HD7755.10 421 (191) 421 (191) 460 (209) 460 (209) mil / 13 micron 0.502 mil / 13 micron 0.532 mil Mol / 14 micron 0.519 mil / 13 micron 0.543 mil / 14 micron 0.528 mil / 13 micron tizKWm ____- Density g / cubic Li 0.9489 0.949 0.9502 0.949 0.9468 0.9489 26 inches (66 cm) zi: throw 1 day ___ 26 inch (66 cm) throw: 7 days 355 g 308 g 327 g. 325 g Nm nm 351 g 308 g 314 g 344 g 301 g 360 g MD tear resistance G / mil (mPa). 22 (0.87) 16 (0.63) 25 (0.98) 15 (0.59) 22 (0.87) 15 (0.59) TD tear strength g / mil (mPa) 97 (3.82) 102 (4.02 ) 77 (3.03) 84 (3.31) 100 (3.94) 81 (3.19) 1% Secant MD psig (mPa) 161,000 (1110) 200,200 (1380) 159,000 (1096) 183,800 (1267) 156,200 (1077) 178,700 (1232) 1% secant TD psig (mPa) 184,500 (1272) 212,500 (1465) 163,500 (1127) 206,600 (1425) 161,400 (1113) 212,500 (1465) MD ultimate tension psig (mPa) 14445 (100) 14347 (99) 12574 ( 87) 15110 (104) 12934 (89) 15609 (108) TD Ultimate tension psig (mPa) 13369 (92) 12124 (84) 10785 (74) 12278 (85) 11727 (81) 11482 (79) Ultimate elongation% 285 293 246 296 253 299 Ultimate elongation% 317 393 305 377 340 377 Haze% 59.6 64 57.8 62.0 56.9 60.9 45 degree gloss 13.6 10.8 13.4 12.0 14.9 11.9 、 Instructions θ3 (Please read the precautions on the back first fSR write this page )

— P 訂·- 經濟部智慧財產局員工消費合作社印製 MDM幾器方向，TD =橫向，UT Str =極限抗張強度 U · E1 ο n g =極限伸長率 ESCORHNH H D 77 5 5.1 0爲一種聚乙烯聚合物，其可: Exxon Γ h ^ ^— P order ·-The direction of printing MDM devices by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, TD = transverse, UT Str = ultimate tensile strength U · E1 ο ng = ultimate elongation ESCORHNH HD 77 5 5.1 0 is a polyethylene Polymer which can: Exxon Γ h ^ ^

nemical Company, Houston，Texas 獲得，具有一 7 |」]1」，及[25的〜[11^’丨80,000的卜^， 〇.L)5克/立方趨米I 沧以’其由雙反應器系統產生。 本 紙張尺度適用 準（CNS)A‘l 規格（210 X 297 公釐） 86- 1245773 Λ7 B7 五、發明說明) 實施例節I 一實施例9 : 將數桶粒狀樣品（按上述聚合程序用2 . 3的莫耳觸 媒比（觸媒A /觸媒B )製得者）與1 〇 〇 〇 p p m的 IrganoxTM 1 076 及丨 500ppm 的 IrgafosTM 1 06 8 及 1 5 00ppm 的硬 脂酸鈣滾動混合。將經滾動混合粒狀樹脂在2 1 / 2 〃 (6 . 3 5公分）的Prodex混練線上以4〇〇T ( 2〇4 °C )造粒。將由此製得的九粒在裝配著有一 5 0毫米單螺 桿（1 8 ·· 1 L / D比例）及1 0 0毫米模隙爲1毫米 的環行模頭之擠壓機5 0毫米ApUne吹膜線上擠壓成膜。 擠壓條件爲：4 0 0 °F ( 2 0 4 °C )的模頭溫度，輸出率 1 0 0磅/小時（4 6公斤/小時）。一套典型的溫度分 布爲··料桶1 1 /料桶1 2 /滑塊接合器/底部接合器/ 豎直式接合器/模底/模中/模頂的溫度分別爲：3 8 0 °F/400°F/400°F/400°F/400°F/400 °F/410T/41〇T(193°C/204°C/2〇4 〇C/204°C/204〇C/204°C/2 1 0°C/2 1 0 t )。將九粒樣品以9 2英尺/分鐘（4 8釐米/秒）的 線上速度擠壓產生1 . 0密爾（2 5微米）的膜樣品及在 線上速度184英尺/分鐘（94釐米/秒）下以4 · 0 吹爆比（B U R )產生0 · 5密爾（1 3微米）的膜樣品 。這兩種情況下產生的泡沬都顯示出極好穩定性’呈典型 的內縮式酒瓶狀。吹製泡沬的F L Η (霜線高度）對 1 . 0密爾（2 5微米）及〇· 5密爾（1 2 . 5微米） 的膜分別保持在3 6英寸（9 1 · 4趨米）及4 0英寸（ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公沒） -87 - (請先閱讀背面之注意事項寫本頁) 裝 線· 經濟部智慧財產局員工消費合作社印製 1245773 Λ7 ___B7__ 五、發明說明（85 ) 1〇1 . 6歷米）。在相同的擠壓條件下，擠Μ腿頭與發 動機的負載表現出比ES CORE NETM HD7 7 5 5.10 ( —種習用系 列反應器產品，由 Exxon Chemical Company, iVIt Belvue， Houston，Texas製造）稍微高。所得膜的性質列於表I B中 。所有的膜樣品都經調理到2 3 °C ’ 5 0 %濕度，4 0小 時。0 . 5毫升的膜（12 . 5微米）落錘抗衝擊強度爲 3 8〇克，比ESC〇RENETM HD77 5 5.1 0的3 30克較爲高。 (請先閱讀背面之注意事寫本頁)Nemical Company, Houston, Texas, with a 7 | "] 1", and [25 ~ [11 ^ '丨 80,000 bu ^, 〇.L) 5 grams / cubic trend meter I Cang Yi's double reaction Device system. The size of this paper applies to the standard (CNS) A'l (210 X 297 mm) 86- 1245773 Λ7 B7 V. Description of the invention) Example Section I Example 9: Several barrels of granular samples (used in the above polymerization procedure) Molar catalyst ratio of 2.3 (producer of catalyst A / catalyst B)) and 1000 ppm of IrganoxTM 1 076 and 500 ppm of IrgafosTM 1 06 8 and 1 500 ppm of calcium stearate roll mixing. The rolled and mixed granular resin was granulated on a 2 1/2 〃 (6.35 cm) Prodex kneading line at 400 T (204 ° C). Nine pellets thus obtained were equipped with a 50 mm ApUne extruder equipped with a 50 mm single screw (1 8 · · 1 L / D ratio) and a 100 mm circular die with a 1 mm die gap. The film is extruded to form a film. The extrusion conditions are: die temperature of 400 ° F (204 ° C), output rate of 100 pounds per hour (46 kg / hour). A typical set of temperature distributions is: • Tank 1 1 / Tank 1 2 / Slide adapter / Bottom adapter / Vertical adapter / Mold bottom / Mold / Top temperature: 3 8 0 ° F / 400 ° F / 400 ° F / 400 ° F / 400 ° F / 400 ° F / 410T / 41〇T (193 ° C / 204 ° C / 2 04 ° C / 204 ° C / 204 ° C / 204 ° C / 2 1 0 ° C / 2 1 0 t). Nine samples were squeezed at a line speed of 92 feet / minute (48 cm / second) to produce 1.0 mil (25 micron) film samples and a line speed of 184 feet / minute (94 cm / second) A film sample of 0. 5 mils (13 microns) was produced at a burst ratio (BUR) of 4.0. The foam produced in both cases showed excellent stability ', which is typical of a constricted wine bottle. Blown bubble 沬 (frost line height) to 1.0 mil (25 micron) and 0.5 mil (12. 5 micron) films were maintained at 36 inches (9 1 · 4 trend) M) and 40 inches (this paper size applies to China National Standard (CNS) A4 specifications (210 X 297)) -87-(Please read the precautions on the back first to write this page) Printed by the Consumer Cooperative 1245773 Λ7 ___B7__ V. Description of the invention (85) 101.6 calendar meters). Under the same squeeze conditions, the load of the squeeze M leg and the engine showed a slightly higher load than ES CORE NETM HD7 7 5 5.10 (a custom series reactor product, manufactured by Exxon Chemical Company, iVIt Belvue, Houston, Texas). . The properties of the resulting film are listed in Table IB. All membrane samples were conditioned to 23 ° C ′ 50% humidity, 40 hours. The 0.5 millimeter film (12.5 micron) has a drop impact strength of 380 g, which is higher than the 3 30 g of ESCORENETM HD77 5 5.1 0. (Please read the note on the back to write this page)

—裝 P . 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -88 - 1245773 Λ7 B7 五、發明說明（86 ) 經濟部智慧財產局員工消費合作社印製 表[B Escorene™7755 聚合物B L·(克/10分） 0.08 0.062 L·!(克/10 分） 10 10.02 Li/L 134 160.5 密度(克/立方釐米） 0.952 0.9485 輸出量(磅/小時X公斤/小時） 104(47) 100(47) 模頭速率(磅/小時/模內） 約8 約8 模頭壓力psi/(mPa) 7,200(50) 7600(53) 發動機負荷(安培） 56 61 BUR 4 4 霜線高度(英寸)(釐米） 36(91.4) 40(101.6) 36(91.4) 40(101.6) 熔融裂縫 j\w w J\w 泡沬穩定性 良好 良好 良好 導出率(英尺/分鐘)(米/秒） 92(0.5) 185(0.9) 92(0.5) 184(0.9) 膜規格(密爾X微米） 1(25) 0.5(12.5) 1(25) 0.5(12.5) 落錘抗衝擊強度(克） 250 330 290 360 抗張強度(psigXMpa) 機器方向 8,400(58) 11,300(78) 8100(56) 11400(79) 橫向 7,900(55) 10,400(72) 7230(50) 9520(66) 伸長率(％) 機器方向 350 230 410 330 橫向 570 390 580 410 Elmendorf抗撕強度(克/密爾)(克/微米） 機器方向 25(0.98) 22(0.87) 24(0.95) 33(1.30) 橫向 142(5.59) 72(2.83) 205(8.07) 71(2.80) 模數(psi)(MPa) 機器方向 127,000(876) 144,000(993) 131500(907) 135350(933) 橫向 146,000(1007) 169,000(1165) 160250(1105) 156300(1078) M D =機器方向， T D =橫向 (請先閱讀背面之注意事項:寫本頁)—Installation P. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -88-1245773 Λ7 B7 V. Description of the Invention (86) Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives [B Escorene ™ 7755 Polymer BL · (g / 10min) 0.08 0.062 L ·! (G / 10min) 10 10.02 Li / L 134 160.5 Density (g / cm3) 0.952 0.9485 Output Amount (lb / hr X kg / hr) 104 (47) 100 (47) Die speed (lb / hr / in-mold) About 8 About 8 Die pressure psi / (mPa) 7,200 (50) 7600 (53) Engine Load (Amp) 56 61 BUR 4 4 Frost line height (inches) (cm) 36 (91.4) 40 (101.6) 36 (91.4) 40 (101.6) Melt crack j \ ww J \ w Foam stability is good Good good export Rate (ft / min) (m / s) 92 (0.5) 185 (0.9) 92 (0.5) 184 (0.9) Membrane specifications (mil X micron) 1 (25) 0.5 (12.5) 1 (25) 0.5 (12.5 ) Drop impact strength (g) 250 330 290 360 Tensile strength (psigXMpa) Machine direction 8,400 (58) 11,300 (78) 8100 (56) 11400 (79) Lateral 7,900 (55) 10,400 (72) 7230 ( 50) 9520 (66) Elongation (%) Machine direction 350 230 410 330 Transverse direction 570 390 580 410 Elmendorf Tear strength (g / mil) (g / micron) Machine direction 25 (0.98) 22 (0.87) 24 (0.95 ) 33 (1.30) Horizontal 142 (5.59) 72 (2.83) 205 (8.07) 71 (2.80) Modulus (psi) (MPa) Machine direction 127,000 (876) 144,000 (993) 131500 (907) 135350 (933) Horizontal 146,000 (1007) 169,000 (1165) 160250 (1105) 156300 (1078) MD = machine direction, TD = landscape (please read the note on the back first: write this page)

—i I 裝 訂： 本紙張尺度適用中國國家標準（CNS)A4規i (210 X 297公隹） -89- 1245773 Λ7 B7 五、發明說明（?7 ) 實施例節[一窗施例1 0 : 按照實施例9的程序，將數桶粒狀樣品（聚合物C按 上述聚合程序及觸媒莫耳比例（觸媒A比觸媒B )爲 〇.7 3 2製得，聚合物D按上述聚合程序及觸媒莫耳比 例（觸媒A比觸媒B )爲2 · 6製得）與lOOOppm的 IrganoTlM 1067，1500ppm 的硬脂酸鈣及 1500ppm 的 Ii:gafQSTMlQ68滾動混合，然後按實施例9中所述予以造粒和 擠壓。所有的膜都調理到2 3 °C，5 0 %濕度5 0小時。 從聚合物C及聚合物D中所製〇 · 5密爾（1 2 · 5微米 )的膜展現出3 8 0克的落錘抗衝擊強度，超過 ESC〇RENETM HD77 5 5.1 0的330克。這些數據歹ij於表I C中。 (請先閱讀背面之注意事項寫本頁) 裝 訂. •線· 經濟部智慧財產局員工消費合作社印製 90 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公* ) 1245773 7 Β 五、發明說明) 經濟部智慧財產局員工消費合作社印製 丧[C 樣品 聚合物C 聚含物D Escorcne 7755 反應溫度rc) 35 85 C：(psigj(kPa) 220(1517) 220(1517) H:/C:(莫耳） 0.0014-0.0016 0.00102 C:/C。(莫耳') 0.0075-0.0078 0.00531-0.00586 Μη 14,600 16,400 Mw 309,100 298,200 291,500 Mw/Mn 21.2 18.2 15.7 HMW/LiViW 53.8/46.2 50.5/49.5 12(克/10分鐘） 0.056 0.049 0.08 m(克AO分鐘） 6.48 6.7 10 MFRCti/Ii) 115.8 138 134 密度(克/立方釐米） 0.9487 0.9461 0.952 輸出率(猜/小時)(公斤/小時） 102(46) 102(46) 100(45) 模頭速率(碌/小時/模內）· 〜8 〜8 10 頭壓（psigXMpa) 8,120(56) 7,890(54) 7,230(50) 發動機負載(安培） 64.5 63 59 BUR 4 4 4 霜線尚度(英寸X蠻米） 40(101.6) 40(101.6) 36(91.4) 40(101.6) 36(91.4) 40(101.6) 熔化破裂 無 無 無 泡沬穩定性 普通 良好. 良好 良好 良好 良好 膜規格(密爾X微米） 1(25.4) 0.5(12.7) 1(25.4) 0.5(12.7) 1(25.4) 0.5(12.7) 落錘抗衝擊強度(克） 200 380 200 380 250 330 抗張強度 機器方向(psig)(mPa) 10,3〇〇 (71) 19,900 (137) 9，900 (68) 15,500 (107) 8,400 (58) 11,3〇〇 (78) 橫向(psig)(mPa) 7,900 (55) 13,800 (95) 8,400 (58) 14,500 (100) 7,900 (55) 10,400 (72) 伸長率(％) 機器方向 320 240 290 250 350 230 橫向 630 385 610 350 570 390 Elmendorf抗撕強度 機器方向(克/密爾)(克/微米） 24(0.95) 21(0.83) 36(1.42) 36(1.42) 25(0.98) 22(0.87) 橫向(克/密爾)(克/微米） 410(16.1) 87(3.4) 350(13.3) 66(2.6) 142(5.6) 72(2.8) 模數 ί幾器方向(千psigXMpa) 105(724) 120(827) 103(710) 110(758) 127(876) 144(993) 横向(psigXMpa) 128(883) 126(869) 129(889) 114(786) 146 (1007) 169(1165)—I I Binding: This paper size applies the Chinese National Standard (CNS) A4 Regulation i (210 X 297 cm) -89- 1245773 Λ7 B7 V. Description of the invention (? 7) Example section [一 窗 实施 例 1 0: According to the procedure of Example 9, several barrels of granular samples (Polymer C according to the above-mentioned polymerization procedure and the molar ratio of the catalyst (catalyst A to catalyst B) were prepared as 0.72, and polymer D was prepared as described above. Polymerization procedure and catalyst mole ratio (made from catalyst A to catalyst B) is 2. 6) and IrganoTlM 1067 at 1000 ppm, calcium stearate at 1500 ppm and Ii: gafQSTMlQ68 at 1500 ppm, and then mixed according to Example 9 Pelletize and squeeze as described. All films were conditioned to 23 ° C, 50% humidity for 50 hours. The 0.5 mil (12. 5 micron) film made from polymer C and polymer D exhibited a drop weight impact strength of 380 grams, exceeding 330 grams of ESCORENETM HD77 5 5.10. These data 歹 ij are in Table IC. (Please read the notes on the back first to write this page) Binding. • Thread · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 90 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 public *) 1245773 7 Β V. Description of the invention) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [C Sample polymer C Polymer D Escorcne 7755 Reaction temperature rc) 35 85 C: (psigj (kPa) 220 (1517) 220 (1517) H : / C: (Mole) 0.0014-0.0016 0.00102 C: / C. (Mole ') 0.0075-0.0078 0.00531-0.00586 Μη 14,600 16,400 Mw 309,100 298,200 291,500 Mw / Mn 21.2 18.2 15.7 HMW / LiViW 53.8 / 46.2 50.5 / 49.5 12 (g / 10 minutes) 0.056 0.049 0.08 m (g AO minutes) 6.48 6.7 10 MFRCti / Ii) 115.8 138 134 Density (g / cm3) 0.9487 0.9461 0.952 Output rate (guess / hour) (kg / hour) 102 ( 46) 102 (46) 100 (45) Die speed (lu / hour / in-mold) · ~ 8 ~ 8 10 Head pressure (psigXMpa) 8,120 (56) 7,890 (54) 7,230 (50) Engine load (Amp) 64.5 63 59 BUR 4 4 4 Frost line stillness (inch X bary rice) 40 (101.6) 40 (101.6) 36 (91.4) 40 (10 1.6) 36 (91.4) 40 (101.6) Melt and rupture No non-foaming Stability is generally good. Good Good Good Good film specifications (mil X micron) 1 (25.4) 0.5 (12.7) 1 (25.4) 0.5 (12.7) 1 (25.4) 0.5 (12.7) Drop weight impact strength (g) 200 380 200 380 250 330 Tensile strength Machine direction (psig) (mPa) 10,300 (71) 19,900 (137) 9,900 (68 ) 15,500 (107) 8,400 (58) 11,3〇 (78) Lateral (psig) (mPa) 7,900 (55) 13,800 (95) 8,400 (58) 14,500 (100) 7,900 (55) 10,400 (72) Elongation (%) Machine direction 320 240 290 250 350 230 Transverse direction 630 385 610 350 570 390 Elmendorf Tear strength machine direction (g / mil) (g / micron) 24 (0.95) 21 (0.83) 36 (1.42) 36 (1.42 ) 25 (0.98) 22 (0.87) Horizontal (g / mil) (g / micron) 410 (16.1) 87 (3.4) 350 (13.3) 66 (2.6) 142 (5.6) 72 (2.8) Module Direction (thousand psigXMpa) 105 (724) 120 (827) 103 (710) 110 (758) 127 (876) 144 (993) Horizontal (psigXMpa) 128 (883) 126 (869) 129 (889) 114 (786) 146 (1007) 169 (1165)

Alpine線，2英寸的螺桿，4英寸（10.2釐米）的模頭，40密爾（1016 微米）的模縫，410下（210°(：)的模頭設定溫度。 (請先閱讀背面之注意事項寫本頁) _ 本紙張义度適用中國國家標準（CNS)A4觇格（210 x 297公釐） .以. 1245773 A7 137 五、發明說明（89 ) 除以上實施例以外，其他有關用本文所述觸媒系統進 行聚合作用的變化包括： 1 ·可將化合物I溶解在一溶劑，最好是甲苯中，以 形成合意重量％溶液，然後與其他觸媒系統組合。 2.觸媒A可用〇·5〇重量％甲苯溶液，觸媒B可 用0 . 2 5重量％己烷溶液，而於觸媒A與觸媒B經分開 活化然後混合在一起（平行活化）時，以觸媒B與觸媒A 的莫耳比例爲0 · 7使用，或於觸媒A先被活化，然後加 入觸媒B (順序活化）時，以觸媒B與觸媒A的莫耳比例 爲2 . 2至1 · 5使用。 3 ·提高或降低反應溫度以分別縮小或擴大M w/ Μ η 〇 4 .改變滯留時間以影響產品屬性。變化越大，影響 越大。1至5時，最好是4小時的停留時間會產生良好的 產品屬性。 5 .將觸媒用產生一無粒帶的方式噴在反應器中。這 無粒帶可以透過6英寸的管子用5 0，0 0 0磅/小時的 循環氣流產生。觸媒可以用氮氣霧化氣透過噴嘴予以霧化 0 6 .活化劑，最好是Μ M A〇 3 A，可用在異戊烷 ，己烷或庚烷中7重量％鋁的溶液’以足夠提供1 0 0比 3 0 0 的A 1 / Z r比例之進料速度使用。 7 ·觸·Α!^ΜΜΑ〇 3Α線上混合’然後線上加 入觸媒Β，両:將混合物導入反應器中。 (請先閱讀背面之注意事項寫本頁〕Alpine wire, 2 inch screw, 4 inch (10.2 cm) die, 40 mil (1016 micron) die seam, 410 die (210 ° (:) die setting temperature. (Please read the note on the back first Matters written on this page) _ The meaning of this paper applies to the Chinese National Standard (CNS) A4 grid (210 x 297 mm). 1245773 A7 137 V. Description of the invention (89) In addition to the above examples, other relevant use of this document The changes in the polymerization of the catalyst system include: 1. Compound I can be dissolved in a solvent, preferably toluene, to form a desired weight% solution, and then combined with other catalyst systems. 2. Catalyst A is available 0.50% by weight toluene solution, catalyst B can use 0.25% by weight hexane solution, and when catalyst A and catalyst B are separately activated and then mixed together (parallel activation), catalyst B and The mole ratio of catalyst A is 0 · 7, or when catalyst A is activated first and then catalyst B is added (sequential activation), the mole ratio of catalyst B to catalyst A is 2.2 to 2. Use 1 · 5 · 3 · Increase or decrease the reaction temperature to reduce or expand the M w / Μ η 〇 04. Change Retention time affects product attributes. The greater the change, the greater the impact. From 1 to 5, a residence time of preferably 4 hours will produce good product attributes. 5. Spray the catalyst in a way that produces a grainless belt. In the reactor. This pellet-free belt can be generated through a 6-inch tube with a circulating air flow of 50,000 pounds per hour. The catalyst can be atomized with a nitrogen atomizing gas through a nozzle. 6 Activator, preferably It is M MA 03 A, which can be used in a solution of 7 wt% aluminum in isopentane, hexane or heptane at a feed rate sufficient to provide an A 1 / Z r ratio of 100 to 300. 7 · Touch · A! ^ ΜΜΑ〇3Α online mixing 'then add catalyst B online, 両: introduce the mixture into the reactor. (Please read the precautions on the back to write this page]

All 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公a ) - 92 - 1245773 A7 B7___ 一 五、發明說明（9〇 ) 8 ·觸媒A與Μ M A〇 3 A線上混合，觸媒B與 Μ M A Ο 3 A線上混合，然後這兩種經活化的觸媒線上 混合，再將其導入反應器中。 下面實施例節I I的實施例使用一種觸媒系統，此觸 媒系統包括一種具有千基脫離基的含第1 5族金屬觸媒。 實施例節I I .觸媒系統包括具有苄基脫離基的含第i 族金屬觸媒 按前面實施例節I製備：〔（2，4，6 — M e 3 C 6 Η 2 ) N H C Η 2 C Η 2〕2 或（N Η 配位子）’ 及{〔（ 2，4，6 - Μ e 3 C 6 Η 2 ) Ν C Η 2 C Η 2〕2 Ν Η } Ζ r (CH2Ph)2 或（Zr - ΗΝ3)。 {〔（2，4，6 — Me3C6H2)NCH2CH2〕2 NH} ZrCl2 或（Zr CI2 — HN3)之製備將 5 . 4 8〇克的Z r ( N M e 2 ) 4 ( 2〇· 4 8毫莫耳：） 溶解於一 2 5 0毫升圓底燒瓶中所裝5 0毫升戊烷中°加 入 6 · 656 克〔（2，4，6 - Me3C6H2) NHCH2CH2〕2 NH (20 · 48毫莫耳）的戊大元 經濟部智慧財產局員工消費合作社印製 溶液（5 0毫升），然後將溶液攪拌2小時。混合醯胺{ 〔（2，4，6 - M e 3 C 6 Η 2 ) N C Η 2 C Η 2〕‘2 N H } Ζ r ( Ν Μ e 2 ) 2以質子Ν Μ R鑑定，但不分離出° Η N M R ( C 6 D 6 ) ό 6 . 9 4 ( m ^ 4 ) ’All Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 malea)-92-1245773 A7 B7___ 15. Explanation of the invention (9〇) 8 · Catalyst A It is mixed with Μ MA〇3 A line, catalyst B is mixed with Μ MA 〇 3 A line, then these two activated catalyst lines are mixed, and then they are introduced into the reactor. The following embodiments of the following embodiments use a catalyst system. The catalyst system includes a Group 15 metal-containing catalyst having a thousands of radicals. Example Section II. The catalyst system includes a Group i metal-containing catalyst having a benzyl leaving group according to the previous Example Section I: [(2,4,6 — M e 3 C 6 Η 2) NHC Η 2 C Η 2] 2 or (N Η ligands) 'and {[((2,4,6-Μ e 3 C 6 Η 2) Ν C Η 2 C Η 2] 2 Ν Η} Z r (CH2Ph) 2 or (Zr-ΗΝ3). Preparation of {[(2,4,6 — Me3C6H2) NCH2CH2] 2 NH} ZrCl2 or (Zr CI2 — HN3) 5.48 g of Z r (NM e 2) 4 (20.4 · 8 mmol) Ear:) Dissolved in 50 ml of pentane in a 250 ml round-bottomed flask ° Added 6 · 656 g [(2,4,6-Me3C6H2) NHCH2CH2] 2 NH (20 · 48 mmol) The employee of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs printed a solution (50 ml) of the cooperative, and then stirred the solution for 2 hours. Mixed amidine {[(2,4,6-Me 3 C 6 Η 2) NC Η 2 C Η 2] '2 NH} Z r (Ν Μ e 2) 2 was identified by the proton NM R but was not isolated ° ° NMR (C 6 D 6) ό 6. 9 4 (m ^ 4) '

m，2) ，2.59(m，4) ，2.45(s 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -93 - 1245773 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（91 ) 2.43(s，6)，2.27(s’6)，2.2〇C s ，6 ) : 1 . 8 Ο ( m，1 )。真空脫除溶劑。將剩餘 物溶解在甲苯中，然後一份地加入6 · 0克的 C · 1 S 1 M e 3 ( 5 5毫莫耳）。將溶液攪拌2 4小時。真 空脫除溶劑，並將固體懸浮於戊烷中。過濾收集固體並用 戊烷洗（5 . 5 2 8克，5 4 %產率）。二氯化物丨〔（ 2，4，6 — M e 3 C 6 Η 2 ) N C Η 2 C Η 2〕2 N Η } ZrCl2 係以質子 NMR 鑑定。iH N M R ( C s D e ) 0'6.88(s，2)，6.81(s，2)，3·32 (m，2)，2·86(γπ，2)，2.49(s，6) ，2.47(m，4) > 2 . 3 9 ( s > 6 ) ，2·12 (s ，6 ) ，N H不淸楚。 觸媒A (用於本實施例節I I ) 之製備 於一 1 0 0毫升圓底燒瓶中的2，0 5 1克的MAO (6 · 8 3 6克3 0重量％甲苯中溶液，可Albemarle Corporation, Baton Rouge，Louisiana 獲得）和 7 · 2 8 5 克 甲苯內加入〇 · 1 4 5克的Z r C 1 2 — Η N 3。將溶液攪 拌1 5分鐘。加入5 · 0 7 0克的氧化矽（Da vision 948， 在600°C的溫度下鍛燒過，可從W.R. Grace, Davision D i v丨s丨ο η，B a 11丨m o r e，M a r y 1 a n d獲得）並混合。將混合物在真 空乾燥一夜獲得7 . 0 1 1克的成品觸媒，具有0 . 3 6 重量％的锆，A 1 / Z r的比例爲1 2 2 : 1。 觸媒B (用於本實施例節I I )之製備 • J------1---.------ (請先閱讀背面之注音？事項寫本頁) · 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _ 94 - 1245773 A7 137 經濟部智慧財產局員工消費合作社印製 五、發明說明（?2 ) 於一 1 0 0毫升圆底燒瓶中的0 · 8 0 1克的Μ A〇 . 67 0克30重量％甲苯中溶液，可Albemnde Corporation，Baton Rouge，Louisiana 獲得）和 4 . 6 7 9 克 甲苯內加入0 · 0 7 〇克的Z r — Η N 3。將溶液攪拌1 5 分鐘。加入2，1 3 0克的氧化矽（Da vision 9 4 8，在600°C 的溫度下鍛燒過，可從wi Grace, Davision Division， Baltimore，Maryland獲得）並混合。將混合物在真空乾燥一 夜獲得2 . 8 9 9克的成品觸媒，具有0 . 3 5重量％的 錯，Al/Z r的比例爲12〇♦ 1 。 實施例節I I 一比較例I用觸媒A進行漿相乙烯聚合 聚合係在一裝配有一機械攪拌器，一用來控溫的外部 水套，一隔膜入口及一排氣口，及一乾燥的氮和乙烯的調 節供給口之1升壓熱反應器中，於漿相中實施。將反應器 烘乾並在160° C的溫度下除氣。加入異丁烷（400 毫升）作爲稀釋劑並用氣密性注射筒加入0 . 7毫升2 5 重量％三辛基鋁己烷溶液作爲一種淸除劑。將反應器加熱 到9 0 °C。在乙烯的壓力下加入〇 . 2 0 0克的成品觸媒 A，再用1 4 3 p s 1 g ( 9 6 8 k P a )的乙烯加壓。 持續聚合4 0分鐘，同時將反應器溫度保持在9 0 °C，且 以固定乙烯流保持在1 4 3 p s 1 g ( 9 8 6 k P a )。 透過迅速冷卻並放出來停止反應。得到1 〇 . 5克的聚乙 烯（流動指數（F I )=無流_，活性=2 0 9克聚乙烯 /毫莫耳觸媒·大氣壓·小時）。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-95 - (請先閲讀背面之注意事項寫本頁) 裝 訂. •f 1245773 經濟部智慧財產局員工消費合作社印製 Λ7 Β7 五、發明說明（93 )m, 2), 2.59 (m, 4), 2.45 (s) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -93-1245773 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs V. Description of the invention (91) 2.43 (s, 6), 2.27 (s'6), 2.20 C s, 6): 1.8 (m, 1). The solvent was removed in vacuo. The residue was dissolved in toluene, and 6.0 g of C · 1 S 1 M e 3 (55 mmol) was added in one portion. The solution was stirred for 24 hours. The solvent was removed in vacuo and the solid was suspended in pentane. The solid was collected by filtration and washed with pentane (5.528 g, 54% yield). Dichloride 丨 [(2, 4, 6 — Me 3 C 6 Η 2) N C Η 2 C Η 2] 2 N Η} ZrCl2 was identified by proton NMR. iH NMR (C s D e) 0'6.88 (s, 2), 6.81 (s, 2), 3.32 (m, 2), 2.86 (γπ, 2), 2.49 (s, 6), 2.47 (m, 4) > 2. 3 9 (s > 6), 2.12 (s, 6), NH is not bad. Catalyst A (used in Section II of this example) Preparation of 2.01 g of MAO (6. 8 36 g 30% by weight toluene solution in a 100 ml round bottom flask), Albemarle Corporation, Baton Rouge, Louisiana) and 7. 2 8 5 g of toluene were added with 0.1 4 5 g of Z r C 1 2 —ΗN 3. The solution was stirred for 15 minutes. Add 5.07 g of silicon oxide (Da vision 948, calcined at 600 ° C, available from WR Grace, Davision D iv 丨 s 丨 ο η, B a 11 丨 more, Mary 1 and Get) and mix. The mixture was dried in the vacuum overnight to obtain 7.01 g of the finished catalyst, with 0.36 wt% zirconium, and the ratio A 1 / Z r was 1 2 2: 1. Preparation of Catalyst B (used in Section II of this embodiment) • J ------ 1 ---.------ (Please read the note on the back? Matters to write on this page) · Size of this paper Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) _ 94-1245773 A7 137 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 0.50 g of M A 0.67 g of 30% by weight solution in toluene, available from Albemnde Corporation, Baton Rouge, Louisiana) and 4.679 g of toluene were added with 0.77 g of Z r — Η N 3. The solution was stirred for 15 minutes. Add 2,130 grams of silicon oxide (Da vision 9 48, calcined at 600 ° C, available from Wi Grace, Davision Division, Baltimore, Maryland) and mix. The mixture was dried under vacuum overnight to obtain 2.889 g of the finished catalyst, with a fault of 0.35% by weight, and an Al / Zr ratio of 120%. Example Section II A Comparative Example I Slurry-phase ethylene polymerization using catalyst A is equipped with a mechanical stirrer, an external water jacket for temperature control, a diaphragm inlet and an exhaust port, and a dry Nitrogen and ethylene are supplied to the slurry phase in a pressure-boosting thermal reactor. The reactor was dried and degassed at a temperature of 160 ° C. Isobutane (400 ml) was added as a diluent and 0.7 ml of a 25% by weight trioctyl aluminum hexane solution was used as a scavenger using an airtight syringe. The reactor was heated to 90 ° C. 0.20 g of finished catalyst A was added under the pressure of ethylene, and then pressurized with 143 ps 1 g (986 kPa) of ethylene. Polymerization was continued for 40 minutes while the reactor temperature was maintained at 90 ° C, and was maintained at 1 4 3 p s 1 g (9 8 6 k P a) with a fixed ethylene stream. The reaction was stopped by rapid cooling and release. 10.5 g of polyethylene was obtained (flow index (F I) = no flow, activity = 209 g polyethylene / mole catalyst · atmospheric pressure · hour). This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -95-(Please read the notes on the back to write this page) Binding. • f 1245773 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Λ7 Β7 5. Description of the invention (93)

讶例節ί I 一度施例2 m觸媒B進行乙Μ喂m發ASurprise example: I once applied 2m catalyst B for BM and m hair A

聚合係在一裝配有一機械攪拌器，一用來控溫的外部 水套，一隔膜入口及一排氣口，及一乾燥的氮和乙烯的調 節供給口之1升壓熱反應器中，於漿相中實施。將反應器 烘乾並在1 6 0 3C的溫度下除氣。加入異丁烷（：4 0 0毫 升）作爲稀釋劑並用氣密性注射筒加入0 · 了毫升2 5重 量％三辛基鋁己烷溶液作爲一種淸除劑。將反應器加熱到 9〇°C。在乙烯的壓力下加入0 · 1 0 0克的成品觸媒B ，再用1 4 4 P s 1 g ( 9 9 3 k P a )的乙烯加壓。持 續聚合3 0分鐘，同時將反應器溫度保持在9 0 °C，且以 固定乙烯流保持在1 4 4 p s 1 g ( 9 9 3 k P a )。透 過迅速冷卻並放出來停止反應。得到1 1 · 8克的聚乙燒 (流動指數（F I )二無流動，活性二6 4 1克聚乙烯/ 毫莫耳 觸媒·大氣壓·小時）。 從以上顯示的數據看，在相同的條件下，本發明具有 經取代烴脫離基的含第1 5族金屬觸媒，尤其是有芳基取 代基的烷基者，比含有鹵素的相同化合物具有遠較爲高的 產率。 以下實施例節I I I的實施例係用包括一種氧化矽結 合鋁活化劑的觸媒系統。 窗施例節I I I .包括氧化矽結合鋁的觸媒系統 按®施例節I所述準備：〔（2 ，4 ，6 — Μ e . C . Η 2 ) Ν Η C Η 2 C Η 2 ] ·： Ν Η (配位子）, 本紙張尺度適用中國國家標準（CNS)A4蜆格（210 X 297公;?έ ) -96 - (請先閱讀背面之注意事項寫本頁) 裝 1245773 經濟部智慧財產局員工消費合作社印製 Λ7 B7_____ 五、發明說明（94 ) 及{ |: ( 2，4，6 - M eC η Η 2 ) M C Η」C Η」.]j Ν Η } Ζ r ( C Η ·2 Ρ h ) 2 或（Ζ r - Η Ν ! ) ° 氧化矽結合鋁（S l -〇—A 1 ( C 6 F 5 ) 2 )的備 將 4 0 . 6 8 6 克的氧化矽（Davison 948，在 600° C 的溫度下鍛燒’可從 Maryland，Baltimore，Davision Dmsion，W.R· Grace獲得）在一 5 〇 0毫升的圓底燒瓶中 所裝300毫升甲苯中攪和。加入固體A 1 (C6F5) 3 甲苯（15 · 470克，24 · 90毫莫耳）並將混合物 攪拌3 0分鐘。使混合物靜置1 8小時。過濾分離出氧化 矽結合鋁，在真空下乾燥6小時，產率爲4 9 . 2 1 1克 。按EP 0694 548 A1所述方法準備Al( C 6 F 5 ) 3甲苯，其以其全文倂於本文作爲參考。 觸媒A (用於本實施例節I I I )之製備 於1 · 0 0 0克的氧化矽結合鋁（上面實施例4 ) / 2〇毫升甲苯中加入Zr—HN‘3 (〇.〇76克， 〇· 1 2 4毫莫耳）/5毫升甲苯。將混合物攪拌3 0分 鐘。氧化矽無色變成橘紅色。過濾分離氧化矽結合鋁並在 真空下烘乾6小時，產出率爲1 · 〇 5 1克。最終過渡金 屬載量爲1 1 6微莫耳/克，過渡金屬對氧化矽結合鋁。 m例節I I I 一實施例1闲觸媒A進行乙烯-己烷漿相 衆合 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公；^ ) (請先閱讀背面之注意事項^^、寫本頁> 訂· 1245773 Α7 Β7 經濟部智慧財產局員工消費合作社印製The polymerization was carried out in a pressurized thermal reactor equipped with a mechanical stirrer, an external water jacket for temperature control, a diaphragm inlet and an exhaust port, and a dry nitrogen and ethylene regulated supply port. Implemented in the slurry phase. The reactor was dried and degassed at a temperature of 160 ° C. Isobutane (400 ml) was added as a diluent and 0.5 ml of a 25% by weight trioctyl aluminum hexane solution was used as a scavenger using an airtight syringe. The reactor was heated to 90 ° C. 0. 100 grams of finished catalyst B was added under the pressure of ethylene, and then pressurized with 1 4 4 P s 1 g (9 3 3 k P a) of ethylene. The polymerization was continued for 30 minutes while keeping the reactor temperature at 90 ° C and at a constant ethylene flow of 144 ps 1 g (993 kpa). The reaction was stopped by rapid cooling and release. 1 1.8 g of polyethylene was obtained (flow index (F I) di no flow, active di 641 1 g polyethylene / mole catalyst · atmospheric pressure · hour). From the data shown above, under the same conditions, the Group 15 metal catalyst with a substituted hydrocarbon leaving group of the present invention, especially the alkyl group having an aryl substituent, Much higher yields. The following examples, Sections II and I, use a catalyst system that includes a silicon oxide bonded aluminum activator. Window Example Section III. The catalyst system including silicon oxide and aluminum is prepared as described in Example Section I: [(2, 4, 6 — M e. C. Η 2) Ν Η C Η 2 C Η 2] ·: Ν Η (ligand), this paper size is applicable to Chinese National Standard (CNS) A4 grid (210 X 297 male;?) -96-(Please read the precautions on the back first to write this page) Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau Λ7 B7_____ V. Description of Invention (94) and {|: (2, 4, 6-M eC η Η 2) MC Η 「C Η」.] J Ν Η} Z r ( C Η · 2 ρ h) 2 or (Z r-Η Ν!) ° The preparation of silicon oxide combined with aluminum (S 1-〇—A 1 (C 6 F 5) 2) will oxidize 4 0.68 g Silicon (Davison 948, calcined at 600 ° C. 'available from Maryland, Baltimore, Davision Dmsion, WR Grace) was stirred in 300 ml of toluene in a 5000 ml round bottom flask. Solid A 1 (C6F5) 3 toluene (15.470 g, 24.90 mmol) was added and the mixture was stirred for 30 minutes. The mixture was allowed to stand for 18 hours. The silica-bound aluminum was separated by filtration and dried under vacuum for 6 hours with a yield of 49.2 1 g. Al (C 6 F 5) 3 toluene was prepared according to the method described in EP 0694 548 A1, which is incorporated herein by reference in its entirety. Catalyst A (used in Section III of this example) was prepared from 1.0 g of silicon oxide combined with aluminum (Example 4 above) / 20 ml of toluene was added with Zr-HN'3 (0.076 g 0.12 4 mmol) / 5 ml of toluene. The mixture was stirred for 30 minutes. Silicon oxide is colorless and turns orange-red. The silicon oxide-bound aluminum was separated by filtration and dried under vacuum for 6 hours. The yield was 1.05 g. The final transition metal loading was 116 micromoles / gram, and the transition metal-to-silicon oxide bonded aluminum. Example III. Example 1 Example 1. Idle catalyst A for ethylene-hexane slurry. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 males; ^) (Please read the precautions on the back first ^ ^ 、 Write this page > Order 1245773 Α7 Β7 Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs

五、發明說明巧） 聚合係在一裝配有一機滅攪拌器，一闬來控溫的外部 水套，一隔膜入口及一排氣口，及一乾燥的氮和乙燏的調 節供給口之1升壓熱反應器中，於漿相中實施。將反應器 烘乾並在1 6 0 °C的溫度下除氣。加入異丁烷（4 0 0毫 升）作爲稀釋劑，3 5毫升的1 -己烯並用密性注射筒加 入0 . 7毫升2 5重量％三辛基鋁己烷溶液作爲一種淸除 劑。將反應器加熱到6 0 °C。在乙烯的壓力下加入 〇.10〇克的成品觸媒A，再用78ps1(538 k P a )的乙烯加壓。持續聚合3 0分鐘，同時將反應器 溫度保持在6 0 °C，且以固定乙嫌流保持在7 8 P s i ( 5 3 8 k P a )。透過迅速冷卻並放出來停止反應。得到 7〇· 0克的共聚物（流動指數（F I )=無流動，活性 二2320克聚乙烯/毫莫耳 觸媒·大氣壓·小時，加 入1〇，5重量—己烯）。 下面實施例節I V的實施例係使用含第1 5族金屬觸 媒的溶液進料。 實施例節I V含第1 5族金屬觸媒的溶液進料 按實施例節I所述準備：〔（2，4，6-M e 3 C 6 Η 2 ) N H C H a C Η 2 ] ： ( Ν Η 配位子或前 體—化合物 I )及{ 〔 （ 2，4，6 — Μ e C β Η 2 ) Ν C Η 2 C Η 2〕2 ·Ν Η } Ζ r* ( C Η .2 Ρ ti ) 2 (化合物 I (請先閱讀背面之注意事項寫本頁) __霞 Ρ · 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -98- 1245773 Λ7 B7 五、發明說明@6 ) ΜΜΛ_U1於本窗施例節I v )之製備 ------------裝--- (請先閱讀背面之&意事項寫本頁) (1 _ · 5_重曩甲苯中） 注=以下所有的程序均在一手套箱中進行。 1 ·稱1 ο 〇克的純化甲苯放入一1升的錐瓶中’此 錐瓶裝配有〜經Teflon塗.覆的攪拌棒。 2·加入7.28克的肆？基鉻。 3 ·將溶液放在攪動器上並攪拌5分鐘。所有的固體 都溶解。 4 ·加入5 . 4 2克的化合物I。 5 ·加入另一份5 5 1克的純化甲苯並將混合物攪拌 1 5分鐘。溶液中無固體殘留。 線』 6 ·將觸媒溶液倒入一乾淨經沖滌過的1升Whitey樣 品筒中，予以標記，從手套箱中取出，並將之置於儲存區 域以待操作。 實施例節I V —實施例1 經濟部智慧財產局員工消費合作社印製 在溫度爲8 5 °C，反應器總壓力爲3 5 0 P s 1 g ( 2 . 4mPa)的條件下，在14英寸（35 · 6釐米） 的領試工廠規模氣相反應器中製造乙烯-己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙烯以每小時約4 0磅 (1 8公斤/小時）的速率給到反應器內，己烯以每小時 約0 · 6磅（0 · 3公斤/小時）的速率給到反應器內並 將氫以5毫磅/小時的速率給到反應器內。以約5 - 8磅 本紙張尺度適用令國國家標準（CNS)A4規格（210 X 297公釐）-99 - 1245773 A7 B7 五、發明說明（97 ) /小時的速率將氮氣給到反應器内作爲贿充氣體。製造速 率爲約2 7磅/小時。反應器配一通氣器’該通氣器含 有約1 9 Ο Ο P P Η的循環氣流。（通氣器爲一裝置，用 來在流化床氣相反應器中創造一無粒子區°參看美國專利 第5 ，6 9 3 ，7 2 7號）。在通氣器氣流中放置一錐形 觸媒注射噴嘴，該噴嘴的管口大小爲0 · 〇 4 1英寸（ 0 . 1 1釐米）。將1重量％觸媒Α在甲苯中的溶液與輔 觸媒（Μ Μ A〇一3 A，1重量％鋁在己烷中，（ Μ Μ A 0 3 A是在庚烷中的改質甲基鋁氧烷，可透過商 業手段從Akzo Chemical，Inc.，獲得7其商品名爲改質甲基 鋁氧烷3A型，奇涵蓋在美國專利第5，041 ，584 中）線內混合，再將其透過注射口注射入流化床中。 Μ Μ A〇與觸媒皆經控制以使鋁比鉻的莫耳比例爲4〇0 :1。視需要也將氮與異戊烷給入注射噴口中以保持穩定 的平均粒徑‘。獲得一單峰聚合物具有標稱0 . 2 8 d g / m 1 η ( I 2i)及0 · 9 3 5克/立方釐米的屬性。依反 應器質量平衡基礎計算剩餘锆爲1 · 6 3 p p m w。 實施例節I V —竇施例2 : 在溫度爲8 5 °C ’反應器總壓力爲3 5 0 p s 1 g ( 2 . 4 m P ai )的條件下，在1 4英寸（3 5 . 6麓米） 的領試工廠規模氣相反應器中製造乙烯-己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙烯以每小時約4 0磅 (1 8公斤/小時）的速率給到反應器内，己烯以每小時 (請先閱讀背面之注意事 寫本頁) 經濟部智慧財產局員Η消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐） -100 - 1245773 Λ7 B7 五、發明說明巧） 約3 · 5磅（1 . 6公斤/小時）的速率給到反應器内並 將氫以約2 5毫磅/小時的速率給到反應器內°以約5 -8膀/小時的速率將氮氣，給到反應、器內'作爲補充氣體°製 造速率爲約2 0磅/小時。反應器配備一通氣器，該通氣 器含有約19 0 OPPH的循環氣流。（通氣器爲一裝置 ，用來在流化床氣相反應器中創造一無粒子區。參看美國 專利第5，693，727號）。在通氣器氣流中放置一 錐形觸媒注射噴嘴，該噴嘴的管口大小爲〇 · 〇 4 1英寸 (〇· 1 1釐米）。將1重量％觸媒A在甲苯中的溶液， 〇 . 22PPH的1 一己烯與輔觸媒（MMAO——3A， 4重量％鋁在異戊烷中）線內混合，再將其透過注射口注 射入流化床中。Μ Μ A〇與觸媒皆經控制以使鋁比鉻的莫 耳比例爲7 4 6 : 1。視需要也將氮與異戊烷給入注射噴 口中以保持穩定的平均粒徑。獲得一單峰聚合物其具有標 稱 1.2dg/min(l2) ? 29 . 7dg/min ( I 2 1 ) ，I 2 ^ / I 2 的比例爲 2 3 . 9 ，及〇· 9 1 6 5 經濟部智慧財產局員工消費合作社印製 克/立方釐米的屬性。依反應器質量平衡基礎計算剩餘鉻 爲 0 · 89ppmw。 實施例節I V —實施例3 在溫度爲1 0 5 °C ’反應器總壓力爲3 5 0 p s l g (2 · 4mPa)的條件下，在14英寸（35 · 6燈米 )的領試工廠規模氣相反應器中製造乙烯-己烯共聚物。 該反應器配有水冷卻型熱交換器。將乙烯以每小時約4〇 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐）-1〇1 - 1245773 Λ7 B7 五、發明說明（?9 ) f請先閱讀背面之注意事項寫本頁) 磅（1 8公斤/小時）的速率給到反應器内，己烯以每小 時約0 · 6磅（〇 . 3公斤/小時）的速率給到反應器內 並將氫以約6毫磅/小時的速率給到反應器內。以約5〜 8磅/小時的速率將氮氣給到反應器內作爲補充氣體。製 造速率爲約2 4磅/小時。反應器配備一通氣器，該通氣 器含有約1 6 0 〇 p p H的循環氣體流。（通氣器爲一裝 置，用來在流化床氣相反應器中創造一無粒子區。參看美 國專利第5 ，693，727號）。在通氣器氣流中放置 一錐形觸媒注射噴嘴，該噴嘴的管口大小爲0 ♦ 0 5 5英 寸（0 · 14釐米）。將1 · 5重量％觸媒A在甲苯中的 溶液與輔觸媒（^11^八〇一3厶’1.8重量％鋁在25 %庚烷/ 7 5 %己烷溶液中）線內混合’再將其透過注射 口注射入流化床中。M M A 0與觸媒皆經控制以使鋁比锆 的莫耳比例爲3 2 〇 : 1。視需要也將氮與異戊烷給入注 經濟部智慧財產局員工消費合作社印奴 射噴口中以保持穩定的平均粒徑。獲得一單峰聚合物其具 有標稱〇.67dg/min(l2i) ’及0.9358 克/立方釐米的屬性。依反應器質量平衡基礎計算剩餘鉻 爲 2 · 33ppmw。 實施例節I V -實施例4„: 在溫度爲8 5 °C ’反應器總壓力爲3 5 0 p s i g ( 2 · 4 m P a )的條件下’在1 4英寸.（3 5 · 6潑米） 的領試工廠規模氣相反應器中製造乙烯-己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙烯以每小峙約3 6磅 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐）-1〇2 - 1245773 Λ7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（100 ) 斤/小時）的速率給到反應器内，己烯以_ (1 ο · 〇 ^ 〜 防〔1 · 6公斤/小時）的速率給到反應器 小時約3 . b防、 內並將氫以約2 8毫磅/小時的速率給到反應器內。以約 5 一 8磅/小時的$ $ !1夺S i，給劳·！ S應、器θ ί乍，爲》甫％ ^體 。制造速率爲約1 8磅/小時。反應器配備一通氣器’該 通氣器含有約χ9〇〇ΡΡΗ的循環氣流。（通氣器爲一 裝置，用來在流化床氣相反應器中創造一無粒子區。參看 帛國專利第5 ，693，727號）。在通氣器氣流中放 置一錐形觸媒注射噴嘴，該噴嘴的管口大小爲0 · 〇 4 1 英寸（〇 . 11釐米）。將1重量％觸媒A在甲苯中的溶 液，0 . 2 2 p P H的1 一己嫌與輔觸媒（M M A〇一 3 A，4重量％鋁在異戊丨完中）線內混合’再將其透過注 射口注射入流化床中。M M A〇與觸媒皆經控制以使鋁比 锆的莫耳比例爲9 2 5 : 1 °視需要也將氮與異戊烷給入 注射噴口中以保持穩定的平均粒徑。獲得一單峰聚合物其 具有標稱 1 · 7dg/min (12) ，41 · 7dg/ min ( I 2 1 ) ，I 2 1 / I 2 的比例爲 2 4 · 1 ，及 〇· 9 1 7克/立方釐米的屬性。依反應器質量平衡基礎 計算剩餘鉻爲〇 . 9 4 ρ p m w。 實施例節I V -窗施例5 : 在溫度爲8 5 °C，反應器總壓力爲3 5 0 p s i g ( 2 · 4 m P a )的條件下，在1 4英寸（3 5 · 6燈米） 的領試工廠規模氣相反應器中製造乙烯一己烯共聚物u該 .1-------------·— (請先閱讀背面之注意事項寫本頁〕 訂· 丨線 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -103- 1245773 Λ7 _ B7_____ 五、發明說明0〇1 ) 反應器配有水冷卻型熱交換器。將乙烯以每小時約〇膀 (1 8公斤/小時）的速率給到反應器內，己烯以每小時 約0 . 6磅（0 · 3公斤/小時）的速率給到反應器內並 將氫以3 · 5毫磅/小時的速率給到反應器內。以約5 -8磅/小時的速率將氮氣給到反應器內作爲補充氣體。製 造速率爲約2 2磅/小時。反應器配備一通氣器，該通氣 器含有約150OPPH的循環氣流。（通氣器爲一裝置 ，用來在流化床氣相反應器中創造一無粒子區。參看美國 專利第5，69 3，72 了號）。在通氣器氣流中放置一 錐形觸媒注射噴嘴，該噴嘴的管口大小爲〇 · 〇 4 1英寸 (0·11釐米）。將1重量％觸媒A在甲苯中的溶液’ 與輔觸媒（MMAO — 3A，1重量％鋁在己烷中）線內 混合，再將其透過注射口注射入流化床中。Μ M A 0與觸 媒皆經控制以使鋁比鉻的莫耳比例爲4 5 0 : 1。視需要 也將氮與異戊院給入注射噴口中以保持穩定的平均粒徑。 獲得一單峰聚合物其具有標稱〇 · l〇dg/ml· η ( 1 2 !)及0 . 9 3 1克/立方釐米的屬性。依反應器質量 平衡基礎計算剩餘锆爲1 · 3 6 P P m w。 實施例節I V -實施例6 : 在溫度爲8 5 °C，反應器總壓力爲3 5 0 P s l g ( 2 · 4 m P a )的條件下，在1 4英寸（3 5 . 6潑米） 的領試工廠規模氣相反應器中製造乙烯-己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙烯以毎小時約4 0磅 (請先閱讀背面之注意事項寫本頁〕 t裝 寫太 訂. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -104 - 經濟部智慧財產局員工消費合作社印製 1245773 Λ7 B7 五、發明說明（102 ) I ]_ 8公斤/小時）的速率給到反應器内’己烯以每小時 約0.5磅（0.23公斤/小時）的速率給到反應器內 並將氫以約4毫磅/小時的速率給到反應器內。以約5 -8磅/小時的速率將氮氣給到反應器內作爲補充氣體。製 造速率爲約2 0磅/小時。反應器配備一通氣器，該通氣 器含有約2 0 5 0 P P Η的循環氣流。（通氣器爲一裝置 ，用來在流化床氣相反應器中創造一無粒子區。參看美國 專利第5，6 9 3，7 2 7號）。在通氣器氣流中放置一 錐形觸媒注射噴嘴，該噴嘴的管口大小爲〇 · 〇 4 1英寸 (〇.11釐米）。將1重量％觸媒Α在甲苯中的溶液與 輔觸媒（Μ Μ A〇一 3 A，4重量％鋁在異戊烷中）線內 混合，再將其透過注射口注射入流化床中。M iM A 0與觸 媒皆經控制以使鋁比鉻的莫耳比例爲1 5 5 0 : 1。視需 要也將氮與異戊烷給入注射噴口中以保持穩定的平均粒徑 。獲得一單峰聚合物其具有標稱〇 · 3 6 dg/m 1 η ( 1 2 ^ )及0 .. 9 4 3克/立方釐米的屬性。依反應器質量 平衡基礎計算剩餘锆爲2 · 5 P p m w。 實施例節I V -實施例7 : 在溫度爲8 5 °C，反應器總壓力爲3 5 0 P s 1 g ( 2 · 4 m P a )的條件下，在1 4英寸（3 5 · 6釐米） 的領試工廠規模氣相反應器中製造乙烯-己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙烯以每小時約4 0磅 (1 8公斤/小時）的速率給到反應器內’己烯以每小時 (請先闓讀背面之注意事項寫本頁) I!裝 寫士 訂： 本紙張尺度適用中國國家標準（CNS)A4規格（21〇χ 297公釐） -1〇5 - 1245773 A7 B7 五、發明說明O03 ) 約0.6磅（0.3公斤/小時）的速率給到反應器内並 將氫以約1 2毫磅/小時的速率給到反應器內。以約5〜 8磅/小時的速率將氮氣給到反應器內作爲補充氣體。製 造速率爲約2 0磅/小時。反應器配備一通氣器’該通氣 器含有約2 0 5 Ο P P Η的循環氣流。（通氣器爲一裝® ，用來在流化床氣相反應器中創造一無粒子區。參看美國. 專利第5，6 9 3，7 2 7號）。在通氣器氣流中放置〜 錐形觸媒注射噴嘴，該噴嘴的管口大小爲0 · 〇 4 1英寸 (〇.1 1釐米）。將1重量％觸媒Α在甲苯中的溶液與 輔觸媒（MMAO — 3A，4重量％鋁在異戊烷中）線內 混合，再將其透過注射口注射入流化床中。Μ Μ A 0與觸 媒皆經控制以使鋁比锆的莫耳比例爲8 6 8 : 1。.視需要 也將氮與異戊烷給入注射噴口中以保持穩定的平均粒徑。 獲得一單峰聚合物其具有標稱3.5dg/miη (121 )，〇♦ 1 1 5 d g / m i η ( I 2 ) ， I 2 ι / I 2 的比例 爲3 0 · 2和0 · 9 4 9克/立方釐米的屬性。依反應器 質量平衡基礎計算剩餘鉻爲2 · 5 p p m w。 實施例節I V -實施例8 乂 在溫度爲8 5 °C ’反應器總壓力爲3 5 0 P s l g ( 2 · 4mPa)的條件下’在14英寸（35 · 6鐘米） 的領試工廠規模氣相反應器中製造乙烯-己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙烯以每小時約4 0膀 (1 8公斤/小時）的速率給到反應器內’己嫌以每小時 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-106 - Γ請先閱讀背面之注意事項寫本頁) 丨裝 訂· 經濟部智慧財產局員工消費合作社印製 1245773 A7 B7 五、發明說明（104 ) (請先閱讀背面之注意事項！寫本頁) 約1 · 1磅的速率給到反應器內並將氫以1 2毫磅/小時 的速率給到反應器內。以約5 - 8磅/小時的速率將氮氣 給到反應器內作爲補充氣體。製造速率爲約2 5磅/小時 。反應器配備一通氣器，該通氣器含有約1 9 Ο Ο P PH 的循環氣流。（通氣器爲一裝置，用來在流化床氣相反應 器中創造一無粒子區。參看美國專利第 5，69 3，727號）。在通氣器氣流中放置一錐形觸 媒注射噴嘴，該噴嘴的管口大小爲0 . 0 4 1英寸（ 〇.11釐米）。將1重量％觸媒A在甲苯中的溶液與輔 觸媒（Μ Μ A〇一 3 A，4重量％鋁在異戊烷中）線內混 合，再將其透過注射口注射入流化床中。Μ Μ A 0與觸媒 皆經控制以使鋁比鉻的莫耳比例爲8 4 2 : 1。視需要也 將氮與異戊烷給入注射噴口中以保持穩定的平均粒徑。獲 得一單峰聚合物其具有標稱41 · 2dg/mi η ( 121 )，1 · 2 2 d g / m 1 η ( I 2 ) ，I 2 ι / I 的比例爲 33 · 8和Ο · 9 40克/立方釐米的屬性。依反應器質 量平衡基礎計算剩餘锆爲2 . 7 7 p p m w。 經濟部智慧財產局員工消費合作社印製 實施例節I V -實施例9 : 在溫度爲9 0 °C，反應器總壓力爲3 5 0 p s i g ( 2 · 4mPa)的條件下，在14英寸（35 · 6釐米） 的領試工廠規模氣相反應器中製造乙烯-己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙烯以每小時約4 8磅 的速率給到反應器內’己烯以每小時約〇 · 6磅（0 · 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-107- 1245773 __B7_____ 五、發明說明（105 ) 公斤/小時）的速率給到反應器内並將氫以約L 0毫磅/ 小時的速率給到反應器內。以約5〜8磅/小時的速率將 氮氣給到反應器內作爲補充氣體。製造速率爲約2 3磅/ 小時。反應器配備一通氣器’該通氣器含有約1 6 0 0 P P Η的循環氣流。（通氣器爲一裝置，用來在流化床氣 相反應器中創造一無粒子區。參看美國專利第5，6 9 3 ，7 2 7號）。在通氣器氣流中放置一錐形觸媒注射噴嘴 ，該噴嘴的管口大小爲0·055英寸（1·4釐米）。 將1 · 5重量％觸媒.Α在甲苯中的溶液與輔觸媒（ ““厶〇一3八，1.8重量％鋁在25%庚烷/75% 己烷溶液中）線內混合，再將其透過注射口注射入流化床 中。Μ Μ A〇與觸媒皆經控制以使鋁比锆的莫耳比例爲 2 6 5 : 1。視需要也將氮與異戊烷給入注射噴口中以保 持穩定的平均粒徑。獲得一單峰聚合物其具有標稱0 · 3 dg/m i n ( l2i)和0 · 9 3 3克/立方釐米的屬性 。依反應器質量平衡基礎計算剩胃余锆爲2 · 3 8 p p m w 〇 實施例節I V -實施例1 〇 : 一 在溫度爲9 5 °c，反應器總壓力爲3 5 0 p s 1 g ( 2 . 4 m P a )的條件下’在1 4英寸（3 5 · 6釐米） 的領試工廠規模氣相反應器中製造乙烯一己烯共聚物。該 反應器配有水冷卻型熱交換器。將乙嫌以每小時約4 5磅 的速率給到反應器內’己烯以每小時約0 · 6膀（〇 . 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）-108 - (請先閱讀背面之注意事項寫本頁〕 訂· 經濟部智慧財產局員工消費合作社印製 1245773 A7 ______B7_ 五、發明說明（106 ) 公斤/小時）的速率給到反應器内並將氫以約6毫睹/小 時的速率給到反應器內。以約5〜8磅/小時的速率將氮 氣給到反應器內作爲補充氣體。製造速率爲約2 5磅/小 時。反應器配備一通氣器，該通氣器含有約1 6〇〇 P P Η的循環氣流。（通氣器爲一裝置，用來在流化床氣 相反應器中創造一無粒子區。參看美國專利第 5，6 9 3，了 2 7號）。在通氣器氣流中放置一錐形觸 媒注射噴嘴，該噴嘴的管口大小爲0 · 0 5 5英寸（ 1 · 4釐米）。將1 · 5重量％觸媒Α在甲苯中的溶液與 輔觸媒（1^1^[六〇一3八，1.8重量％鋁在2 5%庚烷 / 7 5 %己烷溶液中）線內混合，再將其透過注射口注射 入流化床中。Μ Μ A〇與觸媒皆經控制以使鋁比鉻的莫耳 比例爲3 5 0 ·· 1。視需要也將氮與異戊烷給入注射噴口 中以保持穩定的平均粒徑。獲得一單峰聚合物其具有標稱 〇· 4dg/mi n ( I2i)和〇 · 934克/立方釐米 的屬性。依反應器質量平衡基礎計算剩餘鉻爲2 . 2 了 (請先閱讀背面之注意事項寫本頁) —裝 訂·V. Description of the invention) The polymerization system is equipped with an on-off mixer, an external water jacket for temperature control, a diaphragm inlet and an exhaust port, and a regulated supply port for dry nitrogen and acetylene. In a pressurized thermal reactor, it is carried out in the slurry phase. The reactor was dried and degassed at a temperature of 160 ° C. Isobutane (400 ml) was added as a diluent, 3.5 ml of 1-hexene and 0.7 ml of a 25% by weight trioctyl aluminum hexane solution was used as a scavenger in a tight syringe. The reactor was heated to 60 ° C. Under the pressure of ethylene, 0.10 g of the finished catalyst A was added, and then pressurized with 78 ps of ethylene (538 kPa). Polymerization was continued for 30 minutes, while the reactor temperature was maintained at 60 ° C, and was maintained at 7 8 P s i (5 3 8 k P a) with a fixed B-flow. The reaction was stopped by rapid cooling and release. 70.0 g of copolymer was obtained (flow index (F I) = no flow, active 2320 g polyethylene / mole catalyst · atmospheric pressure · hour, added 10.5 weight-hexene). The examples in the following Example IV are based on the use of a solution containing a Group 15 metal catalyst. Example Section IV The solution feed containing a Group 15 metal catalyst is prepared as described in Example Section I: [(2,4,6-M e 3 C 6 Η 2) NHCH a C Η 2]: (Ν Η Ligands or precursors—Compound I) and {[((2,4,6 — Μ e C β Η 2) Ν C Η 2 C 2 2] 2 · N Η} Z r * (C Η .2 Ρ ti) 2 (Compound I (please read the notes on the back to write this page first) __ Xia P · This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -98- 1245773 Λ7 B7 V. Description of the invention @ 6) Preparation of ΜΜΛ_U1 in the section of this window I) ------------ install --- (Please read the & intention on the back to write this page) (1 _ • 5_ in heavy toluene) Note = All procedures below are performed in a glove box. 1 · Weigh 1 g of purified toluene into a 1-liter conical flask. This conical flask is equipped with a ~ Teflon-coated stir bar. 2 · Join 7.28 grams of wanton? Base chromium. 3 • Place the solution on a stirrer and stir for 5 minutes. All solids are dissolved. 4. Add 5.42 grams of Compound I. 5. Add another 5 1 g of purified toluene and stir the mixture for 15 minutes. No solids remained in the solution. Line ”6 • Pour the catalyst solution into a clean, washed 1 liter Whitey sample cylinder, mark it, remove it from the glove box, and place it in the storage area for operation. Example Section IV—Example 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at a temperature of 85 ° C and a total reactor pressure of 350 P s 1 g (2.4 mPa) at 14 inches An ethylene-hexene copolymer was manufactured in a pilot plant-scale gas phase reactor (33.6 cm). The reactor was equipped with a water-cooled heat exchanger. Ethylene was fed into the reactor at a rate of about 40 pounds (18 kg / hour) per hour, and hexene was fed into the reactor at a rate of about 0.6 pounds (0.3 kg / hour) per hour and Hydrogen was fed into the reactor at a rate of 5 lb / hr. Applicable national standard (CNS) A4 specification (210 X 297 mm) -99-1245773 A7 B7 at a paper size of about 5-8 pounds. Nitrogen is fed into the reactor at a rate of (97) / hour. As a bribe inflatable body. The manufacturing rate is about 27 pounds per hour. The reactor is equipped with a ventilator 'which contains a circulating gas stream of about 190 〇 P P Η. (The aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor. See U.S. Patent Nos. 5,693,7 and 27.). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator, and the nozzle size of the nozzle was 0 · 0.41 inch (0.11 cm). A solution of 1% by weight of Catalyst A in toluene and a secondary catalyst (MMA 03-3 A, 1% by weight aluminum in hexane, (MMA 0 3A is a modified form of heptane in heptane) Aluminoxane can be obtained through commercial means from Akzo Chemical, Inc., and its trade name is Modified Methylalumoxane Type 3A, which is covered by US Patent No. 5,041,584. It was injected into the fluidized bed through the injection port. Μ A 〇 and the catalyst were controlled so that the molar ratio of aluminum to chromium was 400: 1. Nitrogen and isopentane were also injected into the injection if necessary. Nozzle to maintain a stable average particle size '. A unimodal polymer was obtained with properties of nominal 0.2 8 dg / m 1 η (I 2i) and 0.95 35 g / cm 3. Depending on the quality of the reactor The remaining zirconium was calculated to be 1.6 3 ppmw based on the balance. Example Section IV-Sinus Example 2: At a temperature of 8 5 ° C 'the total pressure of the reactor is 3 50 ps 1 g (2.4 m P ai) Under the conditions, an ethylene-hexene copolymer was manufactured in a pilot plant-scale gas phase reactor of 14 inches (35.6 feet). The reactor was equipped with a water-cooled heat exchanger. At the rate of about 40 pounds (18 kg / hour), hexene was fed into the reactor at an hourly rate (please read the note on the back to write this page). The member of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives printed this paper. Applicable to China National Standard (CNS) A4 specification (210x297 mm) -100-1245773 Λ7 B7 V. Description of the invention The rate of about 3 · 5 pounds (1.6 kg / hour) is given to the reactor and hydrogen is supplied at a rate of A rate of about 25 milli-pounds / hour was fed into the reactor. Nitrogen was fed into the reactor at a rate of about 5-8 bpm / hour, and as a make-up gas, the manufacturing rate was about 20 pounds / hour. The reactor was equipped with a ventilator, which contained a circulating gas flow of about 190 OPPH. (Aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor. See U.S. Patent No. 5,693,727). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator, and the nozzle size of the nozzle was 0. 041 inches (0.11 cm). A solution of 1% by weight of Catalyst A in toluene, 0.02PPH of 1-hexene, and a secondary catalyst (MMAO-3A, 4% by weight of aluminum in isopentane) were mixed in a line, and then passed through the injection port. Injected into a fluidized bed. Both M M A0 and the catalyst are controlled so that the molar ratio of aluminum to chromium is 7 4 6: 1. Nitrogen and isopentane were also fed into the injection nozzle as needed to maintain a stable average particle size. A unimodal polymer was obtained which had a nominal 1.2 dg / min (l2)? 29.7 dg / min (I 2 1) with a ratio of I 2 ^ / I 2 of 2 3.9 and 0.91 6 5 Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs print attributes in grams per cubic centimeter. The residual chromium calculated on the basis of the mass balance of the reactor was 0 · 89 ppmw. Example Section IV—Example 3 Scale of a pilot plant at 14 inches (35 · 6 light meters) at a temperature of 105 ° C 'total reactor pressure of 3 50 pslg (2 · 4mPa) An ethylene-hexene copolymer is produced in a gas phase reactor. The reactor was equipped with a water-cooled heat exchanger. Apply ethylene at about 40 paper per hour to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) -101-1245773 Λ7 B7 V. Description of the invention (? 9) f Please read the note on the back first Matters written on this page) were fed into the reactor at a rate of 18 pounds per hour, and hexene was fed into the reactor at a rate of about 0.6 pounds per hour (0.3 kg per hour) A rate of about 6 milli-pounds per hour was fed into the reactor. Nitrogen was fed into the reactor as a make-up gas at a rate of about 5 to 8 pounds per hour. The manufacturing rate is about 24 pounds per hour. The reactor was equipped with a ventilator which contained a circulating gas flow of about 16 00 p p H. (The aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor. See U.S. Patent No. 5,693,727). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator. The nozzle size was 0 ♦ 0 5 5 inches (0 · 14 cm). A 1.5% by weight solution of Catalyst A in toluene was mixed in-line with a secondary catalyst (^ 11 ^ 800.3 厶 '1.8% by weight of aluminum in a 25% heptane / 75% hexane solution). It is then injected into the fluidized bed through the injection port. Both M M A 0 and the catalyst are controlled so that the molar ratio of aluminum to zirconium is 3 2 0: 1. Nitrogen and isopentane were also injected as needed into the Indo-Slave spray nozzle of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to maintain a stable average particle size. A unimodal polymer was obtained which had properties of nominally 0.67 dg / min (l2i) 'and 0.9358 g / cm3. The residual chromium calculated on the basis of the reactor mass balance was 2 · 33 ppmw. Example Section IV-Example 4: at a temperature of 8 5 ° C 'with a total reactor pressure of 350 psig (2.4 mPa) at 14 inches. (3 5 · 6 splashes M) of a pilot plant-scale gas-phase reactor to manufacture ethylene-hexene copolymers. The reactor is equipped with a water-cooled heat exchanger. Ethylene is used at approximately 36 pounds per square meter. CNS) A4 specification (210 x 297 mm)-102-1245773 Λ7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The invention description (100 jin / hour) is given to the reactor, hexene Give the reactor about 3 hours at a rate of _ (1 ο · 〇 ^ ～ 〔1 · 6 kg / hour). Inside the reactor, and give hydrogen into the reactor at a rate of about 28 milli-pounds per hour. . At about 5 to 8 pounds per hour to win Si, give labor! S should, the device θ 乍, as the "%" body. The manufacturing rate is about 18 pounds per hour. The reactor is equipped A ventilator 'This ventilator contains a circulating gas stream of about χ 900 PP. (The ventilator is a device used to create a particle-free zone in a fluidized bed gas phase reactor. Lao Patent No. 5,693,727). A cone-shaped catalyst injection nozzle is placed in the air flow of the ventilator, and the nozzle size of the nozzle is 0. 〇4 1 inch (0.11 cm). 1% by weight Solution of Catalyst A in toluene, 0.2 2 p PH of 1 was mixed with auxiliary catalyst (MMA 03 A, 4% by weight of aluminum in isoprene), and then injected through injection Oral injection into the fluidized bed. MMA〇 and catalyst are controlled so that the molar ratio of aluminum to zirconium is 9 2 5: 1 ° If necessary, nitrogen and isopentane are also injected into the injection nozzle to maintain a stable Average particle size. A unimodal polymer was obtained with nominal 1.7 dg / min (12), 41. 7 dg / min (I 2 1), and a ratio of I 2 1 / I 2 of 2 4 · 1, and 〇 · 9 1 7 g / cm3. Calculate the remaining chromium as 0.9 4 ρ pmw based on the mass balance of the reactor. Example Section IV-Window Example 5: At a temperature of 8 5 ° C, the total pressure of the reactor Ethylene-hexene copolymer was manufactured in a pilot plant-scale gas phase reactor at 14 inches (3 5 · 6 light meters) under conditions of 350 psig (2.4 mPa). 1- - ---------- · — (Please read the notes on the back to write this page first) Order 丨 The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) -103- 1245773 Λ7 _ B7_____ 5. Description of the invention 0〇1) The reactor is equipped with a water-cooled heat exchanger. Ethylene was fed into the reactor at a rate of about 0 kg (18 kg / hour) per hour, and hexene was fed into the reactor at a rate of about 0.6 pounds (0.3 kg / hour) per hour and Hydrogen was fed into the reactor at a rate of 3.5 millilbs per hour. Nitrogen was fed into the reactor as a make-up gas at a rate of about 5-8 pounds per hour. The manufacturing rate is about 22 lbs / hour. The reactor was equipped with an aerator containing a circulating gas stream of about 150 OPPH. (Aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor. See U.S. Patent No. 5,69 3,72). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator, and the nozzle size of the nozzle was 0. 401 1 inch (0.11 cm). A solution of 1% by weight of catalyst A in toluene was mixed with an auxiliary catalyst (MMAO-3A, 1% by weight of aluminum in hexane) and injected into a fluidized bed through an injection port. Both MM A 0 and the catalyst are controlled so that the molar ratio of aluminum to chromium is 4 50: 1. If necessary, nitrogen and isoprene were also injected into the injection nozzle to maintain a stable average particle size. A unimodal polymer was obtained which had properties of nominally 0.1 dg / ml · η (12!) And 0.931 g / cm 3. The remaining zirconium was calculated as 1 · 3 6 P P m w on the basis of reactor mass balance. Example Section IV-Example 6: Under conditions of a temperature of 85 ° C and a total reactor pressure of 350 P slg (2.4 mPa), at 14 inches (35.6 pounces) ) To produce ethylene-hexene copolymers in pilot plant-scale gas phase reactors. The reactor was equipped with a water-cooled heat exchanger. Ethylene is about 40 pounds per hour (please read the note on the back to write this page) t is too prescriptive. The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese national standard (CNS) A4 specification ( 210 X 297 mm) -104-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1274573 Λ7 B7 V. Description of the invention (102) I] _ 8 kg / hour) is given to the reactor 'hexene at an hour A rate of about 0.5 pounds (0.23 kg / hour) was fed into the reactor and hydrogen was fed into the reactor at a rate of about 4 milli pounds / hour. Nitrogen was fed into the reactor as a make-up gas at a rate of about 5-8 pounds per hour. The manufacturing rate is about 20 pounds per hour. The reactor was equipped with a ventilator, which contained a circulating gas flow of about 2 0 50 P P Η. (Aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor. See U.S. Patent Nos. 5,6 9 3, 7 2 7). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator, and the nozzle size of the nozzle was 0. 041 1 inch (0.11 cm). A solution of 1% by weight of Catalyst A in toluene was mixed with an auxiliary catalyst (MM A03-3 A, 4% by weight of aluminum in isopentane), and then injected into a fluidized bed through an injection port. in. M iM A 0 and the catalyst are controlled so that the molar ratio of aluminum to chromium is 155 0: 1. If necessary, nitrogen and isopentane are also fed into the injection nozzle to maintain a stable average particle size. A unimodal polymer was obtained which had properties of nominally 0.36 dg / m 1 η (1 2 ^) and 0. .93 g / cm 3. The remaining zirconium was calculated based on the mass balance of the reactor to be 2 · 5 P p m w. Example Section IV-Example 7: At a temperature of 8 5 ° C and a total reactor pressure of 3 50 P s 1 g (2 · 4 m P a), at 14 inches (3 5 · 6 Cm) of a pilot plant-scale gas phase reactor to manufacture ethylene-hexene copolymers. The reactor was equipped with a water-cooled heat exchanger. Feed ethylene into the reactor at a rate of about 40 pounds per hour (18 kg / hour). Hexene per hour (please read the precautions on the back to write this page) I! The paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm)-105-1245773 A7 B7 V. Description of the invention O03) The rate of about 0.6 pounds (0.3 kg / hour) is fed into the reactor and Hydrogen was fed into the reactor at a rate of about 12 millilbs / hour. Nitrogen was fed into the reactor as a make-up gas at a rate of about 5 to 8 pounds per hour. The manufacturing rate is about 20 pounds per hour. The reactor is equipped with a ventilator 'which contains a circulating gas flow of about 2 0 5 0 P P Η. (The aerator is a pack of ® used to create a particle-free zone in a fluidized bed gas phase reactor. See U.S. Patent No. 5,6 9 3, 7 2 7). Place a ~ cone catalyst injection nozzle in the air flow of the ventilator with a nozzle size of 0 · 〇 4 1 inch (0.1 1 cm). A solution of 1% by weight of Catalyst A in toluene was mixed with an auxiliary catalyst (MMAO-3A, 4% by weight of aluminum in isopentane), and then injected into the fluidized bed through an injection port. Both M M 0 and the catalyst are controlled so that the molar ratio of aluminum to zirconium is 868: 1. If necessary, nitrogen and isopentane are also fed into the injection nozzle to maintain a stable average particle size. A unimodal polymer was obtained which had a nominal 3.5 dg / miη (121), 〇 1 1 5 dg / mi η (I 2), and the ratio of I 2 ι / I 2 was 3 0 · 2 and 0 · 9 4 9 g / cm3 property. The residual chromium calculated on the basis of the reactor's mass balance was 2 · 5 p p m w. Example Section IV-Example 8 乂 At a temperature of 8 5 ° C 'with a total reactor pressure of 3 50 P slg (2 · 4 mPa)' at a pilot plant of 14 inches (35 · 6 m) Production of an ethylene-hexene copolymer in a large-scale gas phase reactor. The reactor was equipped with a water-cooled heat exchanger. Ethylene is fed into the reactor at a rate of about 40 bph (18 kg / hr) per hour. 'It has been suspected that the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -210 is applied at the paper size per hour. -Γ Please read the precautions on the back and write this page first) 丨 Binding · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1245773 A7 B7 V. Invention Description (104) (Please read the precautions on the back first! Write this page) A rate of 1.1 pounds was fed into the reactor and hydrogen was fed into the reactor at a rate of 12 milli-pounds per hour. Nitrogen was fed into the reactor as a make-up gas at a rate of about 5-8 pounds per hour. The manufacturing rate is about 25 pounds per hour. The reactor was equipped with a ventilator, which contained a circulating gas stream of approximately 19 OO P PH. (Aerator is a device used to create a particle-free zone in a fluidized bed gas phase reactor. See U.S. Patent No. 5,69 3,727). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator, and the nozzle size of the nozzle was 0.041 inches (0.11 cm). A solution of 1% by weight of Catalyst A in toluene was mixed with an auxiliary catalyst (MM A03-3 A, 4% by weight of aluminum in isopentane), and then injected into a fluidized bed through an injection port. in. Both M M A 0 and the catalyst are controlled so that the molar ratio of aluminum to chromium is 8 4 2: 1. If necessary, nitrogen and isopentane were also fed into the injection nozzle to maintain a stable average particle size. A unimodal polymer was obtained which had a nominal 41 · 2dg / mi η (121), 1 · 2 2 dg / m 1 η (I 2) and the ratio of I 2 ι / I was 33 · 8 and 0 · 9 40 G / cm3 properties. The remaining zirconium was calculated to be 2.77 p p m w based on the mass balance of the reactor. Printed in Section IV-Example 9 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Example 9: at a temperature of 90 ° C and a total reactor pressure of 350 psig (2.4 mPa) at 14 inches (35 · 6 cm) pilot-scale plant-scale gas phase reactor for ethylene-hexene copolymer production. The reactor was equipped with a water-cooled heat exchanger. Ethylene was fed into the reactor at a rate of about 48 pounds per hour. Hexene was about 0.6 pounds per hour (0.3) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -107- 1245773 __B7_____ V. Description of the invention (105 kg / hour) is given to the reactor and hydrogen is given into the reactor at a rate of about 0 milli-pounds per hour. Nitrogen was fed into the reactor at a rate of about 5 to 8 pounds per hour as make-up gas. The manufacturing rate is about 23 pounds per hour. The reactor is equipped with a ventilator 'which contains a circulating gas flow of about 16 0 P P Η. (Aerator is a device used to create a particle-free zone in a fluidized bed gas reactor. See U.S. Patent Nos. 5,693,7 and 27.). A cone-shaped catalyst injection nozzle was placed in the air flow of the ventilator, and the nozzle size was 0.055 inches (1.4 cm). A 1.5% by weight catalyst.A solution in toluene was mixed in-line with a cocatalyst ("" 0.38, 1.8% by weight aluminum in a 25% heptane / 75% hexane solution), and then It is injected into the fluidized bed through the injection port. Both M M A0 and the catalyst are controlled so that the molar ratio of aluminum to zirconium is 2 65: 1. If necessary, nitrogen and isopentane were also fed into the injection nozzle to maintain a stable average particle size. A unimodal polymer was obtained which had properties of nominally 0.3 dg / min (12i) and 0.93 g / cm3. Based on the basis of the reactor mass balance, the residual gastric zirconium was calculated to be 2.38 ppmw. Example IV-Example 1 〇: at a temperature of 9 5 ° c, the total reactor pressure is 3 50 ps 1 g (2 4 m P a) under conditions of 1 4 inches (3 5 · 6 cm) in a pilot plant-scale gas phase reactor to produce ethylene-hexene copolymers. The reactor was equipped with a water-cooled heat exchanger. Feed Hexene into the reactor at a rate of about 45 pounds per hour. Hexene is about 0.66 per hour (0.3 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297) ) -108-(Please read the precautions on the back to write this page first) Order · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed on 1245773 A7 ______B7_ V. The rate of invention (106) kg / h is given to the reactor and Hydrogen was fed into the reactor at a rate of about 6 milliseconds per hour. Nitrogen was fed into the reactor as a make-up gas at a rate of about 5 to 8 pounds per hour. The manufacturing rate was about 25 pounds per hour. The reactor Equipped with a ventilator, which contains a circulating gas stream of about 16,000 PPΗ. (The ventilator is a device used to create a particle-free zone in a fluidized bed gas phase reactor. See US Patent No. 5, 6 9 3, No. 2 7). A cone-shaped catalyst injection nozzle is placed in the air flow of the ventilator, and the nozzle size is 0 · 0 5 5 inches (1 · 4 cm). Solution of Catalyst A in toluene and cocatalyst (1 ^ 1 ^ [6038, 1.8% by weight of aluminum 2 5% heptane / 75% hexane solution) mixed in-line, and then injected into the fluidized bed through the injection port. Μ A〇 and catalyst are controlled so that the molar ratio of aluminum to chromium Is 3 5 0 · 1. 1. If necessary, nitrogen and isopentane are also fed into the injection nozzle to maintain a stable average particle diameter. A unimodal polymer is obtained which has a nominal value of 0.4 dg / min (I2i) and 〇 · 934g / cm3 attribute. Calculate the remaining chromium as 2.2 based on the mass balance of the reactor (please read the precautions on the back first to write this page) —binding ·

P 經濟部智慧財產局員工消費合作社印製 中 V I 節 。 例 W施 m 實 例 施 表 於 列 皆 據 數 得 所 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -109 - 1245773 Λ7 五、發明說明（107 ) 表I ί 實施例 溫度°。 H2/C2 C6/C2 12 dg/min 121 dg/min 密度 克/立方厘 米 殘餘Zr ppmw 1 85 0.0015 0.0043 N/a 0.28 0.935 1.63 2 85 0.008 0.0410 1.2 29.7 0.9165 0.89 3 105 0.0015 0,0050 N/a 0.67 0.9358 η οο Z.JJ 4 85 0.0087 0.0405 1.7 41.7 0.917 0.94 5 85 0.0006 0.0051 N/a 0.1 0.931 1.36 6 85 0.0023 0.0012 N/a 0.36 0.943 2.50 7 85 0.0051 0.0013 0.115 3.5 0.949 2.50 . 8 85 0.014 0,0154 1.22 41.2 0.940 2.77 9 90 0.0015 0.0050 N/a 0.3 0.933 2.38 10 95 0.0015 0.0050 N/a 0.4 0.934 2.27 (請先閱讀背面之注意事項1|1^寫本頁) 裝 •線 眚施例節I V -實施例J 1 : 經濟部智慧財產局員工消費合作社印製 依據上面實施例4製造的3 0 0磅（1 3 8公斤）的 聚乙烯（稱爲聚合物A )在Werner-F丨eiderer ZSK-30雙螺 桿擠壓機上與 1000ppmIrganoxTM 1076 和 1500ppm 1巧&丨'〇3^ 1 068於溶融溫度2 0 0°(：混練形成九粒。接著在一 Gloucester吹膜擠壓線上，速度爲1 8 8磅/小時（8 5公 斤/小時），熔融溫度爲3 9 0 T ( 1 9 9 °C ) ，2 4英 寸（6 1趨米）的霜線高度，2 · 5吹爆比和6 0密爾（ 1 5 2 4微米）模縫，將九粒吹塑成1 . 0密附（2 5微 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐）.11〇 . 1245773 Λ： _Β7_ 五、發明說明Ο08 ) 米）的膜，在同等條ί牛下操阼ESC〇RENE「MHD7755. 10 ι Ex :(ο n C he m 1 c a 1 Co mpany，M t · Be 1'/ ue，Te xas 的一種 ί專統系列 反應器產品）作爲對比。所有膜接經調理到2 3 t，5〇 %濕度40小時。其數據皆列在表I I I和IV中3 -------------.---裝--- (請先閱讀背面之：^意事項寫本百二 訂· -線. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） -111 - A7 1245773 __ β7 五、發明說明Ο09 ) 經濟部智慧財產局員工消費合作社印製 表[[[ π ΓΜ Escorene 聚合物A ： Escorene™ _: LL3002.32 1.8克/10分 MI : LL3001.63 b^/10^ _： 1076 1 Ιΐί/L·____； 29 24 27 丸粒密度克/立方釐米 0.918 0.918 0.918 模頭壓力psi/ ( mPa ) 2690 ( 19) 2470 ( 17) 3380 (23) 發動機負荷，％ 43 31.2 50.4 膜規格（密爾）（微米） 1 (25) 1 (25) 1 (25) 膜密度，克/立方釐米 0.917 0.916 0.917 26吋（66公分）落錘抗衝擊強度，克 136 168 149 Elmendorf抗撕強度，克/密爾（克/微 米）MD 310 (12.7) 254 ( 10.4) 223 (9.1) Elmendorf抗撕強度，克/密爾（克/微 米）TD 609 (24.9) 630 (25.7) 753 (30.7) 1%正割模數psi ( MPa ) MD 30430 (210) 31580 (218) 31320 (216) 1%正割模數psi ( MPa ) TD 38950 (269) 42120 (290) 39750 (274) 極限抗張強度psi ( Mpa ) MD 7444 (51 ) 8551 (59) 8880 (61 ) 極限抗張強度psi ( Mpa ) TD 6498 (45) 9892 (68) 6894 (48) 極限伸長率％&03 641 546 552 極限伸長率％了0 793 694 756 45°光澤度 40 79 23 濁度％ 22 4.4 20 (請先閱讀背面之注意事項寫本頁〕 !裝 . 本紙張尺度適用中國國家標準（CNs〉A4規格（210 x 297公釐）-112 - 1245773 A7 B7 五、發明說明（110 ) 表[V 經濟部智慧財產局員工消費合作社印製 聚合物A EXCEED™ 實施例 1.3 MI ： 350D60 I:，克/1 〇分 1.35 1 I 2 1 / I ： ‘ 23 16 九粒密度克/立方釐米 3.918 3.9 18 模頭壓力P S1 / (m P a) : 3010(21) ： 3810(26) 發動機負荷，％ 37.2 56.7 膜規格（密爾）（微米） 1(25) 1(25) 膜密度，克/立方釐米 0.916 0.916 26吋（66公分）落錘抗衝擊強度， 克 276 646 Elmendorf抗撕強度，克/密爾（ 克/微米）MD 219? 264? Elmendorf抗撕強度，克/密爾（ 克/微米）TD 616? 392? 1%正割模數psi(MPa)MD 31100(214) 29040(200) 1%正割模數psi(MPa)TD 41470(286) 33050(228) 極限抗張強度psi(Mpa)MD 9017(62) 9986(69) 極限抗張強度psi(Mpa)TD 7684(53) 8535(59) 極限伸長率％ M D 529 504 極限伸長率％TD 690 646 45°光澤度 74 25 濁度％ 5 2 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐）-113 - (請先閱讀背面之注意事項AW寫本頁) 1245773 A7 B7 五、發明說明) 下列實施例V節的實施例係使用一混合觸媒系統的溶 液進料，其包括一含第1 5族金屬觸媒和一龐大配泣子茂 合金屬觸媒。 實施例節V ·甸栝一含第1 5族_金屬觸媒和一龐大配位j 茂合金屬觸媒的混合觸媒系統溶液進料 觸媒1 爲了此實施例節V，觸媒1爲茚基鉻三特戊酸鹽，一 龐大配位子茂合金屬型化合物，由實施例節I中所述製備 者。 觸媒1的製備- 1重量％的己烷中溶液 所有步驟都是在手套箱內操作的。 2 ·將一升的純化己烷倒入配有聚四氟乙烯塗層攪拌 棒的1 L錐形燒瓶中。 5 ·加入6 · 6 7克印锆三特戊酸鹽乾粉。 經濟部智慧財產局員工消費合作社印製 6 ·把溶液放入磁化攪拌器上攪拌1 5分鐘。所有固 體都溶解在溶液中。 把溶液倒入一淸潔經沖滌的1 一升 Whitey樣品鋼瓶 ，貼上標簽，移出手套箱，放置於存儲處直到要使用。 觸媒2 爲了這實施例節V，依實施例節[中所述製備觸媒2 本紙張尺度適用中國國家標準（CNS〉A4規格（210 X 297公釐） -114 - 1245773 Λ7 ___B7__ 五、發明說明Ο 1 2 ) r ( 9，4，6 — M e :! C H ： ) NRCHiCH：}： N H配位子（配位子1 )和丨（2 ’ 4 ’ 6 — M e 3 C 6 Η 2 ) N H C: Η 2 C Η 2 丨 2 N H 丨 Ζ r (CH2Ph)2(化合物 ί)。 觸媒2之製備一 1 . 5重量％的甲苯中溶液 注意··下列所有步驟都是在手套箱內操作的。 8 .稱1 〇 〇克的純化甲苯加到配有聚四氟乙烯塗層 攪拌棒的1升錐形燒瓶中。 9 .加入7 · 28克的四苄锆。 1〇·把溶液放在攪動器上攪拌5分鐘。所有固體都 溶解在溶液中。 1 1 .加入5 · 4 2克的配位子I 。 1 2 .加入另一份5 5 1克的純化甲苯，將混合物攪 拌1 5分鐘。溶液中沒有固體殘留。 1 3 .把觸媒溶液倒入一淸潔經沖滌的1 一升Whitey 樣品鋼瓶內，貼上標簽，移出手套箱，放置於存儲處直到 經濟部智慧財產局員工消費合作社印製 作 操 要 例 施 實 I V 節 例 施 實 爲 度 溫 在 S P 〇 5 3 爲 力 壓 總 器 應 反 在 下 件 寸 英 物器 聚氣 共 ΰ -^、、J 烯 I 己· 一 配 烯器 乙應 造反 製。 中器 器換 應交 反熱 條相型 的氣卻 } 模冷 a 規水 P 廠有 mH 配 4 試器 . 領應 2 的反 5 米 釐 該該 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -11 5 1245773 A7 B7 五、發明說明013 ) 通氣器具有約1 6 Ο Ο p p Η的循環氣流.（通®器爲--裝置，用來在流化床氣相反應器中創造一無粒子區。參看 美國專利第5 ，6 9 3 ’ 7 2 7號）。在通氣器氣流中放 置一錐形觸媒注射噴嘴’該噴嘴的管口大小爲〇 · 〇 5 5 英寸（1 · 4釐米）。在觸媒塡料前，乙烯的壓力爲約 2 2〇P s i g ( 1 · 5 M p a ) ，]_ —己院濃度爲約 〇.3莫耳％，氫的濃度爲約〇.12莫耳％。 將觸媒2溶解成〇 · 5重量％的甲苯溶液’然後以 1 2立方釐米/小時的速度給入反應器。將M M A 0 - 3 A，1重量％鋁）輔觸媒以4 Ο Ο : 1的鋁/鉻莫耳比 和觸媒2在反應器前的給料線中混合。產率爲約2 4磅/ 小時（1 0 . 9公斤/小時）。此外，也將氮以5 · 0磅 /小時（2 · 3公斤/小時），1 一己烷以Ο · 1磅/小 時（0 · 0 5公斤/小時），和異戊烷以0 · 2磅/小時 (〇· 0 9公斤/小時）的速度給入注射噴口。聚合物的 流動指數爲〇 · 3 1 ’密度爲0 · 9 3 5克/立方釐米。 達到此之後，把觸媒2的觸媒進料速率減少到6立方釐米 /小時並將Ο · 1 2 5重量％觸媒1己烷溶液進料以1 3 立方釐米/小時的速率加入注射線。整個添加次序爲己烯 ，與混合觸媒1的M M A〇、觸媒2溶液，然後異戊烷和 氮。整個系統中錯/锆比爲約5 Ο Ο ϋ在加入觸媒1的6 小時內，該雙峰型聚合物有標稱的1 2 · 9 dg/m l η (I 2 L ) ，1 3 Ο M F R (溶融流 _ 比 I 2 ι / I 2 )和 〇· 9 5 3克/立方M米的密度。樹脂的平均拉徑g 本紙張尺度適用中國國家標準（CNS)A4蜆格（210 X 297公釐） -116 - -----r---· —I (請先I之注意事項 寫本ί . -線 經濟部智慧財產局員工消費合作社印製 1245773 Λ7 _— B7 _ 五、發明說明（114 ) 〇.0479英寸CO · 12趦米）。X射線螢光测Μ出 〇· 7 p p m w的剩餘i告。 本文所述的所有文件都倂於本文作爲參考，包括圧何 先前文件及/或測試程序。如同從前面槪括說明和特殊具 體實施例所明瞭者’雖然本發明種種形式都已闡述過，但 是對其可以做出各種修改而不違離本發明旨意和範圍。正 是在本發明範圍內使用兩種或多種含第1 5族金屬化合物 與一或多種龐大配位子茂合金屬觸媒系統及/或一或多種 傳統型觸媒系統。因此’本發明無意受彼等所限制。 (請先閱讀背面之注意事項寫本頁) 裝 明 說 略 簡 的 式 圖 經濟部智慧財產局員工消費合作社印製 圖圖圖圖圖圖圖圖圖 2 5 6 7 8 9 例例例例例例例例例 述述述述述述述述述 闡闉闉闡闡闡闡闡闡 的的的的的的的的的 面面面面面面面面面 下下下下下下下下下 是是是是是是是是是 明明明明明明明明明 說說說說說說說說說 解解解解解解解解解 圖圖圖圖圖圖圖圖圖 的的的的的的的的的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -117-P Printed in Section VI of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Example W.m. Example. Tables are listed in the table. The paper dimensions are applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -109-1245773 Λ7 V. Description of the invention (107) Table I ί Example Temperature °. H2 / C2 C6 / C2 12 dg / min 121 dg / min Density g / cm3 Residual Zr ppmw 1 85 0.0015 0.0043 N / a 0.28 0.935 1.63 2 85 0.008 0.0410 1.2 29.7 0.9165 0.89 3 105 0.0015 0,0050 N / a 0.67 0.9358 η οο Z.JJ 4 85 0.0087 0.0405 1.7 41.7 0.917 0.94 5 85 0.0006 0.0051 N / a 0.1 0.931 1.36 6 85 0.0023 0.0012 N / a 0.36 0.943 2.50 7 85 0.0051 0.0013 0.115 3.5 0.949 2.50. 8 85 0.014 0,0154 1.22 41.2 0.940 2.77 9 90 0.0015 0.0050 N / a 0.3 0.933 2.38 10 95 0.0015 0.0050 N / a 0.4 0.934 2.27 (Please read the precautions on the back 1 | 1 ^ write this page first) J 1: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 300 lbs (138 kg) of polyethylene (referred to as Polymer A) manufactured in accordance with Example 4 above. Werner-F 丨 eiderer ZSK-30 double The screw extruder was mixed with 1000ppm IrganoxTM 1076 and 1500ppm 1 & 丨 ′ 〇3 ^ 1 068 at a melting temperature of 200 ° (: kneaded to form nine pellets. Then on a Gloucester blown film extrusion line, the speed was 1 8 8 Pounds per hour (85 kg / h) with a melting temperature of 3 9 0 T (1 9 9 ° C), frost line height of 24 inches (61 mils), blow-out ratio of 2.5 and 60 mils (152 5 microns) die seam, blown nine pellets into 1.0 dense adhesion (2 5 micro-paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm). 11〇. 1245773 Λ: _Β7_ V. Description of the Invention 〇08) m), operate under the same conditions ESC〇RENE "MHD7755. 10 ι Ex: (ο n C he m 1 ca 1 Co mpany, M t · Be 1 '/ ue, Te xas a kind of special series reactor products) as a comparison. All membrane junction Condition to 2 3 t, 50% humidity for 40 hours. The data are listed in Tables III and IV. 3 -------------. --- --- --- (Please read the back: ^ Italian matter to write this one hundred and two orders--line. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 x 297 mm) -111-A7 1245773 __ β7 V. Description of the Invention 〇09 Printed sheet [[[π ΓΜ Escorene Polymer A: Escorene ™ _: LL3002.32 1.8 g / 10 minutes MI: LL3001.63 b ^ / 10 ^ _: 1076 1 Ιΐί / L · ____; 29 24 27 pills Density g / cm3 0.918 0.918 0.918 Die pressure psi / (mPa) 2690 (19) 2470 (17) 3380 (23) Engine load,% 43 31.2 50.4 Membrane size (mil) (microns) 1 (25) 1 ( 25) 1 (25) Film density, g / cm 0.917 0.916 0.917 26 inch (66 cm) drop weight impact strength, g 136 168 149 Elmendorf tear strength, g / mil (g / micron) MD 310 (12.7 ) 254 (10.4) 223 (9.1) Elmendorf tear strength, g / mil (g / micron) TD 609 (24.9) 630 (25.7) 753 (30.7) 1% secant modulus psi (MPa) MD 30430 (210) 31580 (218) 31320 (216) 1% secant modulus psi (MPa) TD 38950 (269) 42120 (290) 39750 (274) Ultimate tensile strength psi (Mpa) MD 7444 (51) 8551 (59) 8880 (61) Ultimate tensile strength psi (Mpa) TD 6498 (45) 9892 (68) 6894 (48) Ultimate elongation% & 03 641 546 552 Ultimate elongation% 0 793 694 756 45 ° Gloss 40 79 23 Haze% 22 4.4 20 (Please read the notes on the back to write this page first!)! Packing. This paper size applies to Chinese national standards (CNs> A4 size (210 x 297 mm) -112 -1245773 A7 B7 V. Description of the invention (110) Table [V Printed polymer A EXCEED ™ by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Example 1.3 MI: 350D60 I :, g / 10 min 1.35 1 I 2 1 / I : '23 16 Nine grain density g / cm3 3.918 3.9 18 Die pressure P S1 / (m P a): 3010 (21): 3810 (26) Engine load,% 37.2 56.7 Membrane size (mil) (micron) 1 (25) 1 (25) Membrane density, g / cm 0.916 0.916 26 inch (66 cm) drop weight impact strength, 276 646 Elmendorf resistance Strength, g / mil (g / micron) MD 219? 264? Elmendorf tear strength, g / mil (g / micron) TD 616? 392? 1% secant modulus psi (MPa) MD 31100 (214) 29040 (200) 1% secant modulus psi (MPa) TD 41470 (286) 33050 (228) Ultimate tensile strength psi (Mpa) MD 9017 (62) 9986 (69) Ultimate tensile strength psi (Mpa) TD 7684 (53) 8535 (59) Ultimate elongation% MD 529 504 Ultimate elongation% TD 690 646 45 ° gloss 74 25 Haze% 5 2 3 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Centi) -113-(Please read the note on the back AW first to write this page) 1245773 A7 B7 V. Description of the invention) The following examples in section V use a mixed catalyst system solution feed, which includes a Group 1 5 metal catalysts and a large metal wetting metal catalyst. Example Section V—A mixed catalyst system solution containing Group 1_5 metal catalyst and a large coordination j metallocene catalyst is used to feed catalyst 1 For Section V of this embodiment, catalyst 1 is Indenyl chromium trivalerate, a bulky ligand metallocene compound, was prepared as described in Example Section I. Preparation of Catalyst 1-1% by weight solution in hexane All steps were performed in a glove box. 2. Pour one liter of purified hexane into a 1 L Erlenmeyer flask equipped with a Teflon-coated stir bar. 5. Add 6.67 grams of zirconium trivalerate dry powder. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 · Put the solution on a magnetic stirrer for 15 minutes. All solids are dissolved in the solution. Pour the solution into a 1 liter Whitey sample steel bottle cleaned and rinsed, label it, remove it from the glove box, and place it in storage until use. Catalyst 2 For the purpose of Section V of this example, the Catalyst 2 was prepared as described in the section [The paper size is applicable to the Chinese national standard (CNS> A4 specification (210 X 297 mm) -114-1245773 Λ7 ___B7__ V. Invention Explanation Ο 1 2) r (9, 4, 6 — M e:! CH:) NRCHiCH:}: NH ligand (ligand 1) and 丨 (2 '4' 6 — M e 3 C 6 Η 2 ) NHC: Η 2 C Η 2 丨 2 NH 丨 Zr (CH2Ph) 2 (compound ί). Preparation of Catalyst 2-1.5% by weight solution in toluene Note: · All the following steps are performed in a glove box. 8. Weigh 1000 grams of purified toluene into a 1 liter Erlenmeyer flask equipped with a Teflon-coated stir bar. 9. Add 7.28 grams of tetrabenzyl zirconium. 10. Put the solution on a stirrer and stir for 5 minutes. All solids were dissolved in the solution. 1 1. Add 5.42 grams of ligand I. 1 2. Add another 5 1 1 g portion of purified toluene and stir the mixture for 15 minutes. No solids remained in the solution. 1 3. Pour the catalyst solution into a 1 liter Whitey sample cylinder cleaned by Jie Jingjing, label it, remove it from the glove box, and place it in the storage place until printed by the Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs. The implementation of Section IV shows that the temperature and temperature are at SP 〇 3 and the total pressure should be reversed. In the next step, the pressure of the collector should be reduced. ^ ,, Jene I, Hexylene, B, and B should be counteracted. The middle device is replaced with an anti-heating strip-type gas module.} Mold cooling a gauge water P factory has mH with 4 testers. The response of 2 is 5 meters. The paper size is applicable to China National Standard (CNS) A4. Specifications (210 X 297 mm) -11 5 1245773 A7 B7 V. Description of the invention 013) The aerator has a circulating air flow of about 16 〇 0 pp Η. (The aerator is a device that is used to A particle-free zone is created in the reactor. See US Patent No. 5, 6 3 '7 2 7). A cone-shaped catalyst injection nozzle is placed in the air flow of the ventilator. The nozzle has a nozzle size of 0.55 inches (1.4 cm). Before the catalyst was charged, the pressure of ethylene was about 220 sig (1.5 M pa), and the concentration of hydrogen in the courtyard was about 0.3 mol%, and the concentration of hydrogen was about 0.12 mol. %. Catalyst 2 was dissolved into a 0.5% by weight toluene solution 'and then fed to the reactor at a rate of 12 cm3 / hour. M M A 0-3 A, 1% by weight of aluminum) auxiliary catalyst was mixed at an aluminum / chromium molar ratio of 4 OO: 1 and catalyst 2 in a feed line in front of the reactor. The yield is about 24 lbs / hour (10.9 kg / hour). In addition, nitrogen was used at 5.0 pounds / hour (2.3 kg / hour), 1 hexane at 0. 1 pounds per hour (0.5 kg / hour), and isopentane at 0.2 pounds Into the injection nozzle at a rate of 0.9 kg / hour. The polymer had a flow index of 0.31 'and a density of 0.935 g / cm3. After this is achieved, reduce the catalyst feed rate for Catalyst 2 to 6 cm3 / hr and feed 0. 12 5 wt% catalyst 1 in hexane solution to the injection line at a rate of 13 cm3 / hr. . The entire order of addition is hexene, mixed with M M A0 of catalyst 1, catalyst 2 solution, then isopentane and nitrogen. The ratio of zirconium / zirconium in the whole system is about 5 〇 〇 ϋ Within 6 hours after adding catalyst 1, the bimodal polymer has a nominal 1 2 · 9 dg / ml η (I 2 L), 1 3 〇 MFR (melt flow_ ratio I 2 ι / I 2) and a density of 0.953 g / m3. The average diameter of the resin g This paper size is applicable to the Chinese National Standard (CNS) A4 grid (210 X 297 mm) -116------ r --- · —I .-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1245773 Λ7 _ — B7 _ V. Description of the invention (114) 0.0479 inch CO · 12 趦 m). X-ray fluorescence measurement showed 0.7 p p m w remaining. All documents described in this document are incorporated herein by reference, including any previous documents and / or test procedures. As is clear from the foregoing description and specific embodiments, although various forms of the invention have been described, various modifications can be made thereto without departing from the spirit and scope of the invention. It is within the scope of the present invention to use two or more Group 15 metal compounds and one or more bulky ligand-metallocene catalyst systems and / or one or more conventional catalyst systems. Therefore, the present invention is not intended to be limited by them. (Please read the notes on the back first to write this page) Printed diagrams Simplified illustrations Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives Printed diagrams Diagrams Diagrams Diagrams Diagrams Diagrams 2 5 6 7 8 9 Examples Examples Examples The example is the description of the description of the description of the explanation of the explanation of the explanation of the YES YES YES YES YES TALK TALK TALK TALK TALK TALK TALK TALK TALKING Applicable to China National Standard (CNS) A4 (210 X 297 mm) -117-

Claims (1)

-——— 年月日修(更)正本 94 ft 8 — —· A8 B8 C8 D8 六、申請專利範圍 附件4A条891〇9281號專利申請案 中文申請專利範圍替換本 民國94年8月8日修正 1 · 一種觸媒組成物，其包含一含第1 5族金屬觸媒 化合物’一活化劑，和隨意的一載體，其中該含第1 5族 金屬化合物係由下式所表示 R5 R1· R3- L- —R7 \ •MXn -Z——R° ^-- (請先閱讀背面之注意事項再填寫本頁) 其中Μ爲第3、4或6族金屬 各X獨立地爲一脫離基； η爲0至4的整數； L爲第1 5族原子 Υ爲第1 5族原子 Ζ爲第15族原子 R1與R2獨立地爲Ci — C2Q烴基 碳原子的含雜原子基，選自矽、鍺、錫 子； R 3爲不存在或爲一烴基、氫、鹵素 R 4與R5獨立地爲一烷基、一芳基 烷基，經取代環烷基、環芳烷基，經取代環芳院基或多環 系統； 、11 經濟部智慧財產局員工消費合作社印製 具有多達2 0個 鉛、及磷之雜原 含雜原子基； 經取代芳基、環-———— Revision (revised) of the original 94 ft 8 — — · A8 B8 C8 D8 VI. Patent Application Scope Annex 4A Article 898919281 Chinese Patent Application Replacement of the Republic of China August 8, 1994 Amendment 1 · A catalyst composition comprising an activator containing a Group 15 metal catalyst compound and an optional carrier, wherein the Group 15 metal compound is represented by the formula R5 R1 · R3- L- —R7 \ • MXn -Z——R ° ^-(Please read the notes on the back before filling out this page) where M is a Group 3, 4 or 6 metal and each X is independently a dissociative group Η is an integer from 0 to 4; L is a Group 15 atom; Υ is a Group 15 atom; Z is a Group 15 atom; R1 and R2 are independently a Ci-C2Q hydrocarbon-based heteroatom-containing group selected from silicon , Germanium, tin; R 3 is absent or is a hydrocarbon group, hydrogen, halogen R 4 and R 5 are independently an alkyl group, an aryl alkyl group, a substituted cycloalkyl group, a cycloaralkyl group, a substituted ring Fangyuan-based or multi-ring system; 11, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs with up to 20 lead and phosphorus impurities Heteroatom; substituted aryl, cycloalkyl 1245773 A8 B8 C8 D8 六、申請專利範圍 R6與R'獨立地爲不存在，或爲氫、烷基、鹵素、雜 原子或烴基。 (請先聞讀背面之注意事項再填寫本頁) 2 ·如申請專利範圍第1項之觸媒組成物，其更包含 一茂合金屬觸媒化合物，一傳統過渡金屬觸媒化合物，或 彼等的組合。 3 ·如申請專利範圍第1項之觸媒組成物，其中r 4與 R 5係由下面的式所表者 R121245773 A8 B8 C8 D8 6. Scope of patent application R6 and R 'are independently absent or are hydrogen, alkyl, halogen, heteroatom or hydrocarbon group. (Please read the precautions on the reverse side before filling out this page) 2 · If the catalyst composition of the first patent application scope, it contains a metallocene catalyst compound, a traditional transition metal catalyst compound, or both The combination. 3. The catalyst composition according to item 1 of the patent application scope, wherein r 4 and R 5 are represented by the following formula R12 鍵結到Z或Y 其中R8至R12獨立地各爲氫，〇1至〇4。烷基、鹵 離子、雜原子，含多達4 0個碳原子的含雜原子基。 4 ·如申請專利範圍第3項之觸媒組成物，其中R 9、 R1(}和R12獨立地爲甲基、乙基、丙基或丁基，或其中 R9、Rl。和Rl2爲甲基，且RqaRll爲氫。 經濟部智慧財產局員工消費合作社印製 5 ·如申請專利範圍第1項之觸媒組成物，其中該含 第1 5族金屬觸媒化合物含有至少一個有6或更多碳原子 的經取代烴脫離基。 6 ·如申請專利範圍第1或2項之觸媒組成物，其中 該活化劑包括烷基鋁化合物、鋁氧烷、改質鋁氧烷、非配 位性陰離子、硼烷、硼酸鹽離子化化合物及/或下式所表 的含路以士酸鋁的活化劑 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -2 - 1245773 A8 B8 C8 _____D8 六、申請專利範圍 RnAl ( A r H a l ) 3 - n 其中R爲一單陰離子配位子； (請先閱讀背面之注意事項再填寫本頁) A r H a 1爲鹵化c6芳族或更多碳數的多環芳族烴或 芳環組合體，其中有兩個或更多個環（或稠環系統）彼此 直接連接或一起連接；且 η = 1 至 2。 7 .如申請專利範圍第丨項之觸媒組成物，其中該含第 1 5族金屬觸媒化合物與該茂合金屬觸媒化合物，若存在 時’係與該活化劑接觸形成一反應產物後與該載體接觸。 8 ·如申請專利範圍第1項之觸媒組成物，其係用於製 造多峰型聚合物組成物中的高分子量成分。 9 ·如申請專利範圍第2項之觸媒組成物，其中該茂 合金金屬化合物具有通式 L D M Q 2 ( Υ Ζ ) X η 其中Μ爲第4至6族金屬 !^°爲鍵結到Μ之環戊二烯基型基團， 各Q爲單價陰離子配位子，其係鍵結到Μ者； 經濟部智慧財產局員工消費合作社印製 Q 2 ( Υ Ζ )形成一單電荷多齒配位子； X於η爲2時爲一單價陰離子基或於η爲χ時乂爲二 價陰離子基，且 η爲1或2。 1 〇 ·如申請專利範圍第9項之觸媒組成物，其中χ爲 胺基甲酸根、羧酸根、或其它由Q Υ Ζ.組合所袠的雜嫌丙 基部份體。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） q 1245773 A8 B8 C8 __ D8 六、申請專利範圍 1 1 · 一種將申請專利範圍第1項之觸媒組成物用於 聚合烯烴的用途。 1 2 ·如申請專利範圍第11項之用途，其中該觸媒組 成物更包含一茂合金屬觸媒化合物，一傳統過渡金屬觸媒 化合物，或彼等的組合。 1 3 ·如申請專利範圍第11項之用途，其中該觸媒化 合物及/或該活化劑化合物係在液體載體中導到一氣相或 漿相反應器內。 1 4 ·如申請專利範圍第12項之用途，其係利用一氣 相反應器其中係將至少兩觸媒與至少一活化劑在液體載體 內導到反應器內，其中各觸媒係經獨立地活化且該等觸媒 和該活化劑係在液體載體內組合後才導到反應器內。 1 5 ·如申請專利範圍第12項之用途，其中該等觸媒 係經依序活化者。 1 6 ·如申請專利範圍第1 2項之用途，其中 i )將諸觸媒在液體載體中組合後，將活化劑導到該 液體載體內； 或其中 i i )將諸觸媒在該液體載體內組合後導到一接到反 應器的通道工具內，並於其後將該活化劑從與該觸媒給入 點相同或不同點處導到該通道工具內。 1 7 ·如申請專利範圍第11或12項之用途，其中該含 有該觸媒和活化劑的液體載體係經放置在一將該液體載體 導到反應器內所用的裝置內。 本紙張尺度適用中國國家標準（CNS )八4規格（210X297公釐） (請先聞讀背面之注意事項再填寫本貢) -裝- 、1T 經濟部智慧財產局員工消費合作社印製 -4- 1245773 A8 B8 C8 _ D8 六、申請專利範圍 1 8 ·如申請專利範圍第1 7項之用途’其中係在將活 化劑導到該裝置內之前將該觸媒與液體載體導到該裝置內 〇 (請先閲讀背面之注意事項再填寫本頁) 1 9 ·如申請專利範圍第1 1或1 2項之用途，其中該液 體載體包括一流入或經噴到該反應器中之液體流。 2 0 ·如申請專利範圍第11或1 2項之用途，其中該至 少一觸媒’至少一活化劑和該液體載體係置於一裝置內以 導到反應器內，其中在該第一觸媒和活化劑經導到該裝置 內之後將另外的觸媒導到該裝置內。 2 1 ·如申請專利範圍第11或12項之用途，其中 i )將包括至少一觸媒在一液體載體內的第一組合導 到一連接到反應器的裝置內，及將包括至少一活化劑在一 液體載體內的第二組合導到連接到反應器的裝置內，然後 ’於一段期間後，將在液體載體內的不同觸媒導到該連接 到反應器的裝置內，並接著將該觸媒-活化劑組合導到反應 器內； 或其中 經濟部智慧財產局員工消費合作社印製 i i )將至少一觸媒（a )和至少一活化劑（a )在 液體載體內組合，並將至少一觸媒（b )與至少一活化劑 (b )在一液體內組合，其中該觸媒（b )不同於該觸媒 (a )及/或該活化劑（b )不同於該活化劑（a )，且 其後將兩組合導到一連接到反應器的裝置，且，於其後， 將該等組合導到反應器內； 或其中 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 1245773 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 i i i )將含有觸媒（a )和活化劑（a )的液體載 體導到連接到反應器的裝置中之後將含有該觸媒（b )和 活化劑（b )的液體載體導到連接到反應器的裝置內； 或其中 1 v )將包括至少一觸媒（a )，至少一活化劑（a )和液體導體的第一組成物置於一連接到反應器的一裝置 內，及將包括至少一觸媒（b )，至少一活化劑（b )和 一液體載體的第二組成物，其中該觸媒（b )及/或該活 化劑（b )不同於該觸媒（a )及/或該活化劑（a )， 於該第一組成物經導入後，導到該連接到反應器的裝置內 ，並於其後將合倂的組成物導到反應器內； 或其中 v )將至少一觸媒和液體載體置於一用以導到反應器 內的裝置內’其中在該第一觸媒經導到該裝置中之後，將 另外的觸媒和活化劑導到該裝置內； 或其中 v i )將包括至少一觸媒，至少一活化劑和一液體載 體的第一組成物導到一給到反應器中所用裝置內，其後將 一第二觸媒在一液體載體內加到該給到反應器中所用裝置 內’且其後將一第二活化劑在液體載體內加到該給到反應 器中所用的裝置內，且於其後將整個組合物導到反應器內 〇 2 2 ·如申請專利範圍第11或丨2項之用途，其中該觸 媒化合物及/或該活化劑係在放置到該液體載體中之前即 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1^-------1T------0 (請先閲讀背面之注意事項再填寫本頁) 1245773 AB1CD 六、申請專利範圍 組合在一起，及/或其中該載體爲烷。 (請先閲讀背面之注意事項再填寫本頁) 2 3 ·如申請專利範圍第11或1 2項之用途，其中該觸 媒化合物及/或活化劑化合物係經承載在一載體之上。 2 4 ·如申請專利範圍第11或1 2項之用途，其中該活 化劑包括烷基鋁化合物、鋁氧烷、改質鋁氧烷、非配位性 陰離子、硼烷、硼酸鹽離子化化合物及/或下式所表的含 路以士酸鋁的活化劑 R n A 1 ( A r H a 〇 3 - η 其中R爲一單陰離子配位子； A r Ha 1爲鹵化C6芳族或更多碳數的多環芳族烴或 芳環組合體，其中有兩個或更多個環（或稠環系統）彼此 直接連接或一起連接；且 η = 1 至 2。 2 5 ·如申請專利範圍第11或12項之用途，其中該烯 烴的聚合係選自連續氣相法和連續漿相法。 經濟部智慧財產局員工消費合作社印製 2 6 ·如申請專利範圍第11或12項之用途，其中該烯 烴爲乙烯、或丙烯、或乙烯與至少一種含3至2 0個碳原 子的其它單體。 2 7 ·如申請專利範圍第12項之用途，其中該含第 1 5族金屬化合物對茂合金屬型化合物的莫耳比爲2 0 : 8 0 至 8 0 : 2 0。 2 8 ·如申請專利範圍第11或12項之用途，其更包括 接觸一或多種烯烴以製造聚合物。 2 9 · —種藉由使用申請專利範圍第1項之觸媒組成物 本紙張尺度適用中國國家標準（CNS ) Α4規格（2!〇Χ297公釐） 1245773 ABCD 六、申請專利範圍 於烯烴聚合而製得之聚合物，其中該聚合物具有〇 · 8 9 至0·97克/立方釐米之密度，及1至l〇dg/ mi η或更低者之Ι2ι，〇 · 〇1至100〇dg/ mi η之12，180，000或更高的Mw’及低於 1 0 0 P P hi的灰分含量，及含有可用局解析率質s普術偵 檢之含氮配位子。 3 0 .如申請專利範圍第2 9項之聚合物’其在形成爲 0 · 5密爾（1 3微米）厚度的膜時具有6 0%或更低的 濁度及1 3或更高的4 5 °光澤度，其中該膜係一吹膜或 鑄膜，且其中該膜具有約5克/密爾（〇 · 2 0克/微米 )和2 5克/密爾（1 · 0克/微米）之間的0 · 5密爾 (1 3微米）膜MD抗撕強度。 3 1 · —種包含藉由使用申請專利範圍第1項之觸媒組 成物於烯烴聚合而製得之聚乙烯的組成物，其具有 0 · 910 克/cc 至 0 · 935 克/cc 之密度，1〇 d g/m i η或更低之熔融指數，1 〇%或更低的濁度及 6 0單位或更高的4 5 °光澤度。 3 2 ·如申請專利範圍第3 1項之組成物，其中該聚乙 烯具有0 · 915 — 0 · 930克/cc之密度，5dg / m i η或更低的熔融指數，及7 %或更低的濁度，7 5 單位或更高的4 5 °光澤度，1 5 0克或更大的落錘抗衝 擊強度（依ASTM D 1 7 0 9 Method Α測得者）， 1 0 0克或更大的機械方向Elmendorf抗撕強度，及 5 0 0克或更大的橫向Elmendorf抗撕強度。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝· 、11 經濟部智慧財產局員工消費合作社印製 1245773 A8 B8 C8 D8 六、申請專利範圍 3 3 · —種在單一反應器中以至少兩種觸媒所製得之 以乙烯爲底質的聚合物組成物，其具有大& 80& 121/l2 ^ 立方釐米或更 Ci ΓΛ\} h、、、J M J /1 又 口 ] /J /|u_L /'ίΛ^ \/J //、 1 低於100 ppm的灰分含量，且具有0.945克 高的聚乙烯密度 4 · 一種乙烯聚合物或共聚物，其具有2.0 ppm 锆或 更低的殘留金屬含量，低於或等於12的ί 的Ι21/12，2.0 ppm或更低的殘留氮 的灰分含量。 ，大於或等於80 含釁，及低於100 ppm (請先閱讀背面之注意事項再填寫本頁) •裝 、trBonded to Z or Y where R8 to R12 are each independently hydrogen, 〇1 to 〇4. Alkyl, halide, heteroatom, heteroatom-containing groups containing up to 40 carbon atoms. 4. The catalyst composition according to item 3 of the scope of patent application, wherein R 9, R1 () and R12 are independently methyl, ethyl, propyl or butyl, or R9, R1 and R12 are methyl And RqaRll is hydrogen. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs5. If the catalyst composition of the scope of application for item 1 of the patent, wherein the Group 15 metal catalyst compound contains at least one of 6 or more A substituted hydrocarbon leaving group of a carbon atom. 6 · The catalyst composition according to item 1 or 2 of the patent application scope, wherein the activator includes an alkylaluminum compound, alumoxane, modified alumoxane, non-coordination Anion, borane, borate ionized compound and / or activator containing aluminum leucate as shown in the following formula: This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-2-1245773 A8 B8 C8 _____D8 VI. Patent application scope RnAl (A r H al) 3-n where R is a single anionic ligand; (Please read the notes on the back before filling this page) A r H a 1 is halogenated c6 Polycyclic aromatic hydrocarbons or aromatic ring combinations of aromatic or more carbon atoms, of which two Or more rings (or fused ring systems) are directly connected to each other or together; and η = 1 to 2. 7. The catalyst composition according to item 丨 of the patent application scope, wherein the group 15 metal catalyst The compound and the metallocene catalyst compound, if present, are in contact with the activator to form a reaction product, and then contact the carrier. 8 · As the catalyst composition of the first scope of the patent application, it is used for manufacturing A high molecular weight component in a multimodal polymer composition. 9 · The catalyst composition according to item 2 of the patent application range, wherein the metallocene metal compound has the general formula LDMQ 2 (Υ) X η where M is the fourth To Group 6 metals! ^ ° is a cyclopentadienyl-type group bonded to M, each Q is a monovalent anionic ligand, which is bonded to M; Q is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 (Υ Z) forms a single-charged multidentate ligand; X is a monovalent anionic group when η is 2 or 乂 is a divalent anionic group when η is χ, and η is 1 or 2. 1 〇 · 如Catalyst composition for the scope of application for item 9, wherein χ is urethane, Acid radicals, or other heteropropyl groups formed by Q 袠 Z. combinations. This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) q 1245773 A8 B8 C8 __ D8 VI. Application Patent Scope 1 1 · A use of the catalyst composition in the scope of patent application item 1 for the polymerization of olefins. 1 2 · The use in the scope of the patent scope application item 11, wherein the catalyst composition further comprises a metallocene catalyst Catalyst compound, a traditional transition metal catalyst compound, or a combination thereof. 1 3 · The use according to item 11 of the scope of patent application, wherein the catalyst compound and / or the activator compound is conducted in a liquid carrier into a gas phase or slurry phase reactor. 1 4 · For the purpose of claim 12 in the scope of patent application, it uses a gas-phase reactor in which at least two catalysts and at least one activator are introduced into the reactor in a liquid carrier, wherein each catalyst is independently It is activated and the catalyst and the activator are combined in a liquid carrier before being introduced into the reactor. 1 5 · If the application in the scope of patent application No. 12 is used, these catalysts are activated sequentially. 16 · For the purpose of claim 12 in the scope of patent application, wherein i) the catalysts are combined in a liquid carrier, and the activator is introduced into the liquid carrier; or ii) the catalysts are in the liquid carrier After being combined in vivo, it is guided into a channel tool connected to the reactor, and then the activator is guided into the channel tool from the same or different point from the catalyst feeding point. 17 · The application according to item 11 or 12 of the application, wherein the liquid carrier containing the catalyst and activator is placed in a device for guiding the liquid carrier into the reactor. This paper size applies to China National Standard (CNS) 8-4 specifications (210X297 mm) (please read the precautions on the back before filling in this tribute) -Packed-1T 1245773 A8 B8 C8 _ D8 VI. Application scope of patent 1 8 · If the application of scope of patent application No. 17 is used, the catalyst and liquid carrier are introduced into the device before the activator is introduced into the device. (Please read the precautions on the back before filling out this page) 1 9 · If the application in the scope of patent application No. 11 or 12 is used, the liquid carrier includes a liquid flow flowing into or sprayed into the reactor. 2 0. If the application of the scope of patent application item 11 or 12, wherein the at least one catalyst 'at least one activator and the liquid carrier are placed in a device to lead into the reactor, where the first contact The catalyst and activator are directed into the device and further catalyst is directed into the device. 2 1 · If the purpose of the scope of patent application is 11 or 12, i) the first combination including at least one catalyst in a liquid carrier is introduced into a device connected to the reactor, and at least one activation is included A second combination of agents in a liquid carrier is directed to the device connected to the reactor, and then, after a period of time, different catalysts in the liquid carrier are directed to the device connected to the reactor, and then the The catalyst-activator combination is introduced into the reactor; or printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ii) combining at least one catalyst (a) and at least one activator (a) in a liquid carrier, and Combining at least one catalyst (b) and at least one activator (b) in a liquid, wherein the catalyst (b) is different from the catalyst (a) and / or the activator (b) is different from the activation Agent (a), and then lead the two combinations to a device connected to the reactor, and thereafter, lead these combinations into the reactor; or where the paper size applies the Chinese National Standard (CNS) A4 Specifications (210X297 mm) -5- 1245773 A8 B8 C8 D8 Printed by the Consumers' Cooperative of the Ministry of Economic Affairs of the Ministry of Economic Affairs 6. Scope of patent application iii) After the liquid carrier containing catalyst (a) and activator (a) is introduced into the device connected to the reactor, the catalyst (b ) And the liquid carrier of the activator (b) into a device connected to the reactor; or 1 v) the first composition comprising at least one catalyst (a), at least one activator (a) and a liquid conductor In a device connected to the reactor, and a second composition comprising at least one catalyst (b), at least one activator (b) and a liquid carrier, wherein the catalyst (b) and / or the The activator (b) is different from the catalyst (a) and / or the activator (a). After the first composition is introduced, it is introduced into the device connected to the reactor, and then it is combined. The composition of plutonium is introduced into the reactor; or v) at least one catalyst and liquid carrier are placed in a device for introduction into the reactor, wherein after the first catalyst is introduced into the device Direct additional catalysts and activators into the device; or where vi) will include to One catalyst is missing, the first composition of at least one activator and a liquid carrier is introduced into a device used in the reactor, and then a second catalyst is added to the feed reactor in a liquid carrier. In the device used in the 'and then a second activator is added in a liquid carrier to the device used in the feed reactor, and thereafter the entire composition is introduced into the reactor. 2 2 · As requested The use of item 11 or 2 of the patent scope, wherein the catalyst compound and / or the activator are applied to the Chinese national standard (CNS) A4 specification (210X 297 mm) before the paper size is placed in the liquid carrier 1 ^ ------- 1T ------ 0 (Please read the notes on the back before filling out this page) 1245773 AB1CD 6. The scope of the patent application is combined, and / or the carrier is alkane. (Please read the precautions on the reverse side before filling out this page) 2 3 · If the application of the scope of patent application No. 11 or 12 is used, the catalyst compound and / or activator compound is carried on a carrier. 2 4 · The use as claimed in item 11 or 12 of the scope of patent application, wherein the activator includes an alkylaluminum compound, alumoxane, modified alumoxane, non-coordinating anion, borane, borate ionized compound And / or the activator containing aluminum ethoxylate R n A 1 (A r H a 〇3-η) as shown in the following formula: where R is a monoanionic ligand; A r Ha 1 is a halogenated C6 aromatic or Polycyclic aromatic hydrocarbons or aromatic ring assemblies of more carbon number, in which two or more rings (or fused ring systems) are directly connected to each other or together; and η = 1 to 2. 2 5 · If applied The use of item 11 or 12 of the patent scope, wherein the polymerization of the olefin is selected from the continuous gas phase method and the continuous slurry phase method. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 6 · If the scope of patent application is item 11 or 12 The use, wherein the olefin is ethylene, or propylene, or ethylene and at least one other monomer containing 3 to 20 carbon atoms. 2 7 · The use according to item 12 of the patent application scope, wherein the containing group 15 The molar ratio of the metal compound to the metallocene compound is from 20:80 to 80: 2. 2 8 · For applications in the scope of patent application No. 11 or 12, it also includes contact with one or more olefins to make polymers. 2 9 · —A kind of catalyst composition by using the scope of patent application No. 1 This paper is applicable to China Standard (CNS) A4 specification (2.0 × 297 mm) 1245773 ABCD 6. Application for a polymer prepared by polymerizing olefins, wherein the polymer has a density of 0.89 to 0.97 g / cm3 , And 1 to 10 dg / mi η or lower of Ιιι, 〇1 to 100 dg / mi η of 12,180, or higher Mw 'and ash lower than 100 PP hi Content, and nitrogen-containing ligands containing qualitative and universal detection of available local resolution. 30. If the polymer in the scope of the patent application No. 29 is' the formation of 0. 5 mil (13 micron) The thickness of the film has a turbidity of 60% or lower and a gloss of 45 ° of 13 or higher, wherein the film is a blown film or cast film, and wherein the film has about 5 g / mil ( 0 · 5 mil (13 micron) film MD tear strength between 20 g / micron) and 25 g / mil (1.0 g / micron). 3 1 · -species A composition containing polyethylene prepared by polymerizing an olefin using the catalyst composition of the first patent application range, which has a density of 0.910 g / cc to 0.935 g / cc, 10 dg / Melt index of mi η or lower, turbidity of 10% or lower, and 45 ° gloss of 60 units or higher. 3 2 · The composition according to item 31 of the scope of patent application, wherein the polyethylene has a density of 0 · 915 — 0 · 930 g / cc, a melting index of 5 dg / mi η or less, and 7% or less Turbidity, 45 ° gloss of 75 units or more, drop weight impact strength of 150 grams or more (measured according to ASTM D 1 7 0 9 Method Α), 100 grams or Greater Elmendorf tear strength in the mechanical direction, and transverse Elmendorf tear strength of 500 grams or more. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page)-Packing · 11 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 1245773 A8 B8 C8 D8 Sixth, the scope of application for patent 3 3 · —A kind of polymer composition with ethylene as the substrate produced by at least two catalysts in a single reactor, which has a large & 80 & More Ci ΓΛ \} h ,,, JMJ / 1 and mouth] / J / | u_L / 'ίΛ ^ \ / J //, 1 ash content below 100 ppm, and has a high polyethylene density of 0.945 g4 · An ethylene polymer or copolymer having a residual metal content of 2.0 ppm zirconium or less, an I21 / 12 of less than or equal to 12 and an ash content of 2.0 ppm or less of residual nitrogen. , Greater than or equal to 80, and less than 100 ppm (please read the precautions on the back before filling this page) • equipment, tr 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（2!0X297公釐）Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs