TW527366B

TW527366B - Ethylene and/or alpha-olefin/vinyl or vinylidene aromatic interpolymer compositions

Info

Publication number: TW527366B
Application number: TW089112202A
Authority: TW
Inventors: Stephen F Hahn; Oscar D Redwine; Ravi B Shankar; Francis J Timmers
Original assignee: Dow Chemical Co
Priority date: 1999-06-22
Filing date: 2000-06-21
Publication date: 2003-04-11
Also published as: AR026131A1; WO2000078831A1; AU5324300A; KR20020013933A; EP1200491A1; CN1357014A; CA2384373A1; JP2003503513A

Abstract

The present invention pertains to an interpolymer comprising; (1) from 5 to 85 mol percent of polymer units derived from one or more vinyl or vinylidene aromatic monomers, (2) from 15 to 95 mol percent of polymer units derived from at least one of ethylene and/or a C3-20 alpha-olefin; and (3) from 0 to 20 mol percent of polymer units derived from one or more of ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2); and wherein said interpolymer contains detectable vinyl or vinylidene aromatic monomer triads.

Description

527366 A7527366 A7

五、發明說明（1 ) 本务明係有關包含乙烯基或亞乙烯基芳族單體與乙烯及/或一或多者之α_烯烴單體之異種共聚物之組成物。用以製備此等異種共聚物之催化劑，[(4,5_伸甲基-菲基X 第三丁基醯胺基）二甲基矽烷]二曱基鈦，對於乙烯基或亞乙烯基芳族單體具有顯著之高反應性。形成之異種共聚物含有連續之乙烯基或亞乙烯基芳族單體***，因此能具有超過65莫耳％之乙烯基或亞乙烯基芳族單體***。至最近，乙烯及乙婦基或亞乙烯基芳族單體之共聚合反應使用傳統之以Ti(III)及Ti(IV)為主之齊袼勒α _烯烴聚合反應催化劑非商業上實用之方法。最早之以此等催化劑製備乙烯基芳族單體及α _烯烴之共聚物（特別是苯乙烯及乙烯之共聚物）之努力係不能獲得大量之乙烯芳族單體併入或達成低分子量之聚合物。於聚合物公報V. Description of the Invention (1) The present invention relates to a composition comprising a heteropolymer of a vinyl or vinylidene aromatic monomer and ethylene and / or one or more α-olefin monomers. Catalysts for the preparation of such heterogeneous copolymers, [(4,5_methylene-phenanthryl X tertiary butylamido) dimethylsilane] difluorenyl titanium, for vinyl or vinylidene aromatic Group monomers have significantly high reactivity. The heterogeneous copolymer formed contains continuous vinyl or vinylidene aromatic monomer insertions and therefore can have more than 65 mole% of vinyl or vinylidene aromatic monomer insertions. Until recently, the copolymerization reaction of ethylene and ethynyl or vinylidene aromatic monomers used traditional Ti (III) and Ti (IV) -based Zircon α-olefin polymerization catalysts, which was not commercially practical. method. The earliest efforts to prepare copolymers of vinyl aromatic monomers and α-olefins (especially copolymers of styrene and ethylene) with these catalysts failed to obtain a large amount of ethylene aromatic monomers to incorporate or achieve low molecular weight. polymer. Polymer Bulletin

Bulletin) ’ 20, 237-241 (1988)中，揭示於其間含有丨莫耳％之被併入苯乙烯之苯乙烯及乙烯之共聚物。所報導之聚合物產率係每微莫耳所用之鈦係8.3 χ 1〇·4克之聚合物。但是 ’藉由以二茂金屬錯合物為主之烯烴聚合反應催化劑之來臨’且特別是幾何受限型之催化劑，現在可使乙嫦及其它 α-烯烴與其它乙烯基或亞乙烯基芳族單體共聚合以提供異種共聚物。包含具有多於50莫耳％苯乙烯併入之物料之乙稀及苯乙烯之共聚物已被報導使用柄型二茂金屬錯合物催化劑，如 Arai，Τ·; Ohtsu，Τ·; Suzuki，S·於Macromo/ecw/w 及印W Comm·. 1998及1998，39(1)，220-221所揭本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注咅？事項再填寫本頁) ----------^---------^ I . 經濟部智慧財產局員工消費合作社印製 4 527366 A7 經濟部智慧財產局員工消費合作社印製Bulletin) '20, 237-241 (1988) discloses a copolymer of styrene and ethylene incorporated with styrene in which mol% is contained. The reported polymer yield is 8.3 x 10.4 grams of polymer per micromole of titanium. But 'with the advent of catalysts for the polymerization of olefins based on metallocene complexes', and especially geometrically constrained catalysts, it is now possible to make ethylamidine and other α-olefins with other vinyl or vinylidene aromatics Family monomers are copolymerized to provide heterogeneous copolymers. Copolymers of ethylene and styrene containing materials with more than 50 mole% styrene incorporated materials have been reported to use shank-type metallocene complex catalysts, such as Arai, T ·; Ohtsu, T ·; Suzuki, S · In Macromo / ecw / w and India W Comm ·. The paper sizes disclosed in 1998 and 1998, 39 (1), 220-221 are applicable to China National Standard (CNS) A4 (210 X 297 mm) (please first Read the note on the back? Matters should be filled out on this page) ---------- ^ --------- ^ I. Printed by the Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative 4 527366 A7 Ministry of Economic Affairs Printed by the Intellectual Property Bureau Staff Consumer Cooperative

發明說明（2 示者。此外，美國專利第5,7〇3，187號案描述，，假無規，，乙烯苯乙烯異種共聚物，其特徵在於獨特之單體分佈，其中連續之頭接尾之苯乙烯單體***未被觀察，其係無88二單元組或SSS三單元組。除缺乏序列之頭接尾之笨乙烯單體 ***，異種共聚物内之苯乙烯分佈仍被發現充分分散，因此，”假無規”。假無規共聚物之特殊區別特徵係聚合物主幹上取代之所有苯基或本體受阻基係以2或更多之伸乙基單元分開。於加成聚合反應期間，若乙烯基或亞乙烯基芳族單體被***成長之聚合物鏈内，下一個***之單體需為乙烯或乙烯基或亞乙烯基芳族單體，其係以顛倒方式*** (其中顛係指2,1***，而正常***係丨，2，但熟習此項技藝者能暸解相反者亦係正確，且不會改變本發明異種共聚物之描述或性質）方於顛倒之乙烯基或亞乙烯基芳族單體插入後，下一個單體需為乙烯，因於此點之另一乙烯基或亞乙烯基芳族單體之***會使受阻之取代基比如上所述之最小分離更接近而在一起。此等聚合反應動力學之結果係所用催化劑不會使笨乙稀均聚合成任何察覺之程度，而乙稀及苯乙烯之混合物被快速聚合，且可產生高苯乙烯含量（最高達50莫耳％之苯乙烯）之共聚物。此單體分佈之直接結果係苯乙烯併入之特殊上限係約5〇莫耳％或79重量％之苯乙烯。 WO 98/0999描述”實質無規，，之乙烯苯乙烯異種共聚物，其除包含前述假無規異種共聚物外，亦包含使用特殊 ------- I ^---------線 — # ------ 广請先閲讀背命Μ浲意事頊戽填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格⑽x297公爱y 527366Description of the invention (2). In addition, US Patent No. 5,703,187 describes, false random, ethylene styrene heteropolymer, which is characterized by a unique monomer distribution, in which continuous heads end to tail The insertion of styrene monomer was not observed, and it did not have 88 two-unit group or SSS tri-unit group. Except for the lack of insertion of the stupid vinyl monomer at the beginning and end of the sequence, the styrene distribution in the heterogeneous copolymer was still found to be sufficiently dispersed. Therefore, "false random". The special distinguishing feature of false random copolymers is that all phenyl or bulk hindered groups substituted on the polymer backbone are separated by 2 or more ethylenic units. During the addition polymerization reaction If a vinyl or vinylidene aromatic monomer is inserted into a growing polymer chain, the next monomer to be inserted must be an ethylene or vinyl or vinylidene aromatic monomer, which is inserted in an upside down manner (where Inversion refers to the insertion of 2,1, and normal insertion is 丨, 2, but those skilled in the art can understand that the opposite is also correct and does not change the description or properties of the heteropolymer of the present invention. Vinylidene After the monomer is inserted, the next monomer must be ethylene, because the insertion of another vinyl or vinylidene aromatic monomer at this point will cause the hindered substituents to be closer together than the minimum separation described above. The result of these polymerization reaction kinetics is that the catalyst used will not homogeneously polymerize the ethylene to any appreciable extent, while the mixture of ethylene and styrene is rapidly polymerized and can produce a high styrene content (up to 50 moles) Styrene) copolymer. The direct result of this monomer distribution is that the special upper limit for styrene incorporation is about 50 mole% or 79% by weight of styrene. WO 98/0999 describes "essentially random, In addition to the above-mentioned pseudo-random heterogeneous copolymer, the ethylene-styrene heterogeneous copolymer also includes the use of special ------- I ^ --------- line — # ---- -Please read Memorandum (intentions) first and fill in this page) This paper size is applicable to China National Standard (CNS) A4 specifications x 297 public love y 527366

經濟部智慧財產局員工消費合作社印製二茂金屬錯合物聚合反應催化製得之異種共聚物。使用此等特殊之二茂金屬錯合物聚合反應催化劑造成形成具有獨特單體分佈特徵之異種共聚物。於此分佈中，雖然大部份聚合物鏈於苯乙烯分佈中係假無規，小含量之包含二頭接尾之乙烯基芳族單體***之序列（其係於至少一乙烯*** 之前及之後）被觀察到。其係乙烯/苯乙烯/苯乙烯/乙烯之四單元組，ESSE，其中該四單元組之苯乙烯單體之併入係獨特地以1，2方式產生。因此，此等特殊之實質無規乙烯/苯乙烯異種共聚物於NMR光譜中含有相似於假無規乙烯/苯乙烯異種共聚物之波峰，但亦具出現於437〇_ 44.25ppm之化學位移範圍之強度之另外訊號之特徵。此獨特單體分佈之結果，實質無規乙烯苯乙烯異種共聚物内之苯乙烯併入之上限被升高至約65莫耳％或87 5重量％之苯乙烯。吾等現驚人地發現催化劑，[(4,5_伸甲基·菲基）（第三丁基醯胺基）二曱基矽烷]二甲基鈦，於與乙烯及/或一或多者之α-烯烴單體之聚合反應中對於乙烯基或亞乙烯基芳族單體具有顯著之高反應性，且造成新穎異種共聚物之衣備，其於乙烯/苯乙烯異種共聚物之情況中，包含sss及更高（例如，SSSS，SSSSS等）之序列。此增加催化劑反應性之結果，形成之異種共聚物能展現超過65莫耳％之乙烯基或亞乙稀基芳族單體含量之上限。本發明係有關一種異種共聚物，包含： (1) 5至85莫耳％之衍生自一或多者之乙烯基或亞乙本紙張尺度iffl中國國1¾ (CNS)A4規格咖x 297 - i---^---一---1 1®^--------^---------ΜΙΦ.,-----k.---,-------------- (請先閱讀背面之注意事項再填寫本頁) 527366Heterogeneous copolymers made by the polymerization reaction of metallocene complexes printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The use of these special metallocene complex catalysts results in the formation of heterogeneous copolymers with unique monomer distribution characteristics. In this distribution, although most of the polymer chains are pseudorandom in the styrene distribution, a small amount of two-terminal vinyl aromatic monomer insertion sequences (which are before and after at least one ethylene insertion) )be observed. It is a four unit unit of ethylene / styrene / styrene / ethylene, ESSE, in which the incorporation of the four unit styrene monomer is uniquely produced in a 1,2 manner. Therefore, these special substantially random ethylene / styrene heteropolymers have peaks similar to the pseudo random ethylene / styrene heteropolymers in the NMR spectrum, but they also have a chemical shift range of 437-44.25ppm. The strength of the signal is another characteristic. As a result of this unique monomer distribution, the upper limit of styrene incorporation in the substantially random ethylene styrene heteropolymer is raised to about 65 mole% or 875% by weight of styrene. We have now surprisingly discovered that the catalyst, [(4,5-Methylphenanthrene) (Third-Butylamido) difluorenylsilane] dimethyl titanium, is associated with ethylene and / or one or more The α-olefin monomer has a significantly high reactivity to vinyl or vinylidene aromatic monomers during the polymerization reaction, and results in the coating of novel heteropolymers in the case of ethylene / styrene heteropolymers , Including sequences of sss and higher (eg, SSSS, SSSSS, etc.). As a result of increasing the reactivity of the catalyst, the heterogeneous copolymer formed can exhibit an upper limit of the content of vinyl or ethylene aromatic monomers exceeding 65 mole%. The present invention relates to a heterogeneous copolymer comprising: (1) 5 to 85 mol% of vinyl or ethylene paper derived from one or more paper sizes iffl China 1¾ (CNS) A4 size coffee x 297-i --- ^ --- 一 --- 1 1® ^ -------- ^ --------- ΜΙΦ., ----- k .---, --- ----------- (Please read the notes on the back before filling this page) 527366

經濟部智慧財產局員工消費合作社印製烯基芳族單體之聚合物單元， (2) 15至95莫耳％之衍生自乙烯及/或仏,^ -烯烴之至少一者之聚合物單元；及 (3) 〇至20莫耳〇/〇之衍生自一或多者之非衍生自（1) 及（2)者之乙烯不飽和可聚合單體之聚合物單元；且其中該異種共聚物含有可檢測之乙烯基或亞乙烯基芳族單體三單元組。此間所有提及屬於某些族之元素或金屬時係指cRC Press Inc·，1989出版及擁有版權之元素週期表。再者，任何述及族數者需為使用IUPAC系統命名之此元素週期表所反映之族數。若於任何較低數值及任何較高數值間具有至少2單位之分隔，此間所述及之任何數值包含以一單位增量之較低值至較高值。例如，若其陳述組份含量或方法變數（例如，溫度、壓力、時間）之值係1至90，較佳係2〇至8〇，更佳係30至70，其係指諸如15至85、22至68、43至51、3〇至32 等之值被明確表示於此說明書中。對於少於丨之值，一單位被認為係0.0001、0.001、0.01或01之適當者。此等僅係特別表示者，最低數值及最高數值間之所有可能數值之結合被認為以相似方式明確表示於此說明書中。 “異種共聚物”一辭於此間被用以表示其間至少二種不同單體被聚合製得此異種共聚物之聚合物。此包含共聚物、三元聚合物等。 “可檢測之乙烯基或亞乙烯基芳族單體三單元組，，於此本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Polymer units of alkenyl aromatic monomers printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, (2) 15 to 95 mol% of polymer units derived from at least one of ethylene and / or fluorene, ^ -olefins ; And (3) polymer units derived from one or more of the ethylene unsaturated polymerizable monomers derived from one or more of which are not derived from (1) and (2); and wherein the heteropolymer is copolymerized The substance contains a detectable vinyl or vinylidene aromatic monomer triad. All references to elements or metals belonging to certain groups herein refer to the periodic table of elements published and copyrighted by cRC Press Inc., 1989. Furthermore, any reference to the family number must be the family number reflected in this periodic table of elements named using the IUPAC system. Where there is a separation of at least 2 units between any lower value and any higher value, any value recited herein includes the lower value to the higher value in increments of one unit. For example, if the value of its stated component content or method variables (eg, temperature, pressure, time) is 1 to 90, preferably 20 to 80, and more preferably 30 to 70, it means such as 15 to 85 The values of 22, 68, 43 to 51, 30 to 32, etc. are clearly shown in this specification. For values less than 丨, a unit is considered to be the appropriate one of 0.0001, 0.001, 0.01, or 01. These are only specially indicated, and the combination of all possible values between the lowest value and the highest value is considered to be explicitly expressed in this specification in a similar manner. The term "heterogeneous copolymer" is used herein to mean a polymer in which at least two different monomers are polymerized to obtain the heterogeneous copolymer. This includes copolymers, terpolymers, and the like. "Detectable triad of vinyl or vinylidene aromatic monomers, here the paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

527366 A7527366 A7

’其於乙烯/苯乙烯異種共聚物之情況中包含sss及更高（例如，SSSS、SSSSS等）之序列。催化劑之增加反應性之結果’形成之異種共聚物能展現超過65莫耳％之對乙烯基或亞乙烯基芳族單體含量之上限。經濟部智慧財產局員工消費合作社印製'It includes sequences of sss and higher (for example, SSSS, SSSSS, etc.) in the case of an ethylene / styrene heteropolymer. As a result of the increased reactivity of the catalyst, a heterogeneous copolymer formed can exhibit an upper limit of the vinyl or vinylidene aromatic monomer content exceeding 65 mol%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

一種製備本發明異種共聚物之方法包含於[(4,5-伸甲基-菲基）（第二丁基醯胺基）二甲基矽烷]二甲基鈦及適當活化化合物存在中聚合可聚合單體混合物。使用此催化劑，本發明之異種共聚物可藉由ep_a_0,416,815號案（James C· Stevens等人）及美國專利第5,7〇3，187號案j. Timmers)(二者在此被完全併入以供參考）所述之方法製備。此等聚合反應之較佳操作條件係大氣壓至最高達3〇〇〇大氣壓之壓力及5(TC至20(rc之溫度。於高於個別單體之自動聚合反應S度之溫度時之聚合反應及未反應單體之移除可能造成形成某些含量之均聚物聚合反應產物(其係從自由基聚合反應形成）。於製備本發明異種共聚物時，一含置之無規立構之乙稀基或亞乙烯基芳族均聚物會因於升高溫度時之乙烯基芳族單體之均聚合反應而形成。乙稀基芳族均聚物之存在一般對於本發明目的係無不利，且係可刃受。若要的話，可藉由萃取技術（諸如，液體色譜術或= 對㈣共聚物或乙稀基或亞乙婦基芳族均聚物係非溶劑而 ^溶液沈殿出）而使乙婦基芳族均聚物自異種共聚物分離本發明異種共聚物包含藉由使下述者聚合而製得之異種共聚物：i)乙烯及/或一或多者之α •烯烴單體衣2⑴ (請先閱讀背面之注意事項再填寫本頁) --------^---------A method for preparing a heterogeneous copolymer of the present invention comprises polymerizing a polymer in the presence of [(4,5-methylene-phenanthryl) (second butylamidino) dimethylsilane] dimethyl titanium and a suitable activating compound. Polymerized monomer mixture. Using this catalyst, the heterogeneous copolymers of the present invention can be obtained by ep_a_0,416,815 (James C. Stevens et al.) And U.S. Patent No. 5,703,187 (j. Timmers) Incorporated for reference). The preferred operating conditions for these polymerizations are atmospheric pressure to a pressure of up to 3000 atmospheres and a temperature of 5 ° C to 20 ° C. The polymerization is at a temperature higher than the degree S of the automatic polymerization of the individual monomers. And the removal of unreacted monomers may result in the formation of homopolymer polymerization products (which are formed from free radical polymerization) at a certain content. In the preparation of the heteropolymers of the present invention, a random Ethylene or vinylidene aromatic homopolymers are formed as a result of the homopolymerization of vinyl aromatic monomers at elevated temperatures. The presence of ethylene aromatic homopolymers is generally not relevant for the purposes of the present invention. Unfavorable, and can withstand. If necessary, the solution can be obtained by extraction techniques (such as liquid chromatography or = fluorene copolymers or ethylene or ethylidene aromatic homopolymers). (Ex.) And the separation of ethynyl aromatic homopolymers from heteropolymers. The heteropolymers of the present invention include heteropolymers made by polymerizing: i) ethylene and / or one or more of alpha • Olefin single coat 2⑴ (Please read the precautions on the back first Write this page) -------- --------- ^

本紙張尺度適財目國家標準（CNS)A4規格（21〇 X 297公爱） 527366This paper is a national standard (CNS) A4 specification (21〇 X 297 public love) 527366

經濟部智慧財產局員工消費合作社印製 :或多者之乙縣或亞W基芳其它可聚合之乙烯不飽和單體。及—, ，更二包含’例如’含有3至20(較佳係3至12 ，3至8)個碳原子之喻。特別適合者係乙烯、了小”基-1·戊烯、己烯-1或辛烯]或與一或夕者之丙烯、丁烯_丨、4_ 八式甲基+戊烯、己烯-1或辛稀]結 a之乙烯。此等α-烯烴不含有芳族部份。其它選擇性之可聚合乙婦不飽和單體包含降冰片稀及Cm。烧基或芳基取代之降冰㈣，例示之異種共聚物係乙烯/苯乙烯/降冰片烯及乙烯/苯乙婦/亞乙婦降冰片稀。可被用於製備異種共聚物之適當之乙烯基或亞乙烯基芳族單體包含，例如，以下述化學式表示者：Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs: one or more of B County or Yajifang, other polymerizable ethylenically unsaturated monomers. And-,, and more, the metaphor containing "for example" containing 3 to 20 (preferably 3 to 12, 3 to 8) carbon atoms. Particularly suitable are ethylene, a small group "pentene-1, hexene-1 or octene] or propylene, butene, and 4-octamethyl + pentene, hexene- 1 or dilute] Ethylene A. These α-olefins do not contain aromatic moieties. Other optional polymerizable ethylenically unsaturated monomers include norbornaline and Cm. Burning or aryl substituted ice A. Exemplified heterogeneous copolymers are ethylene / styrene / norbornene and ethylene / acetophenone / ethene norbornane. Suitable vinyl or vinylidene aromatic monomers that can be used to prepare heterogeneous copolymers The body contains, for example, those represented by the following chemical formula:

Ar (CH2)n R* — C =： C(R2)2 其中，R1係選自氫及含有1至4個碳原子之烷基，較佳者係氫或甲基；每一 R2係個別選自氩及具有1至4個碳原子之烷基，較佳者係氫或甲基；Ar係苯基或以1至5個選自鹵基、C!·4之烷基及(^_4之i烷基之取代基取代之苯基；且η係具有〇至4之數值，較佳係0至2，最佳係0。例示之乙烯基芳族單體包含苯乙烯、乙烯基甲苯、α -甲基苯乙烯、第三丁基苯乙烯、氯苯乙烯，包含此等化合物之所有異本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Ar (CH2) n R * — C =: C (R2) 2 where R1 is selected from hydrogen and alkyl groups containing 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is selected individually From argon and an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is phenyl or 1 to 5 alkyl groups selected from halo, C! · 4, and (^ _4 of i-alkyl substituted phenyl; and η has a value of 0 to 4, preferably 0 to 2, most preferably 0. Exemplary vinyl aromatic monomers include styrene, vinyltoluene, α -Methylstyrene, tert-butylstyrene, chlorostyrene, all variants containing these compounds, paper size applicable to China National Standard (CNS) A4 (210 X 297 mm)

10 527366 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（8 ) 構物。特別適合之此等單體包含苯乙烯及其較低烷基或鹵素取代之衍生物。較佳之單體包含苯乙烯、α-甲基苯乙烯、苯乙烯之較低烷基-(q-C4)或苯基環取代之衍生物，諸如，例如，鄰_、間-及對_之曱基苯乙烯，環_素化之苯乙烯’對-乙烯基甲苯或其等之混合物。更佳之芳族乙烯基單體係苯乙烯。形成之異種共聚物可藉由典型之接枝、氫化、官能性化或其它熟習此項技藝者所知之反應改質之。聚合物可被輕易磺化，使用W0 99/20691號案所述之方法（其全部内容在此被併入以供參考），氯化或其它官能化，如相互關連之美國申請案第09/244,921號案（1999年2月4曰申請， R_ E· Drumright等人，其全部内容在此被併入以供參考）所述者。本發明組成物亦可藉由各種不同之交聯方法改質。其包含過氧化物、矽烷、硫、輻射或疊氮化合物為基準之固化系統，但不限於此。各種交聯技術之完整描述係描述於美國專利第5,869,591及5,977,271號案，此等之全部内容在此被併入以供參考。雙固化系統，其係結合熱、濕氣固化及幸§射步驟，可被有效使用之。例如，期望結合石夕烷交聯劑之過氧化物交聯劑，結合輻射之過氧化物交聯劑，結合矽烷交聯劑之含硫交聯劑等。雙固化系統係於美國專利第5,911，940號案揭示及請求，其全部内容在此被併入以供參考。諸如抗氧化劑（例如，受阻之酚，例如，Irganoχ㊣1010 ’ Ciba-Geigy之註冊商標）、亞磷酸鹽（例如，Irgaf〇s@16810 527366 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (8) Structure. Particularly suitable for these monomers are styrene and its lower alkyl or halogen substituted derivatives. Preferred monomers include styrene, alpha-methylstyrene, lower alkyl- (q-C4) or phenyl ring-substituted derivatives of styrene, such as, for example, ortho-, meta-, and para- Fluorenylstyrene, cyclized styrene'p-vinyltoluene or mixtures thereof. More preferred is an aromatic vinyl mono system styrene. The heterogeneous copolymers formed can be modified by typical grafting, hydrogenation, functionalization, or other reactions known to those skilled in the art. Polymers can be easily sulfonated using the method described in WO 99/20691 (the entire contents of which are incorporated herein by reference), chlorination or other functionalization, such as the related US Application No. 09 / Case No. 244,921 (filed on February 4, 1999, R. Drumright et al., The entire contents of which are incorporated herein by reference). The composition of the present invention can also be modified by various cross-linking methods. It includes, but is not limited to, peroxide, silane, sulfur, radiation or azide-based curing systems. A complete description of the various crosslinking technologies is described in U.S. Patent Nos. 5,869,591 and 5,977,271, the entire contents of which are incorporated herein by reference. The dual curing system, which combines thermal, moisture curing and firing steps, can be effectively used. For example, it is desirable to combine a peroxide crosslinking agent with a silane crosslinking agent, a peroxide crosslinking agent combining with a radiation, a sulfur-containing crosslinking agent combining with a silane crosslinking agent, and the like. The dual curing system is disclosed and claimed in U.S. Patent No. 5,911,940, the entire contents of which are incorporated herein by reference. Such as antioxidants (for example, hindered phenols, for example, registered trademark of Irganoχ㊣1010 ’Ciba-Geigy), phosphites (for example, Irgaf〇s @ 168

-l·---^-------1 1®^--------訂---------線 1·:---卜--->--------------- (請先閱讀背面之注意事項再填寫本頁} 527366 A7 經濟部智慧財產局員工消費合作社印製五、發明說明（ ’ Clb:Geigy，註冊商標）、υ·ν·穩定齊卜緊貼添加劑(例 k/、丁烯）q動劑（諸如，芥醯胺及/或硬脂醯胺）、抗成鬼d加蜊著色劑、色料、增黏劑、阻燃劑、偶合劑填料塑化劑之添加劑可被包含於本發明組成物内。亦被包含作為本發明組成物之可能組份係各種有機及無機之填料。此等填料之代表性例子包含有機及無機之填料’諸如’自石棉ϋ墨、陶究、玻璃、金屬（諸如，不鏽鋼）或聚合物（諸如，芳族聚酿胺纖維）、滑石、奴黑、碳纖維、碳酸鈣、氧化鋁三水合物、玻璃纖維、大理石灰水泥灰、黏土、長石、石夕石或玻璃、煙燦石夕石、乳化鋁、氧化鎂、纟氧化鎂、氧化銻、氧化鋅、硫酸鋇、石夕酸銘、料酸錢、、二氧化鈦、㈣鹽、氮化銘、Β203、錄粉或粉筆。其它代表性之有機或無機之纖維或礦物填料包含碳酸鹽（諸如，鋇、鈣或鎂之碳酸鹽）；硼酸鹽（諸如，鎂或鋅之硼酸鹽）、氟化物（諸如，鈣或鈉鋁之氟化物）；氫氧化物（諸如，氫氧化鋁）；金屬（諸如，鋁、青銅、鉛或鋅） ;氧化物（諸如，鋁、銻、鎂或鋅之氧化物），或矽或鈦之二氧化物；矽酸鹽（諸如，石棉、雲母、黏土（高嶺土或燒結之高嶺土）、矽酸鈣、長石、玻璃（研磨或片狀之玻璃或中空玻璃球或微球或珠粒、鬚狀物或長絲）、霞石、珍珠岩、葉蠟石、滑石或鈣矽石）；硫酸鹽（諸如，鋇或鈣之硫酸鹽）；金屬硫化物；纖維素（諸如木材或貝殼粉末之型式） ;對苯二甲酸鈣；及液晶。多於一者之此等填料之混合物本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） . —1®^ ^-----------------·--------------- (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 527366 Α7 _ Β7 五、發明說明（1Q ) 亦可被使用。填料亦可與偶合劑及/或起始劑（其係選自有機過氧化物、矽烷、鈦酸鹽、锆酸鹽、多官能性乙烯基化合物、有機疊氮化物及其等之混合物）結合使用之。其它添加劑包含受阻胺穩定劑。此等穩定劑包含受阻三嗪（諸如，被取代之三嗪及三嗪之反應產物）。適合之反應產物包含三嗪與例如二胺及/或環脂族化合物（諸如，環己烧）之反應產物。特別適合之受阻胺穩定劑包含1，3_ 丙烧二胺、队1^，，-1，2-乙烷二基雙-環己烷及過氧化^丁基-2,2,6,6-四甲基-4-派啶胺-2,4,6-三氯-1，3,5·三嘻之反應產物，其係由Ciba-Geigy製得且具有名稱” CG-116，，，其具有 CAS Reg No : 191680-81-6。此等添加劑係以熟習此項技藝者已知之官能性等化含量使用。例如，所用之抗氧化劑之量係避聚合物或聚合物摻合物於聚合物儲存及最終使用期間所用之溫度及環境時進行氧化反應之量。抗氧化劑之此含量一般係以聚合物或聚合物摻合物之重量為基準係〇·〇丨至1〇重量％之範圍，較佳係0.05至5重量％，更佳係〇.丨至2重量❶/❶。相似地，任何其它列舉之添加劑之量係官能性等化量，諸如，使聚合物或合物推合物抗結塊、產生所欲結果、由著色劑或色料提供所欲顏色之量。此等添加劑適當地係以異種共聚物之重里為基準係0.05至50重量％範圍使用之，較佳係〇」至 35重量％，更佳係〇·2至20重量％。填料可適當地以1-9〇重量％之範圍使用之。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 13 I I I ϋ ϋ i I 1 I I I ϋ ϋ ϋ — ϋ ϋ ·1 ϋ I ϋ n ϋ ϋ I ^1 ϋ ϋ n ϋ ϋ I 1 I ϋ ϋ ϋ I ι (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 527366 A7 " ---2Z____ 五、發明說明（U ) 八本，明聚合物可與另外之聚合物摻合，其係包含不同刀子里及/或乙烯基或亞乙烯基芳族單體含量之其它異 ’、來物貝貝上無規之異種共聚物，乙烯基及亞乙烯基之齒化物聚合物（其包含（氣乙烯）及聚（偏氣乙烯）、聚乙烯及其匕來烯烴，其包含LDPE及HDPE、PP、藉由二茂金 =錯合物催化劑製得之均f乙烯職之共聚物，包含貝貝線II乙烯/ α _烯烴共聚物及藉由齊格勒催化劑製得之非均貝之乙烯/α _稀煙共聚物；$乙烯聚合物，包含聚苯稀SB S /、♦物、聚喊、聚碳酸酯、聚苯胺、柏油或其等之任何混合，但不限於此。本發明之異種共聚物或其摻合物可被製成各種不同型式，包含薄膜、纖維、發泡體、片材、射出成型物件、膜、射出吹模物件及壓出型材及乳化液，但不限於此。本 &月之異種共聚物或其摻合物之應用包含抗燃燒物件、壓感性膜原料、塗覆組成物或塗料、地板、天花板及牆壁覆蓋物、地毯襯底、障敝物、襯墊、封蓋及密閉物，但不限於此，且藉由添加傳導性添加劑（諸如，碳黑）各種傳導性應用（包含電裝置、導體護罩、絕緣護罩及其它電線及纜線應用。其它應用包含作為聚苯乙烯及乙烯及/或α -烯烴之均聚物及共聚物之摻合物之相容劑。亦被包含者係磺化竹生物之應用’包含其用於燃料電池之膜、吸水應用及 H VAC設備。決定本發明之乙烯/苯乙烯異種共聚物之組成使用 NMR分析方法可能不明確。此不確性係因苯乙烯三單元 K--------------------訂---------線 J (請先閱讀背面之注意事項再填寫本頁)-l · --- ^ ------- 1 1® ^ -------- Order --------- Line 1 ·: --- Bu --- >- -------------- (Please read the notes on the back before filling out this page) 527366 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description ('Clb: Geigy, Registration Trademarks), ν · ν · stabilizing zibu cling additives (such as k /, butene), q activators (such as erucamide and / or stearylamine), anti-ghost d coloring agents, colorants Additives such as tackifiers, flame retardants, and coupling agent fillers and plasticizers can be included in the composition of the present invention. Possible components of the composition of the present invention are various organic and inorganic fillers. These fillers Representative examples include organic and inorganic fillers such as' asbestos ink, ceramics, glass, metal (such as stainless steel) or polymers (such as aromatic polyamide fibers), talc, slave black, carbon fibers, Calcium carbonate, alumina trihydrate, glass fiber, marble gray cement ash, clay, feldspar, stone spar or glass, smoky stone spar, emulsified aluminum, magnesia, hafnium oxide, antimony oxide, zinc oxide, Barium acid, stone acid acid, acid acid, titanium dioxide, osmium salt, nitrogen oxide, B203, powder or chalk. Other representative organic or inorganic fiber or mineral fillers include carbonates (such as barium, calcium Or magnesium carbonate); borate (such as magnesium or zinc borate), fluoride (such as calcium or sodium aluminum fluoride); hydroxide (such as aluminum hydroxide); metal (such as aluminum , Bronze, lead, or zinc); oxides (such as aluminum, antimony, magnesium, or zinc oxides), or silicon or titanium dioxide; silicates (such as asbestos, mica, clay (kaolin or sintered) Kaolin), calcium silicate, feldspar, glass (ground or flaky glass or hollow glass spheres or microspheres or beads, whiskers or filaments), kaleite, perlite, pyrophyllite, talc or calcium silicon Stone); sulfates (such as barium or calcium sulfates); metal sulfides; cellulose (types of wood or shell powder); calcium terephthalate; and liquid crystals. More than one of these fillers The paper size of the mixture applies to Chinese national standards CNS) A4 size (210 X 297 public love). —1® ^ ^ ----------------- · --------------- (Please read the notes on the back before filling in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527366 Α7 _ Β7 V. Invention Description (1Q) can also be used. Fillers can also be used with coupling agents and / or starting Agents (which are selected from organic peroxides, silanes, titanates, zirconates, polyfunctional vinyl compounds, organic azides, and mixtures thereof). Other additives include hindered amine stabilizers. These stabilizers include hindered triazines (such as substituted triazines and reaction products of triazines). Suitable reaction products include reaction products of triazine with, for example, diamines and / or cycloaliphatic compounds such as cyclohexane. Particularly suitable hindered amine stabilizers include 1,3-propanediamine, 1-,-1,2-ethanediylbis-cyclohexane, and butyl peroxide-2,2,6,6- The reaction product of tetramethyl-4-pyridinamine-2,4,6-trichloro-1,3,5 · tri-hex, which is made by Ciba-Geigy and has the name "CG-116," which Has CAS Reg No: 191680-81-6. These additives are used at functional equivalents known to those skilled in the art. For example, the amount of antioxidant used is to avoid polymer or polymer blends during polymerization. The temperature and the amount of oxidation reaction during storage and final use during the environment. This content of antioxidant is generally based on the weight of the polymer or polymer blend in the range of 0.00 to 10% by weight Preferably, it is 0.05 to 5% by weight, and more preferably 0.1 to 2% by weight ❶ / ❶. Similarly, the amount of any other listed additives is the functional equivalent, such as pushing the polymer or compound The amount of anti-caking, producing the desired result, and providing the desired color by the colorant or colorant. These additives are suitably based on the weight of the heteropolymer A range of 0.05 to 50 wt% of the use, the preferred line square "to 35 wt%, more preferably 1.2 to square-based 20% by weight. The filler may be suitably used in a range of 1 to 90% by weight. This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 13 III ϋ ϋ i I 1 III ϋ ϋ ϋ — ϋ ϋ · 1 ϋ I ϋ n ϋ ϋ I ^ 1 ϋ ϋ n ϋ ϋ I 1 I ϋ ϋ ϋ I ι (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527366 A7 " --- 2Z____ V. Description of the Invention (U) Eight copies, Ming polymerization It can be blended with other polymers, which include other iso's, vinyl and vinylic copolymers with different contents in different knives and / or vinyl or vinylidene aromatic monomer content. Vinyl dentate polymers (including (gas ethylene) and poly (vinylidene)), polyethylene and its olefins, which include LDPE, HDPE, PP, and are prepared by using a ferrocene = complex catalyst Copolymers of average ethylene content, including Beibei line ethylene / α_olefin copolymers and non-uniform ethylene / α_lean smoke copolymers prepared by Ziegler catalysts; $ ethylene polymers, including Polystyrene SB S /, polystyrene, polycarbonate, polycarbonate, polyaniline, asphalt or any combination thereof The heterogeneous copolymer or its blend of the present invention can be made into various types, including films, fibers, foams, sheets, injection molded articles, films, injection blow molded articles, and presses. Profiles and emulsions, but not limited to this. Applications of this & month's hetero-copolymers or blends thereof include anti-combustion articles, pressure-sensitive film materials, coating compositions or coatings, flooring, ceiling and wall coverings , Carpet substrates, barriers, pads, covers, and enclosures, but not limited to them, and by adding conductive additives such as carbon black, various conductive applications (including electrical devices, conductor shields, insulation Shrouds and other wire and cable applications. Other applications include compatibilizers as blends of homopolymers and copolymers of polystyrene and ethylene and / or alpha-olefins. Also included are sulfonated bamboo organisms Applications' include its use in fuel cell membranes, water absorption applications, and H VAC equipment. The composition of the ethylene / styrene heteropolymers of the present invention may not be determined using NMR analysis methods. This uncertainty is due to the styrene triad K -------------------- --------- set line J (Please read the Notes on the back to fill out this page)

527366 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（12 )527366 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (12)

組及更高等級之苯乙烯***於iH及13C皆具有波峰，其無法自以小含量存在於異種共聚物内之遍及之非結晶性無規立構聚苯乙烯均聚物（aPS)之波峰區分。但是，使用液體色譜術（LC，其係使用梯度溶劑極性）能使異種共聚物與aPS 分離’且異種共聚物波峰之滯留時間係指示其苯乙烯含量〇本發明之異種共聚物組成物包含5至85(較佳係20至85 ’更佳係50至85)莫耳％之至少一乙烯基或乙烯基或亞乙烯基芳族單體及15至95(較佳係15至80，更佳係15至50)莫耳％之乙烯及/或至少一具有3至2〇個碳原子之脂族α -烯烴〇本發明異種共聚物之熔融指數（〗2)係大於〇〇5，較佳係0.5至200，更佳係〇·5至1〇〇克/1〇分。本發明異種共聚物之分子量分佈（Mw/Mn)係1.5至20 ，較佳係1.8至10，更佳係2至5。本發明之異種共聚物組成物含有可檢測之乙烯基芳族單體三單元組。於乙烯/苯乙烯異種共聚物之情況中，此係相對應於-SSS-三單元組。此等三單元組亦可為乙烯基或亞乙烯基芳族***之較長序列（諸如，SSSSw單元組、SSSSS五單元組）之一部份。當任何無規立構之聚苯乙烯雜質與聚合物分離，此等三單元組可藉由i3C NMR之波峰存在而檢測之，其係產生於相對應K44 6ppm之乙烯/ 苯乙烯異種共聚物聚合物主幹（ESSSE)之次甲基碳之化學位移。 (請先閱讀背面之注音？事項再填寫本頁) --------^---------^—--------------------Groups and higher grades of styrene have peaks when inserted in iH and 13C, which cannot be found throughout the small amount of non-crystalline atactic polystyrene homopolymer (aPS) that is present in heterogeneous copolymers distinguish. However, the use of liquid chromatography (LC, which uses a gradient of solvent polarity) allows the heteropolymer to be separated from the aPS ', and the residence time of the heteropolymer peak indicates the styrene content. The heteropolymer composition of the present invention contains 5 To 85 (preferably 20 to 85 ', more preferably 50 to 85) mole% of at least one vinyl or vinyl or vinylidene aromatic monomer and 15 to 95 (preferably 15 to 80, more preferably 15 to 50) mole% of ethylene and / or at least one aliphatic α-olefin having 3 to 20 carbon atoms. The melt index ([2]) of the heteropolymer of the present invention is greater than 0.05, preferably It ranges from 0.5 to 200, more preferably from 0.5 to 100 g / 10 minutes. The molecular weight distribution (Mw / Mn) of the heterogeneous copolymer of the present invention is 1.5 to 20, preferably 1.8 to 10, and more preferably 2 to 5. The heterogeneous copolymer composition of the present invention contains a detectable vinyl aromatic monomer triad. In the case of an ethylene / styrene heteropolymer, this corresponds to the -SSS-triad. These triads can also be part of a longer sequence (such as SSSSw, SSSSS pentad) of vinyl or vinylidene aromatic insertion. When any atactic polystyrene impurity is separated from the polymer, these triads can be detected by the presence of the peak of i3C NMR, which is generated by the corresponding K44 6ppm ethylene / styrene heteropolymer polymerization Chemical shift of the methine carbon in the substance backbone (ESSSE). (Please read the Zhuyin on the back? Matters before filling out this page) -------- ^ --------- ^ ------------------ ----

527366 五、發明說明（13 ) 下列範例係例示說明本發明，但非用以以任何方式限制其範圍。範例厕試方法本發明聚合物組成物之分子量係使用紫外線及反射才曰數檢測器之凝膠渗透色譜術便利地指示。為決定本發明異種共聚物之13C NMR化學位移，下列程序及條件被使用。5至1〇重量％之聚合物溶液於含有5〇體積/〇之1，1，2,2_四氯乙烷-^及⑽體積％之於三氣苯内之0.10莫耳二（乙醯基丙酮）鉻之混合物内製得。光譜於13(TC時使用逆式閘去偶合序列（9()。_脈衝寬度及5秒或更多之延遲）獲得。光譜係指於30.000ppm時所指定之聚合物之被隔離之伸甲基訊號。物料測試聚合物樣品係藉由於150 °C時使用10分鐘預熱、於 1000磅力量之3分鐘壓縮之壓縮模製及立即冷卻而形成物理性質決定時所需之形狀。此聚合物之差式掃描熱量術（DSC)於5°c /分之加熱速率及使用杜邦儀器91 〇差式掃描熱量計於氮氛圍下施行之。所有樣品係經由二加熱循環（以移除先前加熱歷史之作用）取侍，且數據對於所有情況之第二次掃瞄報告。裱抗張測試係使用對每一 ASTM D638測試草案使用壓縮模製微抗張棒施行之。樣品於室溫時使用Μ· 54〇7 系列儀裔（0.1英口寸/分之十字頭速率及224·8石旁之負載元 -1¾ (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本紙張尺度適用中國國家標準規^*10 χ 297公冗-- 訂---------線 -----^----------------- 527366 A7 B7 五、發明說明（14 ) 拉伸。平應變破裂韌性、密實之張力單一端緣刻痕幾何樣品被壓縮模製成1” x 1” X 1/8”之矩形。此等矩形被機械製造以提供用以附接至測試裝置之側刻痕及孔洞。預破裂於每一樣品中藉由以液態氮冷卻及以安全刮刀及槌子破裂而形成。破裂韌性測試係使用0.02英吋/分之十字頭速率及 224.8石旁負載單元之instron 8501儀器施行之。動力機械光譜術於矩形棒施行之，其係於l〇〇°C壓縮模製。-100°C至150°C範圍之溫度掃瞄以1拉德/秒之設定頻率及以DMS儀器設定之自動應變函數施行之。密度係使用氦比重瓶測量。Rockwell硬度使用ASTM D785-93 評估。 L.C.分析 0.100及0.102克間之聚合物於30毫升玻璃瓶内稱重。 10亳升之THF被添加。此玻璃瓶被封蓋且置於加熱搖動器上’以便溶解樣品。加熱搖動器之溫度係65°C。溶解後，約1毫升之溶液被轉移至HP 1090 LC自動注射瓶。具有二極體陳列檢測器之Hewlett-Packard 1090 LC(系列號 2541A00700)被用以收集所有色譜術數據。訊號於254nm 及400nm收集。色譜術數據使用Grams 386及Excel軟體處理。二管柱被用以藉由液體色譜術決定樹脂之苯乙烯含量。任一管柱之使用起始係包含決定無規立構聚苯乙烯含量（其波峰係可清淅辨別）。然後，此數值自以13C N.M.R. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (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 - . ----- ϋ I ·1 n 1 ϋ I 線·111 Ί------------------ 17 527366 A7 經濟部智慧財產局員工消費合作社印製 —-------- -五、發明說明（15 ) 決定之樣品之總苯乙烯含量扣除，產生共聚合苯乙烯之重量％。共聚合苯乙烯對滯留時間（於第50百分位數值之色譜波峰）之校正曲線被建構，然後形成之調整被應用於所有新的樣品。此分析使用二型式管柱施行之。此專之第一者係C18管柱，其係自Alltech: Spherisorb 〇DS II 5微米，250 x 4.60mm獲得。於C18管柱上具有防護皆柱。此係RP 8.5微米。下述係用於具C18管柱之HP1090 上使用之儀器條件。溶劑A=乙腈於24.00 流動=1.000 溶劑B=THF 於 24·00%Β=100·0,0= 溶劑C=2-丙醇於25.00 流動=1.000 貯存流1 ; 於25·00ο/〇Β=1·0，00.0 f止時間=30.00 於30.00流動=1.000 後時間=0.0 於30·00ο/〇Β=1·0，00·0 SDS-Config A=l? B=l? C=1 最大壓縮=400 停止時間=系統最小壓縮=8 後時間=1.00分 Β=1·〇, C=0.0 自動平衡=打開注射體積=10.001 波峰寬度=0.100 爐溫度=50.0 光譜範圍=240, 600, 2 於1.00流動=1.000毫升/分貯存光譜=波峰於 1.00%B=1.0, C=0.0 臨界值=1.000 於20.00 流動=1.000 訊號Α=254, 4, 550, 20 於20.00% B=100.0, 00.0 訊號Β=400, 4, 550, 20 此二者之第二及最佳之管柱係自Phenomenex: Nucleosil 5 N02 250 X 4.60mm，5微米，序號243745獲得之硝基管柱。其於硝基管柱上具有防護管柱。其係 Phenomenex Nucleosil 5 N02 30x 4.6nm，5微米 100埃，序本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 18 (請先閱讀背面之注意事項再填寫本頁) _啜訂---- 線垂--------------- 527366 A7 B7 五、發明說明（16 ) 號2437470。下述係於具14汾〇2方法（硝基管柱）之1^1090 上使用之儀器條件。經濟部智慧財產局員工消費合作社印製溶劑A=己烧於24.00 流動=1.000 溶劑B=THF 於24·00%Β=70·0, 00.0 溶劑C=2-丙醇於23.00 流動=1.000 貯存A 1 ; 於23.00%B=70.0，C=0.0 貯存B 1 ; 於24.00 流動=1.000 貯存C 1 ; 於24.00%B=3.0, C=0.0 貯存流1 ; 於30.00 流動=1.000 貯存溫度1 ; K30.00%B=3.0，C=0.0 停止時間=30.00分後時間=0.0分 SDS-Config A=l，B=l，C=1 停止時間=系統流動=1.000毫升/分後時間=1.00分最大壓縮=400巴自動平衡=打開最小壓縮=8 波峰寬度=0.100 百分率 B=3.0，C=0.0 光譜範圍=240, 600, 2 注射體積lO.ODI 貯存光譜=波峰爐溫度=30.0 c 臨界值=1.000 於 1.00 流動=1.000 訊號A=254, 4, 550, 20 於 1·00%Β=1·0, C=0.0 臨界值=1.000 於 1.00%B=3.0，C=0.0 訊號B=400, 4, 550, 20 用以於此管柱上決定苯乙烯含量之回歸方程式係： [苯乙烯]重量％=-84.89 + 10.98*滯留時間（分）製備本發明異種共聚物之範例1-6 Π製備催化劑合成及操作係於惰性氛圍（氬）套箱内完成。溶劑係購自Aldrich. Liquid試劑，且溶劑先以氮飽和，然後於使用前藉由通過活化氧化銘乾燥（如Pangborn，A.B.; Giardello, (請先閱讀背面之注意事項再填寫本頁) t527366 V. Description of the invention (13) The following examples illustrate the invention, but are not intended to limit its scope in any way. Example Toilet Test Method The molecular weight of the polymer composition of the present invention is conveniently indicated by gel permeation chromatography using ultraviolet and reflection detectors. To determine the 13C NMR chemical shift of the heteropolymer of the present invention, the following procedures and conditions were used. 5 to 10% by weight of the polymer solution in 0.1,2,2,2-tetrachloroethane- ^ and ⑽% by volume of 0.10 mole of diethylbenzene (acetamidine) Acetone) chromium in a mixture. The spectrum was obtained at 13 (using the inverse gate decoupling sequence (9 () ._ pulse width and 5 seconds or more delay) at TC. The spectrum refers to the isolated extension of the specified polymer at 30.000 ppm Basic signal. The material test polymer sample was formed into the shape required by the physical properties by compression molding and immediate cooling with a 10 minute preheat at 150 ° C, a 3 minute compression at 1,000 pounds of force. This polymer Differential Scanning Calorimetry (DSC) was performed at a heating rate of 5 ° C / min and using a DuPont Instrument 91 ° Differential Scanning Calorimeter under a nitrogen atmosphere. All samples were passed through a two-heating cycle (to remove the previous heating history) Function) and the second scan report of the data for all cases. The mounted tensile test was performed using compression molded micro-tensile rods for each ASTM D638 test draft. Samples were used at room temperature. · 54〇7 series Yiyi (0.1 inch inch / min crosshead speed and 224.8 stone next to the load element-1¾ (Please read the precautions on the back before filling out this page) Intellectual Property Bureau Staff Consumer Cooperatives Printed paper ruler Applicable to Chinese National Standards ^ * 10 χ 297 public redundant-order --------- line ----- ^ ----------------- 527366 A7 B7 V. Description of the invention (14) Stretching. Flat strain fracture toughness, compact tension, single end edge notched geometric samples are compression molded into a 1 "x 1" X 1/8 "rectangle. These rectangles are mechanically manufactured To provide side nicks and holes for attachment to the test device. Pre-fractures were formed in each sample by cooling with liquid nitrogen and rupturing with a safety blade and mallet. The fracture toughness test uses 0.02 inches per minute The crosshead speed and the 224.8 stone-side load cell are implemented by the instron 8501 instrument. Power mechanical spectroscopy is performed on rectangular rods, which are compression-molded at 100 ° C. Temperature sweeps in the range of -100 ° C to 150 ° C Aiming at a setting frequency of 1 rad / sec and an automatic strain function set by a DMS instrument. Density is measured using a helium pycnometer. Rockwell hardness is evaluated using ASTM D785-93. LC analysis of polymers between 0.100 and 0.102 grams Weigh in a 30 ml glass bottle. 10 liters of THF is added. This glass bottle is capped and placed on a heating shaker ' The sample was dissolved. The temperature of the heating shaker was 65 ° C. After dissolution, about 1 ml of the solution was transferred to the HP 1090 LC auto-injection bottle. Hewlett-Packard 1090 LC with diode display detector (serial number 2541A00700) It was used to collect all chromatographic data. Signals were collected at 254nm and 400nm. Chromatographic data were processed using Grams 386 and Excel software. Two-column columns were used to determine the styrene content of the resin by liquid chromatography. The starting system for the use of any column includes determining the amount of atactic polystyrene (whose peaks are clearly discernible). Then, this value is based on 13C NMR. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page.) -. ----- ϋ I · 1 n 1 ϋ I line · 111 Ί ------------------ 17 527366 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs —---------V. Description of the invention (15) The total styrene content of the sample determined is subtracted to produce the weight% of copolymerized styrene. Copolymerized styrene vs. residence time (chromatographic peak at 50th percentile value) calibration curves were constructed, and the resulting adjustments were applied to all new samples. This analysis was performed using a two-type column. The first of these is a C18 column, which was obtained from Alltech: Spherisorb 〇DS II 5 microns, 250 x 4.60mm. Protected on C18 column. This series is RP 8.5 microns. The following conditions apply to the HP1090 with C18 column. Solvent A = acetonitrile flowing at 24.00 = 1.000 Solvent B = THF at 24.0% B = 100 · 0, 0 = Solvent C = 2-propanol flowing at 25.00 = 1.000 Storage stream 1; at 25 · 00ο / 〇Β = 1 · 0，00.0 f stop time = 30.00 flow at 30.00 = 1.000 time = 0.0 at 30 · 00ο / 〇Β = 1 · 0，00 · 0 SDS-Config A = l? B = l? C = 1 maximum compression = 400 Stop time = System minimum compression = 8 After time = 1.00 minute B = 1 · 〇, C = 0.0 Auto balance = Open injection volume = 10.001 Peak width = 0.100 Furnace temperature = 50.0 Spectral range = 240, 600, 2 at 1.00 Flow = 1.000 ml / min Storage spectrum = peak at 1.00% B = 1.0, C = 0.0 critical value = 1.000 at 20.00 flow = 1.000 signal A = 254, 4, 550, 20 at 20.00% B = 100.0, 00.0 signal B = 400, 4, 550, 20 The second and best column is the nitro column obtained from Phenomenex: Nucleosil 5 N02 250 X 4.60mm, 5 microns, serial number 243745. It has a protective tube column on the nitro tube column. It is Phenomenex Nucleosil 5 N02 30x 4.6nm, 5 microns and 100 angstroms, and the paper size of the sequence is applicable to China National Standard (CNS) A4 (210 X 297 mm) 18 (Please read the precautions on the back before filling this page) Ordering ---- line hanging 527366 A7 B7 V. Invention Description (16) No. 2437470. The following are the conditions of the instrument used on 1 ^ 1090 with the 14 Fen 02 method (nitro column). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Solvent A = Hexane at 24.00 Flow = 1.000 Solvent B = THF at 24 · 00% B = 70 · 0, 00.0 Solvent C = 2-propanol at 23.00 Flow = 1.000 Storage A 1; Store B 1 at 23.00% B = 70.0, C = 0.0; Store C 1 at 24.00 flow = 1. Store C 1 at 24.00% B = 3.0, C = 0.0 Store flow 1; Store at 10.00 = 1.000 Storage temperature 1; K30. 00% B = 3.0, C = 0.0 Stop time = 30.00 minutes time = 0.0 minutes SDS-Config A = l, B = l, C = 1 Stop time = system flow = 1.000 ml / minute time = 1.00 minute maximum compression = 400 bar auto-balance = open minimum compression = 8 peak width = 0.100 percent B = 3.0, C = 0.0 spectral range = 240, 600, 2 injection volume lO.ODI storage spectrum = wave furnace temperature = 30.0 c critical value = 1.000 in 1.00 mobile = 1.000 signal A = 254, 4, 550, 20 at 1.00% B = 1 · 0, C = 0.0 critical value = 1.000 at 1.00% B = 3.0, C = 0.0 signal B = 400, 4, 550 , 20 The regression equation used to determine the styrene content on this column: [styrene] wt% =-84.89 + 10.98 * residence time (minutes) Example 1-6 for preparing heterogeneous copolymers of the present invention Synthesis and agents operating in an inert atmosphere (Argon) tank complete sets. The solvent was purchased from Aldrich. Liquid reagent, and the solvent was saturated with nitrogen, and then dried by activating the oxidized oxide before use (such as Pangborn, A.B .; Giardello, (Please read the precautions on the back before filling this page) t

一OJa ϋ ϋ I ϋ I I _1 ϋ ϋ ϋ ϋ .^1 ϋ ϋ n ϋ ·ϋ ϋ ϋ ^1 ϋ ^1 ϋ ·ϋ a— -I I 19 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 527366 A7 ___B7 _ 五、發明說明（17 ) M.A.; Bmbbs，R.H·; R0sen，R.K; Timmers，F丄於方襪金屬，1996，15，1518-1520所揭示者）。於使用前，含氘之苯於鈉/鉀合金上乾燥並過濾之。伸f基菲購自Lancaster. 配位子及金屬錯合物之NMR光譜於周圍條件時於Vadan 300 MHz NMR光譜計上記錄。共聚物之NMR光譜於 Bruker 600 MHz光譜計上記錄。合成伸甲基菲鋰於存在於50毫升己烷内之4,5·伸甲基菲（〇·485克，255 毫莫耳）添加1.6Μ之於己烷内之n-BuLi (175毫升，2·8〇毫莫耳）。於周圍條件攪拌1天後，溶液出現較深之橙色且小篁之橙色沈澱物形成。於14天後，更多之沈澱物被形成。此藉由使上清液自黏於燒瓶内壁之固體傾析出而隔離。於在減壓下乾煉後，〇·430克被隔離（86%產率）。揮發性物料自上浮液移除以產生撥色固體。此物料之質子Nmr分析顯示其係起始之伸甲基菲。合成（4,5-伸甲基菲基）（第三丁基胺）二甲基矽烷於30亳升THF内之（第三丁基胺基）二甲基矽烷基氣化物（0.436克，2.63毫莫耳）添加櫻桃紅之於2〇毫升THF内之鋰伸甲基菲（0.430克，2.19毫莫耳）溶液。溶液於周圍溫度攪拌隔夜。揮發性物料於減壓下移除。固體殘質於1〇毫升己燒内形成淤漿，且揮發性物料於減壓下移除。固體殘質以總量為30亳升之己烷萃取兩次。萃取物被過濾且揮發性物料於減壓下自混合之過濾物移除，產生〇·69〇克（99。/〇產率）之橙色油。1H NMR光譜係與所欲產物一致。本紙張尺度適用中國國家標準（CNS)A4規格（21〇 χ 297公釐） (請先閲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 • 1111111 11111111 I — — — — — — — — — — — — — — — — — — — — — — 20一 OJa ϋ ϋ I ϋ II _1 ϋ ϋ ϋ ϋ. ^ 1 ϋ ϋ n ϋ · ϋ ϋ ϋ ^ 1 ϋ ^ 1 ϋ · ϋ a— -II 19 This paper standard applies to China National Standard (CNS) A4 (210 X 297 mm) 527366 A7 ___B7 _ 5. Description of the invention (17) MA; Bmbbs, RH ·; R0sen, RK; Timmers, F (disclosed in Sock Metal, 1996, 15, 1518-1520). Before use, benzene containing deuterium is dried over sodium / potassium alloy and filtered. The NMR spectra of the diphenanthrene were purchased from Lancaster. The ligands and metal complexes were recorded on a Vadan 300 MHz NMR spectrometer at ambient conditions. The NMR spectrum of the copolymer was recorded on a Bruker 600 MHz spectrometer. Synthesized methylphenanthrene in 4,5 · methylenephenanthrene (0.548 g, 255 mmol) in 50 ml of hexane was added with 1.6M n-BuLi (175 ml, 2.80 millimoles). After stirring under ambient conditions for 1 day, a darker orange color and a smaller orange precipitate formed in the solution. After 14 days, more precipitate was formed. This was isolated by decanting the supernatant from the solids adhering to the inner wall of the flask. After drying under reduced pressure, 0.430 g was isolated (86% yield). Volatile materials are removed from the float to produce a colored solid. Proton Nmr analysis of this material shows that it is the starting methylphenanthrene. Synthesis of (Third-Butylphenanthryl) (Third-Butylamine) Dimethyl Silane (Third-Butylamino) Dimethyl Silane Vapor in 30 liters of THF (0.436 g, 2.63 Millimolar) A solution of cherry red methylphenanthrene (0.430 g, 2.19 mmol) in 20 ml of THF was added. The solution was stirred at ambient temperature overnight. Volatile materials were removed under reduced pressure. The solid residue formed a slurry in 10 ml of hexane, and the volatile materials were removed under reduced pressure. The solid residue was extracted twice with a total of 30 liters of hexane. The extract was filtered and the volatile material was removed from the mixed filter under reduced pressure, yielding 0.69 g (99% / yield) of an orange oil. The 1H NMR spectrum was consistent with the desired product. This paper size applies to China National Standard (CNS) A4 (21〇χ 297 mm) (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 • 1111111 11111111 I — — — — — — — — — — — — — — — — — — — — 20

經濟部智慧財產局員工消費合作社印製 a成[(4,5-伸甲基菲基）[(第三丁基醯胺基）二甲基矽烷]鈦雙（二甲基醯胺）於50亳升正辛烷内之鈦四醯胺（〇·484克，216亳莫耳) 及（4,5-伸甲基菲基）（第三丁基胺基）二甲基矽烷（〇·69〇克， 2.16¾莫耳）之溶液被加熱且於迴流時攪拌。此反應過程藉由移除小的整份溶液、於減壓下移除揮發性物料及於 C6D6内分析殘質而以m NMR光譜監測之。質子1^/[尺分析顯示α析轉化成所欲產物（例如，於約4 $小時迴流後之 55%轉化率）。數滴鈦四醯胺被週期性添加。於迴流數天後，反應似乎不會進行超過82%轉化率。揮發性物料於減壓下自冷卻混合物移除。殘質被溶於2〇亳升之己烷内且形成之混合物被過濾。揮發性物料於減壓下自過濾物移除，產生暗色粉末（0.950克）。產物之質子NMR分析顯示其係所欲產物及起始配位子之混合物，個別為82/18莫耳％(87 重量％之所欲產物）。合成[(4,5-伸曱基菲基）[(第三丁基醯胺基）二甲基矽烷]鈦二氯化物於溶於40亳升己烷内之上述隔離之雙（醯胺）/配位子混合物（0.83克，ι·83毫莫耳之雙（醯胺））添加三甲基矽烷基氣化物（1.33亳升，ι〇·5毫莫耳）。溶液於迴流攪拌6小時。小的等份之冷卻溶液被移除且揮發性物料於減壓下被移除。殘質被溶於C0F6内且以屮NMR光譜術分析。光譜顯不非常清楚之轉化成單氣化物-單醯胺中間產物。另外之 1 _3毫升之二甲基矽烷基氯化物被添加且被密封之容器於本紙張尺度適时_家標準（CNS)A4規格⑽χ297公爱） 21 ----I —--------^--------- (請先閱讀背面之注意事項再填寫本頁) 527366 A7 五、發明說明（19 周圍/JDL度撥拌8天。然後，溶液被加熱迴流6天。冷卻溶液被置於套箱冷凍器（-25X：)内。形成之固體藉由真空過濾於燒結玻璃上收集。固體殘質以冷己烷（約1〇亳升）清洗一次，然後，固體於減壓下乾燥而產生0.516克（65%產率）。質子NMR分析顯示物料係與非常乾淨之所欲產物一致。合成[(4,5-伸甲基菲基）（第三丁基醯胺基）_二甲基石夕烧]二甲基鈦於30亳升THF内之二氣化物（〇·516克，1.18毫莫耳）添加3 ·0Μ之甲基鎮氣化物（〇,87宅升，2.6亳莫耳），其形成中間產物之顏色變化。於靜置隔夜後，揮發性物料於減壓下移除。固體殘質於己烷内形成淤漿，且揮發性物料於減壓下移除。殘質以己烧萃取數次。萃取物被過濾且揮發性物料於減壓下自混合過濾物移除，產生鮮撥色粉末（〇·392克）。C0D6内之質子及13C之NMR分析顯示所欲產物係以之與THF而成之加成物隔離。假定分子量係467 6克/莫耳，被隔離之產率係71 %。THF加成物（〇··345克）被溶於50毫升，且於迴流加熱6小時。由撥色變成棕黃色之顏色變化被觀察到。揮發性物料於減壓下移除。殘質之質子NMr 分析顯示完全之轉化成新化合物。 2)聚合反應下述溶劑及溶液之所有轉化係使用乾燥純化之氮或氬之氣墊完成。供應之反應器之氣體供料藉由通過A-204 氧化铭及Q 5反應物之管柱而純化。氧化紹係於先前於3 7 5 °0以氮活化，且Q5反應物係於200°C以氮内之5%氫活化。 22 (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本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） I I I I II ϋ^0、> ϋ ϋ H ϋ ϋ I 線丨. — — — "τι------------------ 527366 A7 B7 _ 五 '發明說明（20 ) 催化劑及共催化劑（三（五氟苯基）硼烷）之操作係於惰性氛圍套箱内完成。半批次反應器聚合反應係於二公升之parr反應器（其具有電加熱套管、冷卻用之内部彎曲線圈及底排冰閥）進行。壓力、溫度及阻斷閥係藉由電腦監測控制。Is〇par E 及苯乙烯於溶劑注射槽（裝配至平衡）内測量。然後，形成之浴液自溶劑注射槽添加至反應器。反應器内容物於12〇〇 rpm擾拌。氫藉由差式膨脹（約口⑽psi)自起始為3〇〇 psig 之75毫升注射槽添加。然後，反應器之内容物於所欲乙烯壓力下加熱至所欲操作溫度（9〇。〇。經濟部智慧財產局員工消費合作社印製催化劑’ [(4,5-伸甲基菲基）（第三丁基醯胺基）_二甲基矽烷]二甲基鈦，及共催化劑，三（五氟苯基硼烷，於套箱内混合（於甲苯内之〇·〇〇5〇μ溶液）且經由1/6英吋（0.16公分）管線且使用甲苯促進轉移而自套箱轉移至催化劑注射槽。然後，催化劑槽使用氮加壓，於反應器内容物於所欲操作溫度穩定化後’催化劑溶液經由浸潰管注射於反應器内。溫度藉由使冷的二醇通過内部冷卻線圈而保持之。反應以依需求之乙婦進行所欲時間。於操作期間以相同方式使另外添加之催化劑被製得及添加之。然後’反應裔内容物被排入4公升之氣充氣之容器且以異丙基醇驟冷，且於甲苯内之1〇〇毫克之Irgan〇x 1〇1〇被添加作為抗氧化劑。揮發性物料於140°C真空爐内自聚合物移除，且於自該爐移除前冷卻至5〇°c。反應器條件及聚合反應數據係如第1表所示。 23Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as [(4,5-Methylphenanthrene) [(Third Butylamido) dimethylsilane] Titanium Bis (dimethylamidoamine) at 50 Titanium tetramethylamine (0.484 g, 216 mol) in n-octane and (4,5-methylphenanthryl) (third butylamino) dimethylsilane (0.69 〇g, 2.16¾ mole) solution was heated and stirred under reflux. This reaction process was monitored by m NMR spectroscopy by removing small entire solutions, removing volatile materials under reduced pressure, and analyzing the residues in C6D6. Analysis of protons 1 ^ / [ruler analysis shows that the alpha analysis is converted to the desired product (for example, a 55% conversion rate after about 4 hours of reflux). A few drops of titanium tetrafluorene are added periodically. After several days at reflux, the reaction did not appear to proceed beyond 82% conversion. Volatile materials are removed from the cooled mixture under reduced pressure. The residue was dissolved in 20 liters of hexane and the resulting mixture was filtered. Volatile materials were removed from the filter under reduced pressure to produce a dark powder (0.950 g). Proton NMR analysis of the product showed that it was a mixture of the desired product and the starting ligand, each 82/18 mole% (87% by weight of the desired product). Synthesis of the above isolated bis (fluorenylamine) [(4,5-fluorenylphenanthryl) [(third butylphosphoniumamino) dimethylsilane] titanium dichloride in 40 liters of hexane / Legand mixture (0.83 g, ι · 83 mmol of bis (fluorenamine)) was added with trimethylsilyl gaseous (1.33 liters, ι 0.5 mmol). The solution was stirred at reflux for 6 hours. Small aliquots of the cooling solution were removed and the volatile materials were removed under reduced pressure. The residue was dissolved in COF6 and analyzed by Er NMR spectroscopy. The spectrum was not very clearly converted to the mono-gas-monoamine intermediate. In addition, 1_3 ml of dimethylsilyl chloride is added and the sealed container is timely at the size of this paper _ house standard (CNS) A4 specification ⑽χ297 public love) 21 ---- I ------- --- ^ --------- (Please read the notes on the back before filling this page) 527366 A7 V. Description of the invention (19 around / JDL degree stir for 8 days. Then, the solution is heated to reflux 6 The cooling solution was placed in a box freezer (-25X :). The formed solid was collected by vacuum filtration on sintered glass. The solid residue was washed once with cold hexane (about 10 liters), and then, The solid was dried under reduced pressure to yield 0.516 g (65% yield). Proton NMR analysis showed that the material was consistent with the very clean desired product. Synthesis [(4,5-methylphenanthrene) (third butyl Hydrazine group) _dimethyllithium sulfide] dimethyl titanium in 30 liters of THF (0. 516 g, 1.18 mmol) was added with 3.0 M of methyl ballast 87 liters, 2.6 mol), which changes the color of the intermediate product. After standing overnight, the volatile materials are removed under reduced pressure. The solid residue forms a sludge in hexane. And the volatile material was removed under reduced pressure. The residue was extracted several times with hexane. The extract was filtered and the volatile material was removed from the mixed filter under reduced pressure to produce a freshly colored powder (〇 · 392 g ). Protons in COD6 and 13C NMR analysis show that the desired product is isolated from the THF adduct. Assuming a molecular weight of 467.6 g / mole, the isolated yield is 71%. THF addition The material (0 ·· 345 g) was dissolved in 50 ml and heated at reflux for 6 hours. A color change from color shifting to brownish yellow was observed. Volatile materials were removed under reduced pressure. Analysis of residual protons NMr Complete conversion to a new compound is shown. 2) Polymerization All conversions of the solvents and solutions described below were performed using a dry purified nitrogen or argon air cushion. The gas supply to the supplied reactor was purified by passing through a column of A-204 oxide and Q 5 reactants. The oxide was previously activated with nitrogen at 3 7 5 ° 0, and the Q5 reactant was activated at 200 ° C with 5% hydrogen in nitrogen. 22 (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 x 297 mm) IIII II ϋ ^ 0, > ϋ ϋ H ϋ ϋ I line 丨. — — — " τι ------------------ 527366 A7 B7 _ Five 'invention description (20) catalyst and co-catalyst ( The operation of tris (pentafluorophenyl) borane) is completed in an inert atmosphere box. The semi-batch reactor polymerization was performed in a two-liter parr reactor (which has an electrically heated jacket, an internal curved coil for cooling, and a bottom ice discharge valve). Pressure, temperature and shut-off valves are controlled by computer monitoring. Is〇par E and styrene were measured in a solvent injection tank (assembled to equilibrium). Then, the formed bath was added to the reactor from the solvent injection tank. The reactor contents were stirred at 12,000 rpm. Hydrogen was added by differential expansion (approximately psi) from a 75 ml injection tank starting at 300 psig. Then, the contents of the reactor are heated to the desired operating temperature under the desired ethylene pressure (90.0). The catalyst is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs' [(4,5-methylphenanthrene) Tertiary butylamido) dimethylsilane] dimethyl titanium, and a co-catalyst, tris (pentafluorophenylborane), were mixed in a set box (a 0.005 μm solution in toluene ) And transferred from the casing to the catalyst injection tank via a 1/6 inch (0.16 cm) line and using toluene to facilitate the transfer. Then, the catalyst tank was pressurized with nitrogen and the reactor contents were stabilized at the desired operating temperature. 'The catalyst solution is injected into the reactor through the impregnation tube. The temperature is maintained by passing the cold diol through an internal cooling coil. The reaction is performed as needed for the desired time. Additional additions are made in the same manner during operation The catalyst was prepared and added. Then the contents of the reaction mixture were discharged into a 4 liter gas-filled container and quenched with isopropyl alcohol, and 100 mg of Irgan 0x 1 in toluene. 〇Added as an antioxidant. Volatile Removing material from the polymer in a vacuum oven at 140 ° C, and removed before cooling to 5〇 ° c in a furnace from the reactor and the polymerization reaction conditions as shown in the first line of data in Table 23

I I (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） 6 6 73 2 5 五 A7 ----21___________發明說明（22 ) 藉由此等含aPS之共聚物之資料，於其i3c nmr光譜内之sss三單元體波峰能被指定。非常小之eee三單元組之波峰指示異種共聚物具有非常少之短乙烯序列。此等物料皆展現小含量之結晶性或係非結晶性。結果，此等聚合物之密度隨增加之苯乙烯含量而增加且達 1.06克/cc之密度（aps密度）。分子量數據顯示催化劑能產生高分子量之聚合物。因為雙檢測器被用於GPC分析，其可能檢測分子量範圍之反射‘數除以UV回應值之比例。此比例被發現不會改變太多’其表示組成於整個分子量範圍係相對較均勻；於非常低分子量之苯乙婦含量之些微增加可見於所有範例。此係與此等物料中之aPS存在一致。物料性質以DSC決定之熱轉移係如第III表所示。 (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第III表熱轉移（DSC) 範例苯乙烯 (莫耳％) 苯乙烯 (重量％) Tg，。C Tm，。C □Hf，J/g 1 24.7C 54.9C 31.9 123 26.5 2 45.8C 75.9C 32.5 119 1.7 3 53·8Α(49·0)Β 81·2α(78·1)β 39.7 — 麵· 4 56·6α(52·5)β 82.9a(80.4)b 44.2 — 一 5 63.5Α(60.2)Β 86.6A(84.9)B 55.5 — —— 6 74.6α(73·1)β 91·6α(91·0)β1 70.3 — — A自無硝基管柱之LC數據 B自具C18管柱之LC數據 C自質子NMR數據 -> I n I ϋ · n ϋ -ϋ ϋ ϋ I ϋ II ϋ ^1 I I n l^i n ϋ ϋ ϋ ·ϋ ^1 ϋ I n ϋ ^1 ϋ n 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 25 527366 A7 B7 五、發明說明（23 ) 如預期’此等物料之Tg被發現隨增加之苯乙烯含量而增加。於最後二記載者（其係遠超過較早之假無規物料之組成範圍）顯示於苯乙烯含量達接近1〇〇0/〇時，Tg快速達 aPS(約l〇〇°C )者。需注意無一物料顯示顯著之Tg，其係因 aPS均聚物之故。但是，LC數據顯示於隔離物料中之aps 。具最高結晶性之聚合物（最低苯乙烯含量55重量。/(>8)展現接近120°C之波峰溶融溫度及接近32°c之Tg。微抗張測試及破裂韌性測試被施行以評估此等物料之機械性質’第IV表。短期抗張分析顯示對於最高達約2% 應變之所有物料之於低抗張應力時之高模量之相對較具玻璃性之回應及相對較具線性之應力/應變關係。所有此等物料之楊氏模量係於350,000-430,000 pSi (2.4-3 GPa)範圍内。所有物料係於相對較低之應變時進行延展性屈服，且屈服應變隨增加之苯乙烯含量穩定地移至較低之延長。所有聚合物展現通過屈服點之些微拉升至最終失敗。第IV表微抗張、破裂韌性及硬度數據 (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範例苯乙烯重量％屈服應力 (psi) 屈服時之應變％破裂應力(psi) 破裂時之應變％楊氏模量 (sd) 硬度 1 54.9 - - - • 56 2 75.9 - - - 86 3 78.1 6,870 2.7 6,720 3.1 347,000 (33,000) 86 4 80.4 6,950 2.3 6,550 2.9 365,000 (48,000) 89 5 84.9 7,130 2.1 6,540 4.9 434,000 (36,000) 100 6 91.0 6,320 1.9 6,250 2.5 376,000 (68,000) 99 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） • I 1_ϋ ϋ ϋ ϋ I I i_n n ϋ ·1_ I I ϋ —ϋ ϋ 1 ϋ i^i n ammmf n ϋ I I i^i I I- I _ 26 °^366II (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 6 6 73 2 5 Five A7 ---- 21___________ Description of Invention (22 ) With this information of aPS-containing copolymers, the sss triad peaks in its i3c nmr spectrum can be specified. The peaks of the very small eee triad indicate that the heteropolymer has very few short ethylene sequences. These materials all show a small amount of crystalline or non-crystalline. As a result, the density of these polymers increased with increasing styrene content and reached a density (aps density) of 1.06 g / cc. The molecular weight data show that the catalyst can produce high molecular weight polymers. Because the dual detector is used for GPC analysis, it is possible to detect the ratio of the reflection 'number of the molecular weight range divided by the UV response value. This ratio was found not to change too much 'which indicates that the composition is relatively uniform over the entire molecular weight range; a slight increase in the content of acetophenone at very low molecular weight can be seen in all examples. This is consistent with the aPS in these materials. Material properties The heat transfer determined by DSC is shown in Table III. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Form III Thermal Transfer (DSC) Example Styrene (mol%) Styrene (wt%) Tg. C Tm ,. C □ Hf, J / g 1 24.7C 54.9C 31.9 123 26.5 2 45.8C 75.9C 32.5 119 1.7 3 53 · 8Α (49 · 0) B 81 · 2α (78 · 1) β 39.7 — surface · 4 56 · 6α (52 · 5) β 82.9a (80.4) b 44.2 — 1 5 63.5A (60.2) B 86.6A (84.9) B 55.5 — —— 6 74.6α (73 · 1) β 91 · 6α (91 · 0) β1 70.3 — — A from LC data without nitro column B from LC data with C18 column C from proton NMR data-> I n I ϋ · n ϋ -ϋ ϋ I ϋ II ϋ ^ 1 II nl ^ in ϋ ϋ ϋ · ϋ ^ 1 ϋ I n ϋ ^ 1 ϋ n This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 25 527366 A7 B7 V. Description of the invention (23) As expected 'this The Tg of such materials was found to increase with increasing styrene content. The last two recorders (which are far beyond the composition range of the earlier fake random materials) show that when the styrene content reaches close to 1000/0, the Tg quickly reaches aPS (about 100 ° C). It should be noted that none of the materials showed significant Tg due to the aPS homopolymer. However, the LC data shows the aps in the segregated material. The polymer with the highest crystallinity (minimum styrene content of 55 weights // > 8) exhibits a peak melting temperature close to 120 ° C and a Tg close to 32 ° c. Micro-tensile test and fracture toughness test were performed to evaluate Mechanical properties of these materials' Table IV. Short-term tensile analysis shows a relatively glassy response and a relatively linear response to high modulus at low tensile stress for all materials up to about 2% strain Stress / strain relationship. The Young's modulus of all these materials is in the range of 350,000-430,000 pSi (2.4-3 GPa). All materials undergo ductile yielding at relatively low strains, and the yield strain increases with The styrene content has steadily moved to a lower extension. All polymers exhibit some slight pull-up through the yield point to eventual failure. Table IV Microtensile, fracture toughness, and hardness data (Please read the precautions on the back before filling (This page) Sample printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Weight percent of styrene. Yield stress (psi). Strain at yield.% Rupture stress (psi). Strain at break.% Young's modulus (sd). Hardness 1 54.9---• 56 2 75.9---86 3 78.1 6,870 2.7 6,720 3.1 347,000 (33,000) 86 4 80.4 6,950 2.3 6,550 2.9 365,000 (48,000) 89 5 84.9 7,130 2.1 6,540 4.9 434,000 (36,000) 100 6 91.0 6,320 1.9 6,250 2.5 376,000 (68,000) 99 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) • I 1_ϋ ϋ ϋ II i_n n ϋ · 1_ II ϋ —ϋ ϋ 1 ϋ i ^ in ammmf n ϋ II i ^ i I I- I _ 26 ° ^ 366

⑴貫張力幾何樣品測量。此等實驗被 4成！化聚合物之對於有關施用負載之破裂開始及增生之抗r生。此測補對聚合物之壓縮模製矩形施行，其係被 W刻痕’刀片被用以產生於Μ型刻痕之破裂。然後，抗張負载被施於平面應力之樣品；被製得之樣品理想之厚度系足X避免自^以負载之平面扭曲。負載及替換間形成之關係月b决定用以增生破裂所需之立即應力，其被稱為應力強度因子K1C。亦有用者係界定於指定單位面積上延伸破裂所需能量；此數量係被稱為Gle(破裂能量或臨界應變· 月b里釋放率）’且其與Klc之關係係如方程式丨所示：破裂韋刃性使用宓警 (請先閱讀背面之注咅？事項再填寫本頁) t 經濟部智慧財產局員工消費合作社印製Continuous tension geometry measurement. These experiments were 40%! The resistance of chemical polymers to the onset of rupture and proliferation associated with the applied load. This test is performed on a polymer compression-molded rectangle, which is used by W-notch ' blades to produce cracks in M-notch. Then, the tensile load is applied to the sample with plane stress; the ideal thickness of the prepared sample is enough to avoid plane distortion caused by the load. The relationship between the load and the replacement month b determines the immediate stress required to accumulate the fracture, which is called the stress intensity factor K1C. It is also useful to define the energy required to extend the rupture on a specified unit area; this quantity is called Gle (breaking energy or critical strain · release rate in months b) 'and its relationship with Klc is shown in equation 丨: Use of the police for breaking and cutting edge (please read the note on the back? Matters before filling out this page) t Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Gic=(Klc2/E)(l-D2) (1) 其中E係揚氏模量，且□□係Poisson比例。Klc及GU 之較大值表示增加之破裂韌性。破裂韌性測量未顯示物料之隨被測試樣品之有意義之差異。第V表係具最高苯乙烯含量之四樣品之臨界應力強度因子（K1C)值，及高分子量自由基聚合之聚苯乙烯均聚物之相同測試條件下獲得之數據。共聚物顯示相當較高之K1C及G1C值，及對屈服及破裂之負載量對於共聚物係比聚苯乙烯均聚物更高。有關聚苯乙烯之此等物料之改良韌性可自被併入之乙烯單位之對於破裂測試之時間規格之被施加應力誘發更具延展性之回應之能力產生。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 27 一：口，I ^1 ^1 ^1 ϋ Μϋ I ϋ I ϋ I ϋ I -ϋ n ϋ 11 ιϋ ϋ— ϋ>1 ^^1 i^i ϋ 1 527366 A7 B7 五、經濟部智慧財產局員工消費合作社印製發明說明（25 第V表ES共聚物之破裂韌性數據範例苯乙烯重量％ Klc (Mpa m0.5) 最大負載(碎）屈服點能量 (磅-英吋）破裂能量 (石旁一英口寸） GlcA (J/m2) 範例3 78.1 2.9 59.5 0.95 2.9 3,130 範例4 80.4 2.8 67.6 1.3 2.8 2,770 範例5 84.9 3.4 56.8 0.94 2.1 3,430 範例6 91 2.9 46.6 0.97 2.6 2,880 比較例1 100Β 2.2 28.7 0.34 0.52 l，400c A使用測付之杨氏椒1及〇·33之p〇isson比例計算 B 自由基aPS，Mn=114,720，Mw=282,970，Mw/Mn =2.47 C自Klc使用高分子量PS之公告楊氏模量值（3 i(}pa) 及Poisson比例（0.33)計算（聚合物科學及工程百科全書，第 16冊，第 2版，John Wiley & Sons，1989,第 1-246 頁）非結晶異種共聚物之DMS分析被施行以決定玻璃轉移之位置及鑑定與此等物料有關之其它轉移。玻璃轉移溫度及室内副-Tg儲存模量隨共聚物内增加之苯乙烯含量而增加。於非結晶ES共聚物之剪切損失模量（G”）回應中，此等物料之玻璃轉移溫度被清楚觀察，且寬的□□轉移可於約-50 C及室溫間看到。於聚苯乙烯中，轉移被歸因於主幹鬆弛，其係伴隨苯基環之變位。本發明之高笨乙烯含量異種共聚物之物理性質指示具有改良之抗破裂性。此建議此等異種共聚物可於某些應用提供獨特之實用性。最高苯乙烯含量時之非結晶性異種Gic = (Klc2 / E) (l-D2) (1) where E is Young's modulus and □□ is Poisson ratio. Higher values of Klc and GU indicate increased fracture toughness. Fracture toughness measurements did not show significant differences in the material depending on the sample being tested. Table V is the data obtained under the same test conditions for the critical stress intensity factor (K1C) values of the four samples with the highest styrene content and high molecular weight free-radically polymerized polystyrene homopolymers. The copolymers show considerably higher K1C and G1C values, and the load on yield and cracking is higher for copolymers than for polystyrene homopolymers. The improved toughness of these materials related to polystyrene can result from the ability of the incorporated ethylene units to induce a more malleable response to the time specifications of the burst test. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 27 I: Mouth, I ^ 1 ^ 1 ^ 1 ϋ Μϋ I ϋ I ϋ I ϋ I -ϋ n ϋ 11 ιϋ ϋ — ϋ > 1 ^^ 1 i ^ i ϋ 1 527366 A7 B7 V. Printed invention description printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (25 Table V Example of fracture toughness data of ES copolymers Table styrene weight% Klc (Mpa m0.5) Maximum load (fragmentation) Yield point energy (lb-inch) Break energy (one inch by the stone) GlcA (J / m2) Example 3 78.1 2.9 59.5 0.95 2.9 3,130 Example 4 80.4 2.8 67.6 1.3 2.8 2,770 Example 5 84.9 3.4 56.8 0.94 2.1 3,430 Example 6 91 2.9 46.6 0.97 2.6 2,880 Comparative Example 1 100B 2.2 28.7 0.34 0.52 l, 400c A Calculated B radical aPS using measured Young's pepper 1 and 0.33 poisson ratio, Mn = 114,720 , Mw = 282,970, Mw / Mn = 2.47 C Calculated from Klc using high molecular weight PS announced Young's modulus value (3 i (} pa) and Poisson ratio (0.33) calculation (Encyclopedia of Polymer Science and Engineering, Volume 16 , 2nd ed., John Wiley & Sons, 1989, pp. 1-246) DMS analysis of amorphous heteropolymers Determine the location of the glass transition and identify other transitions related to these materials. The glass transition temperature and the indoor sub-Tg storage modulus increase with increasing styrene content in the copolymer. Shearing in amorphous ES copolymers In the response to the loss modulus (G "), the glass transition temperature of these materials was clearly observed, and a wide □□ transition can be seen at about -50 C and room temperature. In polystyrene, the transition is attributed It relaxes in the trunk, which is accompanied by the displacement of the phenyl ring. The physical properties of the high-density ethylene content heteropolymer of the present invention indicate improved crack resistance. It is suggested that these heteropolymers can provide unique properties in certain applications. Practicality. Amorphous heterogeneity at the highest styrene content

本紙張尺度-巾目时標⑽X 297·：θ)-ΠΓ：---J (請先閱讀背面之注意事項再填寫本頁) -0 ^1 ^1 ϋ ϋ eat^r«»J ϋ ϋ ϋ I ϋ ϋ I ϋ I n I ϋ n ϋ n — ϋ I I n ϋ ϋ n 1.. ^27366Scale of this paper-Time scale of towel head 巾 X 297 ·: θ) -ΠΓ: --- J (Please read the notes on the back before filling this page) -0 ^ 1 ^ 1 ϋ ϋ eat ^ r «» J ϋ ϋ ϋ I ϋ ϋ I ϋ I n I ϋ n ϋ n — ϋ II n ϋ ϋ n 1 .. ^ 27366

-— JL 五、發明說明（26 ) 一"""' — 、♦物係透明的’如此此等聚合物於膜應用中具使用性且 ;有關aPS中係有利白勺’因為其增加之拿刃性之故。再者，此等新聚合物之發泡體片材可顯示比們片材更佳之彈性，且可於其間需改良之則性之應用中較佳施行之。若展 :見可相容性之組成物可被發現時，此等聚合物亦可被用於早刃化aPS，同時保持良好之透明性。 -------^------1-------訂---------線 I I (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本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 29--- JL V. Description of the invention (26) a " " " '-, the transparent system' so that these polymers are useful in film applications, and the relevant aPS system is advantageous because of its The reason for the increase in edge. Moreover, these new polymer foam sheets can show better elasticity than our sheets, and can be better implemented in applications where the regularity needs to be improved. If the composition is found to be compatible, these polymers can also be used for early sharpening aPS while maintaining good transparency. ------- ^ ------ 1 ------- Order --------- Line II (Please read the precautions on the back before filling this page) Ministry of Economy Wisdom The paper size printed by the Property Cooperative Consumer Cooperative is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 29

Claims

A B CD 527366 令告本I— —、屮清專4範圍第089112202號專利申請案申請專利範圍修正本修正日期：91年9月 1· 一種異種共聚物，包含：亂9, 2兗 (1) 5至85莫耳％之衍生自至少一乙烯基或亞乙烯基芳族單體之聚合物單元， (2) 15至95莫耳％之衍生自乙烯及/或C32〇 α •烯烴之至少一者之聚合物單元；及 (3) 〇至20莫耳％之衍生自一或多者之非衍生自（1) 及（2)者之乙烯不飽和可聚合單體之聚合物單元；且其中該異種共聚物含有可檢測之乙烯基或亞乙烯基芳族單體三單元組。 2·如申請專利範圍第1項之異種共聚物，其中 (1) 組份（1)包含2〇至85莫耳％之衍生自以下述化學式表不之該乙烯基或亞乙烯基芳族單體之聚合物單元： At (CH2)n R1 — C = C(R2)2 其中’ R1係選自氫及含有1至4個碳原子之烷基；每一R2係個別選自氫及具有1至4個碳原子之烷基；Ar係苯基或以1至5個選自！|基、Cl_4之烷基及Cl_4之i烷基之取代基取代之苯基；且11係具有0至4之數值； (2) 15至80莫耳％之衍生自乙烯及/或包含丙烯、4-曱基-1-戊烯、丁烯<、己烯或辛烯―丨之至少一者之該本紙張尺度適用中國國豕標準（CNS ) A4規格（210X297公餐) ~ " -30 - I I I I I I IAB CD 527366 Order I——Qi Qingzhuan 4 Scope No. 089112202 Patent Application Application Amendment of the Patent Scope Amendment Date: September 91 1. A heterogeneous copolymer, including: Random 9, 2 兖 (1) 5 to 85 mole% of polymer units derived from at least one vinyl or vinylidene aromatic monomer, (2) 15 to 95 mole% of polymer units derived from ethylene and / or C32〇α (3) 0 to 20 mol% of polymer units derived from one or more of the ethylene unsaturated polymerizable monomers not derived from (1) and (2); and wherein The heterogeneous copolymer contains a detectable vinyl or vinylidene aromatic monomer triad. 2. The heterogeneous copolymer according to item 1 of the scope of patent application, wherein (1) component (1) contains 20 to 85 mol% derived from the vinyl or vinylidene aromatic monomer represented by the following chemical formula Polymer units: At (CH2) n R1 — C = C (R2) 2 where 'R1 is selected from hydrogen and alkyl groups containing 1 to 4 carbon atoms; each R2 is individually selected from hydrogen and has 1 Alkyl to 4 carbon atoms; Ar is phenyl or selected from 1 to 5! A phenyl group substituted with a substituent of an alkyl group of Cl_4 and an alkyl group of Cl_4; and 11 is a value of 0 to 4; (2) 15 to 80 mol% derived from ethylene and / or containing propylene, The paper size of at least one of 4-fluorenyl-1-pentene, butene <, hexene, or octene is applicable to China National Standard (CNS) A4 (210X297 meal) ~ "- 30-IIIIIII

ABC D 527366 χ、申請專利範圍 a-烯烴之聚合物單元；及 (3)該非衍生之（1)及（2)者之乙烯不飽和可聚合單體’其包含降冰片烯或烷基或c6_1G芳基取代之降冰片烯。 3·如申請專利範圍第1項之異種共聚物，其中： (1) 組份（1)包含50至85莫耳％之衍生自該乙烯基芳族單體之聚合物單元，該單體包含苯乙烯、α -甲基苯乙烯、鄰_、間-及對-甲基苯乙烯，及環鹵化苯乙烯， (2) 15至50莫耳％之衍生自乙烯或乙烯及該α -烯烴之聚合物單元，該α-烯烴係包含乙烯或乙烯及丙烯、 4-甲基-1-戊烯、丁烯d、己烯或辛烯之至少一者；及 (3) 該非衍生之（1)及（2)者之乙烯不飽和可聚合單體係降冰片烯。 4·如申請專利範圍第3項之異種共聚物，其中該組份（1) 係苯乙烯；且組份（2)係乙烯。 5·如申請專利範圍第3項之異種共聚物，其中該組份（1) 係苯乙烯；且組份（2)係乙烯及丙烯、4-甲基-1-戊烯、丁細-1、己烯-1或辛稀·1之至少一者。 6· —種異種共聚物，其係藉由聚合下述者而製得： (a) 至少一乙烯基或亞乙烯基芳族單體 (b) 乙烯及/或C3_2〇a -烯烴之至少一者，及 (c) 選擇性一或多者之非衍生自（1)及（2)者之乙烯不飽和可聚合單體；本紙張尺度適用中國國家標準（CNS) A4規格（21〇χ297公爱）ABC D 527366 χ, a polymer unit of a patented a-olefin; and (3) the non-derived ethylene unsaturated polymerizable monomer of (1) and (2), which contains norbornene or alkyl or c6_1G Aryl substituted norbornene. 3. The heterogeneous copolymer according to item 1 of the scope of patent application, wherein: (1) component (1) contains 50 to 85 mol% of a polymer unit derived from the vinyl aromatic monomer, the monomer comprising Styrene, α-methylstyrene, o-, m-, and p-methylstyrene, and cyclohalogenated styrene, (2) 15 to 50 mol% derived from ethylene or ethylene and the α-olefin A polymer unit, the α-olefin system comprising at least one of ethylene or ethylene and propylene, 4-methyl-1-pentene, butene d, hexene, or octene; and (3) the non-derived (1) And (2) the ethylenically unsaturated polymerizable single system norbornene. 4. The heterogeneous copolymer according to item 3 of the application, wherein the component (1) is styrene; and the component (2) is ethylene. 5. The heterogeneous copolymer according to item 3 of the patent application, wherein the component (1) is styrene; and the component (2) is ethylene and propylene, 4-methyl-1-pentene, butylene-1 , At least one of hexene-1 or dilute · 1. 6. A heterogeneous copolymer prepared by polymerizing: (a) at least one vinyl or vinylidene aromatic monomer (b) at least one of ethylene and / or C3_2〇a-olefin And (c) optionally one or more non-ethylenically unsaturated polymerizable monomers derived from (1) and (2); this paper size applies the Chinese National Standard (CNS) A4 specification (21〇297297) Love)

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申請專利範圍其係於包含[(4,5-伸曱基-菲基）（第三丁基醯胺基）一曱基石夕烧]二甲基鈦之催化劑存在中進行之。如申請專利範圍第6項之異種共聚物，其中： (a)該乙烯基或亞乙烯基芳族單體係以下述化學式表示： Ar (GH2)n R» _ c = C(R2)2 其中，R1係選自氫及含有1至4個碳原子之烷基；每一 R2係個別選自氫及具有1至4個碳原子之烷基；Ar係苯基或以1至5個選自鹵基、（^_4之烷基及Cw之鹵烷基之取代基取代之苯基；且η係具有0至4之數值； (b) 該α -烯烴，其包含丙烯、4-曱基-1-戊烯、丁烯-1、己稀-1或辛稀-1之至少一者； (c) 該非衍生之（1)及（2)者之乙烯不飽和可聚合單體’其包含降冰片烯或烧基或C6-10芳基取代之降冰片烯。 8·如申請專利範圍第7項之異種共聚物，其中該組份卜)係苯乙烯；且組份（b)係乙烯。 9·如申請專利範圍第7項之異種共聚物，其中該組份（心係苯乙烯；且該組份（b)係乙烯及丙烯、4-曱基-i_戊烯、丁稀-1、己烯·1或辛稀·1之至少一者。 1 〇· —種用以製備異種共聚物之方法，其係聚合下述者：本紙張尺度適用中國國家標準（CNS) Α4規格（21〇><297公瘦y ^27366 A8 B8 C8 ^------— 58 _— 申凊專利範圍 (a) 至少一乙烯基或亞乙烯基芳族單體， (b) 乙烯及/或（：3·2〇α-烯煙之至少一者，及 (c) 選擇性之一或多者之非衍生自（1)及（2)者之乙婦不飽和可聚合單體；其係於包含[(4,5·伸曱基-菲基X第三丁基醯胺基）二甲基矽烷]二甲基鈦之催化劑存在中進行之。 11·如申請專利範圍第1〇項之方法，其中： (a)該乙烯基或亞乙烯基芳族單體係以下述化學式表示： At I (CH2)n R1 — C = C(R2)2 其中’R1係選自氫及含有丨至4個碳原子之烷基；每一 R2係個別選自氫及具有1至4個碳原子之烷基；Ar. 苯基或以1至5個選自_基、Ci_4之烷基及Cm之_烷基之取代基取代之苯基；且η係具有〇至4之數值； (b) 該α -烯烴，其包含丙烯、4-曱基-1-戊烯、丁烯 •1、己稀-1或辛稀·1之至少一者； (c) 該非衍生之（1)及（2)者之乙烯不飽和可聚合單體’其包含降冰片烯或烷基或C6_1G芳基取代之降冰片烯。 12·如申請專利範圍第丨丨項之方法，其中該組份（a)係苯乙稀，且組份（b)係乙稀。本紙張尺度適用中國國家標準（CMS) A4規格（2ΐ〇χ297公爱) 33 527366 A B c D 、申請專利範圍 13.如申請專利範圍第11項之方法，其中該組份（a)係苯乙烯；且該組份（b)係乙烯及丙烯、‘甲基_卜戊烯、丁烯 -1、己稀-1或辛稀-1之至少一者。 14· 一種捧合物，包含： A) 申晴專利範圍第1項之異種共聚物；及 B) —或多者之另外之聚合物組份。 15·如申請專利範圍第14項之摻合物，其中該另外之聚合物 ’組份B，係選自實質無規異種共聚物、乙烯基及亞乙烯基之鹵化物、乙烯均聚物、α -烯烴均聚物、乙烯/α -烯烴共聚物、苯乙烯聚合物、聚醚、聚碳酸酯、聚苯胺、柏油或其等之任何混合。 16. —種過渡金屬錯合物，[(4,5_伸甲基-菲基）（第三丁基醯胺基）二甲基矽烷]二甲基鈦。 17. —種催化劑組成物，包含[(4,5-伸曱基-非基）（第三丁基醯胺基）二甲基矽烷]二甲基鈦。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297&I)Scope of patent application It is carried out in the presence of a catalyst containing [(4,5-phenylene-phenanthryl) (third butylphosphoniumamino), monomethylsulfonyl] dimethyl titanium. For example, the heterogeneous copolymer of item 6 in the patent application range, wherein: (a) the vinyl or vinylidene aromatic monosystem is represented by the following chemical formula: Ar (GH2) n R »_ c = C (R2) 2 where R1 is selected from hydrogen and alkyl groups containing 1 to 4 carbon atoms; each R2 is individually selected from hydrogen and alkyl groups having 1 to 4 carbon atoms; Ar is phenyl or selected from 1 to 5 A phenyl group substituted by a halo group, an alkyl group of C ^ _4, and a haloalkyl group of Cw; and η has a value of 0 to 4; (b) the α-olefin, which includes propylene, 4-fluorenyl- At least one of 1-pentene, butene-1, hexane-1 or octane-1; (c) the non-derived ethylene unsaturated polymerizable monomers of (1) and (2), Borne or norbornyl or C6-10 aryl-substituted norbornene. 8. The heterogeneous copolymer according to item 7 of the application, wherein the component b) is styrene; and component (b) is ethylene. 9. The heterogeneous copolymer according to item 7 of the scope of patent application, wherein the component (cardioid styrene; and the component (b) is ethylene and propylene, 4-fluorenyl-i-pentene, butylene-1 , At least one of hexene · 1 or dilute · 1. 1 〇 · ——A method for preparing heterogeneous copolymers, which polymerizes the following: This paper size applies the Chinese National Standard (CNS) A4 specification (21 〇 < 297 public thin ^ 27366 A8 B8 C8 ^ ------— 58 _— Patent application scope (a) at least one vinyl or vinylidene aromatic monomer, (b) ethylene and / Or (: at least one of 3.20α-enefene, and (c) one or more selective ethylenically unsaturated polymerizable monomers not derived from (1) and (2); It is carried out in the presence of a catalyst containing [(4,5 · fluorenyl-phenanthryl X third butyl fluorenylamino) dimethylsilane] dimethyl titanium. 11 · As in the first patent application scope The method of item, wherein: (a) the vinyl or vinylidene aromatic monosystem is represented by the following chemical formula: At I (CH2) n R1 — C = C (R2) 2 where 'R1 is selected from hydrogen and contains丨 Alkyl to 4 carbon atoms; each R2 is individually selected from hydrogen and alkyl having 1 to 4 carbon atoms; Ar. Phenyl or phenyl substituted with 1 to 5 substituents selected from _yl, Ci_4 alkyl, and Cm_alkyl ; And η has a value of 0 to 4; (b) the α-olefin, which contains at least one of propylene, 4-fluorenyl-1-pentene, butene • 1, hexane-1, or octane-1 (C) The non-derived (1) and (2) ethylene-unsaturated polymerizable monomers' which contains norbornene or an alkyl group or a C6_1G aryl-substituted norbornene. The method of item 丨丨, wherein the component (a) is styrene, and the component (b) is ethylene. This paper size is applicable to the Chinese National Standard (CMS) A4 specification (2ΐ〇χ297 公爱) 33 527366 AB c D. Patent application scope 13. The method according to item 11 of the patent application scope, wherein the component (a) is styrene; and the component (b) is ethylene and propylene, 'methyl_pentene, butyl At least one of olefin-1, hexane-1, or octane-1. 14. A support compound comprising: A) a heterogeneous copolymer in the scope of claim 1 of the Shenqing patent; and B) —or more Polymer group 15. The blend according to item 14 of the scope of patent application, wherein the additional polymer 'component B is selected from the group consisting of substantially random heteropolymers, vinyl and vinylidene halides, and ethylene homopolymers. , Alpha-olefin homopolymer, ethylene / alpha-olefin copolymer, styrene polymer, polyether, polycarbonate, polyaniline, asphalt or any mixture thereof. 16. A transition metal complex, [ (4,5-Methenyl-phenanthryl) (third butylamidino) dimethylsilane] dimethyl titanium. 17. A catalyst composition comprising [(4,5-fluorenyl-nonyl) (third butylamidino) dimethylsilane] dimethyl titanium. This paper size applies to China National Standard (CNS) A4 specification (210X297 & I)

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