TW200909460A - Solid catalyst component, catalyst for olefin polymerization, and process for producing olefin polymer using catalyst - Google Patents

Abstract

A solid catalyst component is prepared by contacting (a) a dialkoxy magnesium compound, (b) a tetra-valent titanium halide, and c an electron donor compound of the formula R1R2C(COOR3)(COOR4). A catalyst for olefin polymerization comprises the solid catalyst component, an organoaluminum compound having a formula R5pAlQ3-p, and an external electron donor compound. The catalyst for olefin polymerization is highly active and exhibits high activity for hydrogen. A polymer with high stereoregularity can be obtained at a high yield by polymerizing olefins using the catalyst.

Description

200909460 九、發明說明： 【發明所屬之技術領域】 本發明係關於活性高且對氣活 得高立體規則性聚合物之埽/ 、能夠以高產率獲 觸媒。 二艰σ用固體觸媒成分及 【先前技術】 習知，於丙烯等烯烴類之聚合時， 電子供應性化合物及鹵素作：必二:有含有鎂、鈦、 分。另外，提出有多個於包含該固體而刀之、固體觸媒成 合物及有機石夕化合物之稀烴類聚合用觸媒^在有機紹化 煙類聚合或共聚合之方法。例如，於專=二在J，使稀 分、有機純合物及嶋化合物之出丙觸媒成 烯之聚合方法，上述固體觸媒成 二σ觸媒與丙 使二烧氧基鎂、芳香族二二藉!，200909460 IX. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to a catalyst having high activity and high stereoactivity to a gas, and capable of obtaining a catalyst in a high yield. Solid catalyst component and the prior art It is known that in the polymerization of olefins such as propylene, the electron-donating compound and the halogen are: must contain magnesium, titanium, and a fraction. Further, there has been proposed a method of polymerizing or copolymerizing a plurality of organic hydrocarbons in a catalyst for the polymerization of a rare hydrocarbon polymer containing a solid, a solid catalyst compound and an organic compound. For example, in the polymerization method in which the dilute, the organic pure compound, and the ruthenium compound are formed into a propylene, the above solid catalyst is a bis-catalyst and a propylene-based bismuth oxide and aroma. Family two and two borrowed!,

C 鈦齒化物相接觸所獲得之生成物進行加熱處理而製備。 =而’作為内部電子供應性化合物，亦開發有使用丙二 -欠酉曰化合物代替習知之鄰苯二甲酸g旨化合物之烯烴聚合 用固體觸媒成分，於專利文獻2(曰本專利特表 200|0-516987號公報）中，揭示有包含支持於_化此上、 至少具有Τι-鹵素鍵之鈦化合物、及2_異丙基丙二酸二乙 酯之類之單烷基取代丙二酸二酯的固體觸媒成分。另外， 於專利文獻3(WO03/95504號公報）中，揭示有包含含有烷 氧基之鎂化合物、及2,2-二甲基丙二酸二乙酯等二烷基 97111247 5 200909460 取代丙二酸二酯之固體觸媒成分，上述含有燒氧基之鎮化 合物係使含有含函素之鈦化合物、金屬鎂、醇及相對於上 述金屬鎂1莫耳為0.0001克原子以上的_素原子之鹵素 及/或含i素之化合物反應而獲得。 另外，習知，關於丙二酸二酯，欲獲得2個酯殘基相互 不同者時，反應起始物質與目的生成物之2個酯殘基不同 者之沸點相近’因而有時難以進行分館。 然而，使用如上所述之觸媒所獲得之聚合物，除了汽車 或者家電製品等成型品以外’亦利用於容器或薄膜等各種 用途中。該等係將藉由聚合而生成之聚合物粉末加以溶 融並利用各種成型機而成型，尤其是於利用射出成型等 且製造大型之成型品時’有時要求溶融聚合物之流動性 (炫融流動速率）高，因此，進行多種研究以提高聚合物之 溶融流動速率。 溶融流動速率係大幅依存於聚合物之分子量。於 Ο :二:丙烯聚合時’一般添加氫作為生成聚合物之分子量 =劑二此時於製造低分子量之聚合物之情況下，即為了 =㈣融流動速率之聚合物，通常添加大量氫，值# 到其文全性而於反應器之耐壓 " 旦介六+ 』&方面存在限度，可添加之氫 里亦存在限制。因此’為了 輩驊夕八r 勹；外加更多虱，必須降低聚合之 早體之分壓，於此情況下生 用i #眛 广玍產性會下降。另外，就大量使 用虱之情況而言，亦存在成太士工 里便 開务出如下觸媒，該觸媒能夠係 流動速率之聚入物，即 夕里之虱來製以阿炝融 t 口物即所^對氫活性高，且能夠以高產 97111247 200909460 率獲得高立體規則性聚合物，但上述習知技術並未充 決該課題。 鮮 (專利文獻丨）日本專利特開昭63-3G1G號公報（申請專 利範圍） 月寻 (專利文獻2)日本專利特表2〇〇〇_516987號公報主 專利範圍） ％ (專利文獻3)W0t)3/955G4號公報（申請專利範圍） I7本毛月之目的在於解決上述習知技術中殘留之問題 點，提供具有更高之對氫活性、能夠以高產率獲得高立體 規則性之聚合物之烯烴類聚合用固體觸媒成分、聚合用觸 媒及使用其之烯烴類聚合體之製造方法。 【發明内容】 於上述實際情況中，本發明者為了解決上述習知技術中 所殘留之課題而反覆進行深人研究，結果發現，使用特定 之取代丙二酸二醋作為内部供體（inner donor)而製備之 〇固體觸媒成分具有極高之效果，可解決上述問題，從而完 成本發明。 即用以達成上述目的之本發明提供烯烴類聚合用固體 觸媒成77 |係使鎂化合物（a)、4價之_化鈦化合物⑻ 及以下述通式⑴表示之電子供應性化合物⑷相接 製備： R 丨 R2C(CO〇r3)(c〇〇r4)⑴ (式中，^及R2為齒素原子、碳數1至20之直鏈狀或支鍵 狀烧基 '環烧基、苯基、乙縣、烯丙基、芳烧基及取代 97111247 200909460 有1個或2個鹵素原子之碳數1至10之直鏈狀或支鏈狀 炫基之任一者’可相同或不同。R3表示碳數1〜3之烷基、 環烷基、乙烯基、烯丙基，為碳數2〜20之烷基、環烷 基本基、乙稀基、稀丙基、芳炫基之任一者，R3與R4 不同）。 另外，本發明提供烯烴類聚合用觸媒，其特徵在於係藉 由（A)上述固體觸媒成分、 (B) 以通式（2)表示之有機鋁化合物： R pA 1Q3-P (2) (式中’ R5表示碳數卜4之烷基，Q表示氫原子或者鹵 素原子，p為〇<pg3之實數）、以及 (C) 外部電子供應性化合物所形成。 另外，本發明提供烯烴類聚合體之製造方法，苴特徵在 於’於上料烴類聚合_叙存在下進行職類之聚 (j【實施方式】 作，，備：發明之烯烴類聚合用固體觸媒成分⑷(以 下，二稱：固體觸媒成分⑴」)時所使㈣ ='有時稱為「成分(a)」），可舉出二齒化鎮、二 烧基鎮、處化燒基録、每 氧、 一烷虱基鎂、二芳氧基鎂、卣化烷 氧基鎂或者脂肪酸鎂等。該等 化鎂、二齒化鎂與二燒氧、化s物之中，較佳為二齒 佳為二烷氧基鎂。 ·、之混合物、二烷氧基鎂，特 作為一烧氧基鎮，較佳為 為M通式Mg(〇i〇(〇R")(式中， 97111247 200909460 R及R"表示碳數丨〜10之烧基，可分別相同亦可不同） =不之化合物’更具體而言，可舉出二甲氧基鎂、二乙氧 二f二丙氧基鎂、二丁氧細、乙氧基甲氧基鎂、乙氧 氧基4美了氧基乙氧基鎂等。#夕卜，該等二烧氧基鎮 二、可為使金屬鎂於鹵素或者含鹵素之金屬化合物等之存 在下與醇反應而獲得去。s k _ 用或者併用2種以上。 以-、凡乳基鎮可單獨使 f) "於本务明中，製備固體觸媒成分（A)時所使用之 基鎖為顆粒狀或粉末狀，其形狀可使用不定形或者 古例如於使用球狀二烧氧基鎮之情況下，可獲得且 =良好之粒子形狀與窄粒度分布之聚合體粉末，聚^ Ϊ人聚合體粉末之處理操作性提高，可消除生成 “體粉末中所含有之微粉所引起之堵塞等問題。The product obtained by contacting the C-titanium toothing is heat-treated to prepare. = and 'as an internal electron-supply compound, a solid catalyst component for olefin polymerization using a propylene-anthracene compound instead of a conventional phthalic acid-g compound has been developed, and Patent Document 2 (Japanese Patent Application) JP-A-200-516987 discloses a monoalkyl-substituted C-containing compound which supports a titanium compound having at least a Τι-halogen bond and a 2-ethyl isopropylmalonate. A solid catalyst component of a diacid diester. Further, Patent Document 3 (WO03/95504) discloses a dialkyl group such as a magnesium compound containing an alkoxy group and diethyl 2,2-dimethylmalonate, which is substituted by a substituted alkyl group. The solid catalyst component of the acid diester, wherein the alkoxy group-containing compound is a titanium compound containing a functional element, a magnesium metal, an alcohol, and an atom of 0.0001 gram or more relative to the metal magnesium 1 molar. It is obtained by reacting a halogen and/or a compound containing an element. Further, it is conventionally known that, in the case of the malonic acid diester, when the two ester residues are different from each other, the boiling point of the difference between the reaction starting material and the two ester residues of the intended product is similar. . However, the polymer obtained by using the catalyst as described above is used in various applications such as containers and films, in addition to molded articles such as automobiles and home electric appliances. These polymers are melted by polymer powder produced by polymerization and molded by various molding machines, and in particular, when injection molding or the like is used to manufacture a large-sized molded article, the fluidity of the molten polymer is sometimes required (shadowing The flow rate is high, and therefore, various studies have been conducted to increase the melt flow rate of the polymer. The flow rate of the melt is greatly dependent on the molecular weight of the polymer. Ο Ο : 2: When propylene is polymerized, 'Generally add hydrogen as the molecular weight of the resulting polymer = Agent 2 At this time, in the case of producing a low molecular weight polymer, that is, a polymer having a flow rate of = (IV), a large amount of hydrogen is usually added. The value # is limited to the fullness of the reactor and the pressure resistance of the reactor. There are limits on the hydrogen that can be added. Therefore, it is necessary to reduce the partial pressure of the aggregated early body. In this case, the production of i #眛 广玍 will decline. In addition, in the case of a large number of use of cockroaches, there is also the following catalyst in the Chengtai Shili, the catalyst can be a concentration of the flow rate, that is, the 夕 虱 制 制 制 炝 炝 炝 炝 t t The material has high hydrogen activity and can obtain a high stereoregular polymer at a high yield of 97111247 200909460, but the above-mentioned prior art does not solve this problem. Japanese Patent Laid-Open Publication No. SHO 63-3G1G (Patent Application) Japanese Patent Application Publication No. JP-A No. Hei. No. Hei. No. Hei. No. 2,516,987 (Patent Document 3) W0t) No. 3/955G4 (Scope of Application) I7 The purpose of this month is to solve the problem remaining in the above-mentioned prior art, and to provide a polymerization which has higher hydrogen activity and can obtain high stereoregularity in high yield. A solid catalyst component for olefin polymerization, a catalyst for polymerization, and a method for producing an olefin polymer using the same. SUMMARY OF THE INVENTION In the above-mentioned actual circumstances, the inventors of the present invention repeatedly conducted intensive studies in order to solve the problems remaining in the above-mentioned prior art, and as a result, found that a specific substituted malonic acid diacetate was used as an internal donor. The prepared solid catalyst component has an extremely high effect and can solve the above problems, thereby completing the present invention. In other words, the present invention provides a solid catalyst for olefin polymerization, a magnesium compound (a), a tetravalent titanium compound (8), and an electron-donating compound (4) represented by the following formula (1). Preparation: R 丨R2C(CO〇r3)(c〇〇r4)(1) (wherein, ^ and R2 are a dentin atom, a linear or branched bond group of 1 to 20 carbon atoms, a cycloalkyl group, Phenyl, ethyl, allyl, aryl, and substituted 97111247 200909460 Any one of two or two halogen atoms having a straight or branched chain of 1 to 10' may be the same or different R3 represents an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group, a vinyl group, an allyl group, an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group, an ethylene group, a dilute group, and an aryl group. Either R3 is different from R4). Further, the present invention provides a catalyst for olefin polymerization, characterized by comprising (A) the above solid catalyst component, and (B) an organoaluminum compound represented by the formula (2): R pA 1Q3-P (2) (wherein R5 represents an alkyl group having a carbon number of 4, Q represents a hydrogen atom or a halogen atom, p is a real number of 〇<pg3), and (C) is formed by an external electron-donating compound. Further, the present invention provides a method for producing an olefin-based polymer, which is characterized in that it is subjected to a classification in the presence of a hydrocarbon-based polymerization (J [Embodiment], and is prepared as a solid for olefin polymerization of the invention. In the case of the catalyst component (4) (hereinafter, referred to as "solid catalyst component (1)"), (4) = 'sometimes referred to as "component (a)"), and the two-toothed town, the second-burning town, and the chemicalization are mentioned. Burning base, per oxygen, monoalkylmagnesium, diaryloxymagnesium, deuterated alkoxymagnesium or fatty acid magnesium. Among the magnesium oxide, the magnesium dicalcinate, and the di-oxygenated gas, the bis-alloy is preferably a di-alkoxy magnesium. · a mixture, a dialkoxymagnesium, especially as a burnt-oxygen town, preferably M formula Mg (〇i〇 (〇R") (wherein, 97111247 200909460 R and R" represents carbon number 丨~10 of the base, can be the same or different) = no compound 'more specifically, can be mentioned, magnesium dimethoxide, diethoxy di f dipropoxy magnesium, dibutoxy, ethoxy Magnesium methoxymagnesium, ethoxyoxy group 4 methoxy ethoxy ethoxylate, etc. #卜卜, these two alkoxylates can be used to make metal magnesium in the presence of halogen or halogen-containing metal compounds. The reaction is carried out with an alcohol to obtain sk _ or two or more kinds can be used in combination. -, where the emulsifiable base can be used alone, f) " in the present invention, the base used in the preparation of the solid catalyst component (A) The lock is in the form of granules or powder, and the shape thereof may be amorphous or ancient, for example, in the case of using a spherical bis-oxygen group, a polymer powder having a good particle shape and a narrow particle size distribution, and a poly- Ϊ The handling property of the human polymer powder is improved, and problems such as clogging caused by the formation of the fine powder contained in the bulk powder can be eliminated.

狀烷氧基鎂並非必須為圓球狀，亦可使用橢圓 盥;豆轴二々狀者。具體而言，該粒子之形狀，長軸徑1 。二:…比(1/w)為3以下，較佳為…，更佳W 者3Γ絲基^平均粒徑可使用1至 較佺為5至15〇 。於球狀二 其平均粒徑為U100 :乳絲U况下’ 10 5 A(\ 杈4·為5至50 // m，更佳為 粉少、二=，關於其粒度，較佳係使用微粉及粗 IS 布窄者。具體而言，以下之粒子物 為m:下…〇%以下。另一方面，10“m以上之粒子 為〇/〇以下，較佳為5%以下。進而若以In__表示 97111247 200909460 9 0 %時之粒徑 以下，較佳為 'Dl〇 2以 其粒度分布（此處，D90係以累計粒度為 係累計粒度為1 〇 %時之粒捏.），則為3 下。 如上所述球狀4氧基鎂之製造方法，例如揭示 ^利特開昭58-4觀號公報、日本專利特開昭Μ ^本 號公報、日本專利㈣平3 —74341號公報、日本專 千4-368391號公報、日本專利特開平8 —咖⑽號公汗 製備本發明中固體觸媒成分⑴時所使用之4 。 鈦化合物（b)係自以通式Ti(〇Rl2)nX4n( 1〜4之烧基，…氯、演、蛾等㈣原子，At $4之整數）表示之齒化鈦或烧氧基_化鈦群組中 化合物的1種或者2種以上。 具體而言，作為鹵化鈦，可例示四氣化鈦、四溴化鈦、 四碘化鈦等四_化鈦，作域氧基虐化鈦，可例示甲氧基 三氯化鈦、乙氧基三氯化鈦、丙氧基三氯化鈦、正丁氧： 三氣化鈦、二曱氧基二氣化鈦、二乙氧基二氣化鈦、二 氧基-乳化鈦、二正了氧基二氯化鈦、三甲氧基氯化欽、 ，乙氧基氣化鈦、三丙氧基氣化鈦、三正丁氧基氯化鈦 等。其中，較佳為四鹵化鈦，特佳為四氯化鈦。該等鈦化 合物可單獨使用或者併用2種以上。 製備本發明中之固體觸媒成分（A)時所使用之電子供應 性化合物（c)係以上述通式（1)表示之化合物。該等化合物 為二自素取代丙二酸二酯、烷基及鹵素取代丙二酸二酯、 烧基取代丙—酸二酯或鹵化烧基取代丙二酸二g旨等（以 97111247 200909460 下，亦稱為厂取代丙二酸二醋」）。 y2中’作為齒素原子，為氣原子、溪原子=之' 為氣原子及漠原子。另外上述通式二較: 1甲基或異丁基，R、甲基及第三丁 R:均為異丁基。另外nR2較佳為含有“固以上者之= 石厌、二級碳f者四級碳之碳數3〜10之支鏈狀烷基，特佳 為異丁基、第二丁基、異戊基、新戊基。另外，上述通式 (1)中，作為羰基之酯殘基之R3,較佳為碳數丨〜3之直鏈 狀或者支鏈狀烷基’具體為甲基、乙基、丙基、異丙基， 特佳為甲基或乙基。另外，y較佳為碳數2〜2〇之烷基， 特佳為碳數2〜8之直鏈狀或者支鏈狀烷基，具體為乙 基、丙基、丁基、戊基、己基、庚基、辛基、異丙基、異 丁基、異戊基、新戊基、異己基、異庚基、異辛基。 作為二_素取代丙二酸二酯之具體例，可舉出二氯丙二 酉文甲基乙醋、一氣丙二酸甲基丙g旨、二氯丙二酸曱基丁 酯、二氯丙二酸曱基異丁酯、二氣丙二酸曱基戊酯、二氯 丙二酸曱基新戊酯、二氯丙二酸曱基己酯、二氯丙二酸曱 基異己醋、二氣丙二酸曱基庚g旨、二氯丙二酸曱基異庚 酯、二氣丙二酸曱基辛酯、二氯丙二酸曱基異辛酯、二氯 丙二酸乙基丙酯、二氣丙二酸乙基丁酯、二氯丙二酸乙基 異丁酯、二氯丙二酸乙基戊酯、二氯丙二酸乙基新戊酿、 二氯丙二酸乙基己酯、二氣丙二酸乙基異己酯、二氯呙夂 酸乙基庚酯、二氯丙二酸乙基異庚酯、二氯丙二酸乙基辛 酯、二氣丙二酸乙基異辛酯、二溴代丙二酸曱基乙酯、二 97111247 11 200909460 溴代丙二酸曱基丙酯、二溴代丙二酸曱基丁酯、二溴代丙 二酸曱基異丁酯、二溴代丙二酸曱基戊酯、二溴代丙二酸 曱基新戊酯、二溴代丙二酸曱基己酯、二溴代丙二酸曱基 異己酯、二溴代丙二酸甲基庚酯、二溴代丙二酸甲基異庚 酯、二溴代丙二酸曱基辛酯、二溴代丙二酸曱基異辛酯、 二溴代丙二酸乙基丙酯、二溴代丙二酸乙基丁酯、二溴代 丙二酸乙基異丁酯、二溴代丙二酸乙基戊酯、二溴代丙二 (酸乙基新戊酯、二溴代丙二酸乙基己酯、二溴代丙二酸乙 基異己酯、二溴代丙二酸乙基庚酯、二溴代丙二酸乙基異 庚酯、一溴代丙二酸乙基辛酯、二溴代丙二酸乙基異辛酯 等。 " 作為烷基及鹵素取代丙二酸二酯之具體例，可舉出乙基 氣代丙二酸甲基乙酯、乙基氣代丙二酸曱基丙酯、乙基氣 代丙一酸甲基丁酯、乙基氯代丙二酸乙基丁酯、乙基氣代 丙一酸乙基異辛酯、乙基溴代丙二酸曱基乙酯、乙基溴代 丙二酸甲基丙酯、乙基溴代丙二酸甲基丁酯、乙基溴代丙 二酸乙基丁酯、乙基溴代丙二酸乙基異辛酯、異丙基氣代 丙一酸甲基乙酯、異丙基氯代丙二酸曱基丙酯、異丙基氣 代丙一酸甲基丁酯、異丙基氯代丙二酸乙基丁酯、異丙基 氯代丙二酸乙基異辛酯、異丙基溴代丙二酸甲基乙酯、異 丙基溴代丙二酸甲基丙酯、異丙基溴代丙二酸甲基丁酯、 異丙基溴代丙二酸乙基丁酯、異丙基溴代丙二酸乙基異辛 酯、丁基氯代丙二酸甲基乙酯、丁基氯代丙二酸甲基丙 酉曰丁基氯代丙二酸甲基丁酯、丁基氯代丙二酸乙基丁 97111247 12 200909460 1、丁基氣代丙二酸乙基異辛醋、丁基演代丙二酸甲基乙 酯、丁基溴代丙二酸曱基丙酯、丁基溴代丙二酸甲^丁 =、丁基溴代丙二酸乙基丁酯、丁基溴代丙二酸乙基二辛 酯：異丁基氯代丙二酸曱基乙酯、異丁基氯代丙二酸曱基 丙酯、異丁基氯代丙二酸甲基丁酯、異丁基氯代丙二酸乙 基丁酯、異丁基氣代丙二酸乙基異辛酯、異丁基溴代丙二 酸甲基乙酯、異丁基溴代丙二酸曱基丙酯、異丁基溴代丙 二酸曱基丁酯、異丁基溴代丙二酸乙基丁酯、異丁基溴代 f丙二酸乙基異辛酯等。 作為二烷基取代丙二酸二酯之具體例，可舉出二異丙基 丙二酸曱基乙酯、二異丙基丙二酸甲基丙酯、二異丙基丙 二酸曱基丁酯、二異丙基丙二酸曱基異丁酯、二異丙基丙 二酸曱基戊酯、二異丙基丙二酸甲基新戊酯、二異丙基丙 二酸曱基己酯、二異丙基丙二酸甲基異己酯、二異丙基丙 二酸甲基庚酯、二異丙基丙二酸曱基異庚酯、二異丙基丙 ^二酸甲基辛酯、二異丙基丙二酸曱基異辛酯、二異丙基丙 二酸乙基丙酯、二異丙基丙二酸乙基丁酯、二異丙基丙二 酸乙基異丁酯、二異丙基丙二酸乙基戊酯、二異丙基丙二 酸乙基己酯、二異丙基丙二酸乙基異己酯、二異丙基丙二 ’酸乙基庚酯、二異丙基丙二酸乙基異庚酯、二異丙基丙二 酸乙基辛酯、二異丙基丙二酸乙基異辛酯、二異丁基丙二 酸曱基乙酯、二異丁基丙二酸曱基丙酯、二異丁基丙二酸 曱基丁酯、二異丁基丙二酸曱基異丁酯、二異丁基丙二酸 曱基戊酯、二異丁基丙二酸曱基新戊酯、二異丁基丙二酸 97111247 13 200909460 甲基己酯、二異丁基丙二酸甲基異己酯、二異丁基丙二酸 甲基庚醋、二異丁基丙二酸甲基異庚酯、二異丁基丙二酸 曱基辛酯、二異丁基丙二酸甲基異辛酯、二異丁基丙二酸 乙基丙酯、二異丁基丙二酸乙基丁酯、二異丁基丙二酸乙 基異丁酯、二異丁基丙二酸乙基戊酯、二異丁基丙二酸乙 基新戊s曰、一異丁基丙二酸乙基己酯、二異丁基丙二酸乙 基異己酯、二異丁基丙二酸乙基庚酯、二異丁基丙二酸乙 基異庚s曰、一異丁基丙二酸乙基辛酯、二異丁基丙二酸乙 基異辛酯、第三丁基f基丙二酸曱基乙酯、第三丁基甲基 丙一酉久甲基丙S旨、第二丁基甲基丙二酸甲基丁醋、第三丁 基T基丙二酸曱基異丁酯、第三丁基曱基丙二酸甲基戊 酯、第三丁基甲基丙二酸甲基新戊酯、第三丁基甲基丙二 酸甲基己酯、第三丁基甲基丙二酸甲基異己酯、第三丁基 甲基丙二酸甲基庚酯、第三丁基甲基丙二酸曱基異庚酯、 第二丁基甲基丙二酸甲基辛酯、第三丁基甲基丙二酸甲基 異辛s曰、第二丁基曱基丙二酸乙基丙酯、第三丁基曱基丙 一酉义乙基丁 3曰、第二丁基甲基丙二酸乙基異丁醋、第三丁 基甲基丙一1乙基戊酯、第三丁基甲基丙二酸乙基新戊 西曰第一丁基甲基丙一酸乙基己g旨、第三丁基甲基丙二酸 乙基異己酯、第三丁基甲基丙二酸乙基庚酯、第三丁基甲 基丙二酸乙基異庚酯、第三丁基甲基丙二酸乙基辛酯、第 二丁基甲基丙二酸乙基異辛酯、第三丁基乙基丙二酸甲基 乙s曰、第二丁基乙基丙二酸甲基丙酯、第三丁基乙基丙二 酸甲基丁酯、第三丁基乙基丙二酸甲基異丁酯、第三丁基 97111247 200909460 乙基丙二酸甲基戊酯、第三丁基乙基丙二酸曱基新戊酯、 第三丁基乙基丙二酸曱基己酯、第三丁基乙基丙二酸曱基 異己酯、第三丁基乙基丙二酸曱基庚酯、第三丁基乙基丙 二酸曱基異庚酯、第三丁基乙基丙二酸曱基辛酯、第三丁 基乙基丙二酸甲基異辛酯、第三丁基乙基丙二酸乙基丙 酯、第三丁基乙基丙二酸乙基丁酯、第三丁基乙基丙二酸 乙基異丁酯、第三丁基乙基丙二酸乙基戊酯、第三丁基乙 基丙一酸乙基新戊s旨、第三丁基乙基丙二酸乙基己自旨、第 一 三丁基乙基丙二酸乙基異己酯、第三丁基乙基丙二酸乙基 庚酯、第三丁基乙基丙二酸乙基異庚酯、第三丁基乙基丙 二酸乙基辛酯、第三丁基乙基丙二酸乙基異辛酯、第三丁 基正丙基丙二酸曱基乙酯、第三丁基正丙基丙二酸曱基丙 酯、第三丁基正丙基丙二酸曱基丁酯、第三丁基正丙基丙 二酸曱基異丁酯、第三丁基正丙基丙二酸曱基戊酯、第三 丁基正丙基丙二酸曱基新戊酯、第三丁基正丙基丙二酸曱 〇基己酯、第三丁基正丙基丙二酸曱基異己酯、第三丁基正 丙基丙二酸曱基庚酯、第三丁基正丙基丙二酸曱基異庚 醋、第三丁基正丙基丙二酸曱基辛酯、第三丁基正丙基丙 一酸甲基異辛酯、第三丁基正丙基丙二酸乙基丙酯、第三 •丁基正丙基丙二酸乙基丁酯、第三丁基正丙基丙二酸乙基 異丁s曰、第二丁基正丙基丙二酸乙基戊酯、第三丁基正丙 基丙二酸乙基新戊酯、第三丁基正丙基丙二酸乙基己酯、 第三丁基正丙基丙二酸乙基異己酯、第三丁基正丙基丙二 酸乙基庚酯、第三丁基正丙基丙二酸乙基異庚酯、第三丁 97111247 15 200909460 基正丙基丙二酸乙基辛酯、第三丁基正丙基丙二酸乙基異 辛酯、第三丁基異丙基丙二酸甲基乙酯、第三丁基異丙基 丙二酸曱基丙酯、第三丁基異丙基丙二酸曱基丁酯、第三 丁基異丙基丙二酸曱基異丁酯、第三丁基異丙基丙二酸曱 基戊酯、第三丁基異丙基丙二酸甲基新戊酯、第三丁基異 丙基丙二酸曱基己酯、第三丁基異丙基丙二酸甲基異己 酯、第三丁基異丙基丙二酸曱基庚酯、第三丁基異丙基丙 二酸曱基異庚酯、第三丁基異丙基丙二酸曱基辛酯、第三 丁基異丙基丙二酸曱基異辛酯、第三丁基異丙基丙二酸乙 基丙酯、第三丁基異丙基丙二酸乙基丁酯、第三丁基異丙 基丙二酸乙基異丁酯、第三丁基異丙基丙二酸乙基戊酯、 第三丁基異丙基丙二酸乙基新戊酯、第三丁基異丙基丙二 酸乙基己酯、第三丁基異丙基丙二酸乙基異己酯、第三丁 基異丙基丙二酸乙基庚酯、第三丁基異丙基丙二酸乙基異 庚酯、第三丁基異丙基丙二酸乙基辛酯、第三丁基異丙基 C丙二酸乙基異辛酯、二異戊基丙二酸曱基乙酯、二異戊基 丙二酸甲基丙酯、二異戊基丙二酸甲基丁酯、二異戊基丙 二酸曱基異丁酯、二異戊基丙二酸曱基戊酯、二異戊基丙 二酸甲基新戊酯、二異戊基丙二酸甲基己酯、二異戊基丙 * 二酸曱基異己酯、二異戊基丙二酸曱基庚酯、二異戊基丙 二酸曱基異庚酯、二異戊基丙二酸曱基辛酯、二異戊基丙 二酸曱基異辛酯、二異戊基丙二酸乙基丙酯、二異戊基丙 二酸乙基丁酯、二異戊基丙二酸乙基異丁酯、二異戊基丙 二酸乙基戊酯、二異戊基丙二酸乙基新戊酯、二異戊基丙 97111247 16 200909460 二酸乙基己酯、二異戊基丙二酸乙基異己酯、二異戊基丙 二酸乙基庚酯、二異戊基丙二酸乙基異庚酯、二異戊基丙 二酸乙基辛酯、二異戊基丙二酸乙基異辛酯、異丙基異丁 基丙二酸曱基乙酯、異丙基異丁基丙二酸曱基丙酯、異丙 基異丁基丙二酸甲基丁酯、異丙基異丁基丙二酸曱基異丁 酯、異丙基異丁基丙二酸曱基戊酯、異丙基異丁基丙二酸 曱基新戊酯、異丙基異丁基丙二酸曱基己酯、異丙基異丁 基丙二酸曱基異己酯、異丙基異丁基丙二酸曱基庚酯、異 & 丙基異丁基丙二酸曱基異庚酯、異丙基異丁基丙二酸甲基 辛酯、異丙基異丁基丙二酸曱基異辛酯、異丙基異丁基丙 二酸乙基丙酯、異丙基異丁基丙二酸乙基丁酯、異丙基異 丁基丙二酸乙基異丁酯、異丙基異丁基丙二酸乙基戊酯、 異丙基異丁基丙二酸乙基新戊酯、異丙基異丁基丙二酸乙 基己酯、異丙基異丁基丙二酸乙基異己酯、異丙基異丁基 丙二酸乙基庚酯、異丙基異丁基丙二酸乙基異庚酯、異丙 ϋ基異丁基丙二酸乙基辛酯、異丙基異丁基丙二酸乙基異辛 酯、異丙基異戊基丙二酸曱基乙酯、異丙基異戊基丙二酸 甲基丙酯、異丙基異戊基丙二酸甲基丁酯、異丙基異戊基 丙二酸甲基異丁酯、異丙基異戊基丙二酸甲基戊酯、異丙 基異戊基丙二酸甲基新戊酯、異丙基異戊基丙二酸甲基己 醋、異丙基異戊基丙二酸甲基異己醋、異丙基異戍基丙二 酸甲基庚醋、異丙基異戊基丙二酸甲基異庚醋、異丙基異 戊基丙二酸甲基辛酯、異丙基異戊基丙二酸甲基異辛酯、 異丙基異戊基丙二酸乙基丙酯、異丙基異戊基丙二酸乙基 97111247 17 200909460 丁酯、異丙基異戊基丙二酸乙基異丁酯、異丙基異戊基丙 二酸乙基戊酯、異丙基異戊基丙二酸乙基新戊酯、異丙基 異戊基丙二酸乙基己酯、異丙基異戊基丙二酸乙基異己 酯、異丙基異戊基丙二酸乙基庚酯、異丙基異戊基丙二酸 乙基異庚酯、異丙基異戊基丙二酸乙基辛酯、異丙基異戊 基丙二酸乙基異辛酯等。 … 作為鹵化烷基取代丙二酸二酯之具體例，可舉出雙（氣 甲基）丙二酸甲基丁酯、雙（溴甲基）丙二酸甲基丁酯、雙 (氯乙基）丙二酸甲基丁酯、雙（溴乙基）丙二酸甲基丁酯二 雙（3-氯-正丙基）丙二酸甲基丁酯、雙（3_溴_正丙基）丙二 酸甲基丁酯。 上述取代丙二酸二酯之中，特佳為異丙基溴代丙二酸甲 基丁酯、丁基溴代丙二酸甲基丁酯、丁基溴代丙二酸乙基 丁酯、異丁基溴代丙二酸曱基丁酯、二異丙基丙二酸甲基 丁酯、二丁基丙二酸甲基丁酯、二異丁基丙二酸乙基丁 酯、二異丁基丙二酸甲基乙酯、二異丁基丙二酸乙基異辛 酯、二異丁基丙二酸甲基丁酯、二異戊基丙二酸曱基丁 醋、異丙基異丁基丙二酸甲基丁酿、異丙基異戊基丙二酸 曱基丁酯、第三丁基曱基丙二酸甲基丁酯、雙(3'氯一正丙 基）丙二酸甲基丁酉旨、雙（3_漠_正丙基）丙三酸甲基丁基。 上述電子供應性化合物（c)可單獨使用或者組合使用 2種以上。再者，上述化合物中，酯殘基之「丁基」為正 丁基或異丁基。 另外，製備本發明之固體觸媒成分（A)時，鎂化合物⑷ 97111247 18 200909460 使用二乙氧基錤’作為電子供應性化合物⑹，於R、r4 之酯殘基之烷基使用乙基以外之不同酯殘基之烷基之情 況下:於使各成分相接觸而製備固體觸媒成分之過程中， 乙氧基，之乙氧基與i種電子供應性化合物⑷之醋殘 土會產生交換’最終包含固體觸媒成分中所含 應性化合物⑷，丙二酸二酯化合物成為3種以上。例如 使用二乙氧基鎂作為鎂化合物⑷、使用二異丁基丙二酸 甲基正丁酯作為電子供應性化合物（C)之情況下，固體觸 媒成分中所含有之酯類為二異丁基丙二酸二甲酯、二異丁 基丙二酸甲基乙@旨、二異丁基丙二酸甲基正丁醋、二里丁 基丙二酸乙基正丁酯及二異丁基丙二酸二正丁酯：5 種。如此’使用R3與R4之醋殘基之烧基相互不同之種類 之電子供應性化合物’故最終於固體觸媒成分中生 西曰，藉此亦可獲得咼對氫活性之固體觸媒成分。 Ο 本發明之固體觸媒成分（A)中，作為製備該固體觸媒成 分時所使用之電子供應性化合物，若使用以通式⑴表示 之取代丙二酸二自旨’則能夠以高產率獲得活性高且 = 性良好之高立體規則性聚合物。 乂 ' 於本發明中’固體觸媒成分⑴之製備較佳為於 50〜151TC之烴溶劑（d)中懸浮接觸而進行。作 5 0〜15 0 C之煙溶劑，較佳為使用曱苯、二曱笨、乙美—'、、、 己烷、銭、辛烷、環己烷等。另外，該等可單獨二：： 亦可混合使用2種以上。若使用沸點為& 〇〜15 〇之灼、六 劑，則於反應或清洗時，雜質之溶解度增大，結果所^ = 97111247 19 200909460 之固體觸媒成分之觸媒活性或所獲得之聚合物之立體規 則性提高，於此方面並非較佳。 以下’就各成分之接觸方法加以敍述。本發明之固體觸 媒成分（A)可藉由使上述鎮化合物⑷…賈之齒化欽化合 物（b)、電子供應性化合物（c)相接觸而製備。更具體而 言’可舉出以下方法：使鎮化合物（a)懸浮於4價^齒化 鈦化合物（b)或烴溶劑⑷中，進而接觸電子供應性化合物 ^)⑹及/或4 ^之齒化鈦化合物⑻，而S得固體觸媒成 刀》亥方法中’藉由使用球狀鎂化合物，可獲得球狀且粒 度分布窄（sharp)之固體觸媒成分，另外即使不使用球狀 鎮化合物，例如藉由使用喷霧裝置而使溶液或者懸浮液噴 霧二乾燥（即所謂之喷霧乾燥法）而形成粒子，藉此同樣可 獲得球狀且粒度分布窄之固體觸媒成分。 各成分之接觸，係於惰性氣體環境下，於除去水分等之 狀況下，於具備授拌機之容器中，一邊授掉一邊進行、。於 ^僅使之接觸並獅混合之情況下、或者使之分散或懸浮而 進行改質處理之情況下，接觸温度亦可為室溫附近之相對 低溫區域’於接觸後使之反應而獲得生成物之情況下，較 仏為40〜130 C之溫度區域。反應時之溫度未滿4〇ΐ時， 無法充刀進仃反應，結果所製備之固體觸媒成分之性能不 充分，超過130C時，所使用之溶劑之蒸發變得顯著等， 而難以控制反應。再者，反應時間為1分鐘以上，較佳為 10分鐘以上，更佳為30分鐘以上。 以下，更具體地例不製備本發明之固體觸媒成分（A)時 97111247 20 200909460 之接觸順序。 中間清洗—（d)—(b)> 中間清洗—（d)—(b)〉〉 ⑴⑷〜⑷一(b)-(c)s 最終清洗〜固體觸媒成分U) (2)(a)〜⑷—（c)—(b)s 最終清洗〜固體觸媒成分（A) ⑷—（b)—(c)、《巾間清洗—⑷―（匕）— ㈧）》—最終清洗—固體觸媒成分（a)The magnesium alkoxide does not have to be spherical, and an elliptical 盥 can also be used; Specifically, the shape of the particle has a major axis diameter of 1. Two: ... ratio (1/w) is 3 or less, preferably..., more preferably W. 3 Γ silk base ^ average particle size can be used from 1 to 5 to 15 佺. In the spherical shape, the average particle size is U100: in the case of the milk silk U, '10 5 A (\ 杈4· is 5 to 50 // m, more preferably less powder, two =, regarding the particle size, preferably used Specifically, the following particles are m: lower 〇% or less. On the other hand, particles of 10"m or more are 〇/〇 or less, preferably 5% or less. In__ indicates the particle size below 97111247 200909460 90%, preferably 'Dl〇2 with its particle size distribution (here, D90 is the cumulative particle size of the cumulative particle size of 1%% when the particle is pinched.), Then, it is 3. The method for producing the spherical methoxymagnesium as described above is disclosed, for example, in the publication of the Japanese Patent Laid-Open No. 58-4, the Japanese Patent Laid-Open Publication No. KK, and the Japanese Patent (four) No. 3 - 74341 Japanese Unexamined Patent Publication No. Hei-4-368391, Japanese Patent Application No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〇Rl2)nX4n (1 to 4 of the alkyl group, ... chlorine, olefin, moth, etc. (four) atom, the integer of At $4) represents one of the compounds in the group of titanium or alkoxy-titanium or In particular, as the titanium halide, tetra-titanium such as titanium tetrachloride, titanium tetrabromide or titanium tetraiodide can be exemplified as the titanium oxy-organized titanium, and methoxy trichloride can be exemplified. Titanium, ethoxylated titanium trichloride, propoxy titanium trichloride, n-butoxide: tri-glycolized titanium, dimethoxy oxydicarbide titanium, diethoxy di-titanium oxide, dioxy-emulsified Titanium, di-n-oxytitanium dichloride, trimethoxychlorinated phthalate, ethoxylated titanium hydride, tripropoxy titanium hydride, tri-n-butoxytitanium chloride, etc. Among them, preferably The titanium tetrahalide is particularly preferably titanium tetrachloride. These titanium compounds may be used singly or in combination of two or more. The electron-donating compound (c) used in the preparation of the solid catalyst component (A) in the present invention is a compound represented by the above formula (1), which is a dimorph-substituted malonic acid diester, an alkyl group and a halogen-substituted malonic acid diester, a pyrenyl-substituted propyl-acid diester or a halogenated alkyl group-substituted C-diester. Acid II g is equivalent (to 9711247 200909460, also known as the factory to replace malonic acid diacetate). In y2 'as a fangs atom, is a gas atom, a stream atom = ' is a gas atom and a desert atom. In addition, the above formula II is: 1 methyl or isobutyl, R, methyl and T3 are all isobutyl groups. In addition, nR2 preferably contains "solid" = Stone anodic, secondary carbon f, a carbon chain of 3 to 10, a branched alkyl group, particularly preferably an isobutyl group, a second butyl group, an isopentyl group, a neopentyl group. In (1), R3 which is an ester residue of a carbonyl group is preferably a linear or branched alkyl group having a carbon number of 丨~3, specifically methyl, ethyl, propyl or isopropyl. Is a methyl group or an ethyl group. Further, y is preferably an alkyl group having 2 to 2 carbon atoms, particularly preferably a linear or branched alkyl group having 2 to 8 carbon atoms, specifically ethyl or propyl. Butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl. Specific examples of the di-substituted malonic acid diester include dichloropropane-methylacetoacetate, mono-propylmalonic acid methyl-propyl acrylate, dimercaptobutyl dipropionate, and dichloro Mercaptoisobutyl acrylate, decyl amyl malonate, decyl neopentyl dichloromalonate, decyl hexyl dichloromalonate, decyl isoammonium dichloromalonate, Dimethyl malonate, decyl heptyl dichloromalonate, decyl octyl malonate, decyl isooctyl dichloromalonate, ethyl dichloromalonate Propyl ester, ethyl acetoacetate, ethyl isobutyl dichloromalonate, ethyl amyl dichloromalonate, ethyl neopentyl dichloromalonate, dichloromalonic acid Ethylhexyl ester, ethyl isopropionate dipropionate, ethyl heptyl dichloromethaneate, ethyl isoheptane dichloromalonate, ethyl octyl dichloromalonate, di-propylene Acid ethyl isooctyl ester, mercaptoethyl dibromomalonate, two 97111247 11 200909460 mercaptopropyl bromomalonate, mercaptobutyl dibromomalonate, antimony dibromomalonate Isobutyl butyl ester, decyl ammonyl dibromomalonate, dibromopropyl Acid decyl neopentyl ester, decyl hexyl bromomalonate, decyl isohexyl dibromomalonate, methyl heptyl dibromomalonate, methyl hexyl dibromomalonate Ester, decyloctyl dibromomalonate, decyl isooctyl dibromomalonate, ethyl propyl dibromomalonate, ethyl butyl dibromomalonate, dibromo Ethyl isobutyl malonate, ethyl amyl bromomalonate, dibromopropane di(ethyl neopentyl ester, ethylhexyl bromomalonate, dibromomalonic acid Ethyl isohexyl ester, ethyl heptyl dibromomalonate, ethyl isoheptyl dibromomalonate, ethyl octyl monobromomalonate, ethyl isooctyl dibromomalonate "" As a specific example of the alkyl and halogen-substituted malonic acid diester, ethyl methacrylic acid methyl ethyl ester, ethyl methacrylic acid decyl propyl acrylate, ethyl gas generation Methyl butyl acrylate, ethyl butyl chloromalonate, ethyl isooctyl ethionate, decyl ethyl bromomalonate, ethyl bromopropyl Methyl propyl dicarboxylate, methyl butyl propyl malonate, ethyl bromide Ethyl butyl acrylate, ethyl isooctyl ethyl bromomalonate, methyl ethyl isopropyl acrylate, isopropyl propyl chloromalonate, isopropyl Gas, methyl propyl propionate, ethyl butyl chloropropyl malonate, ethyl isooctyl isopropyl chloromalonate, methyl ethyl isopropyl bromomalonate, Isopropyl bromomalonate methyl propyl acrylate, isopropyl bromomalonate methyl butyl acrylate, isopropyl bromomalonate ethyl butyl ester, isopropyl bromomalonate ethyl Octyl ester, butyl chloromalonate methyl ethyl ester, butyl chloromalonate methyl propyl butyl chloromalonate methyl butyl ester, butyl chloromalonate ethyl butyl 97111247 12 200909460 1, butyl methacrylic acid ethyl isooctyl vinegar, butyl exemplified methyl ethyl malonate, butyl bromomalonyl propionate, butyl bromomalonate Butyl =, ethyl butyl bromomalonate, ethyl dioctyl butyl bromomalonate: decyl chloropropyl malonate, bis, isobutyl chloromalonate Propyl propyl ester, isobutyl chloromalonate methyl butyl ester, isobutyl chloromalonate Butyl ester, isobutyl methacrylic acid ethyl isooctyl ester, isobutyl bromomalonate methyl ethyl ester, isobutyl bromomalonyl propionate, isobutyl bromide Butyric acid butyl acrylate, isobutyl bromomalonate ethyl butyl ester, isobutyl bromo f malonic acid ethyl isooctyl ester, and the like. Specific examples of the dialkyl-substituted malonic acid diester include mercaptoethyl diisopropylmalonate, methylpropyl diisopropylmalonate, and decyl diisopropylmalonate. Butyl ester, decyl isobutyl isopropyl dipropionate, decyl amyl diisopropyl malonate, methyl neopentyl diisopropyl malonate, decyl diisopropyl malonate Hexyl ester, methyl isopropanyl diisopropyl malonate, methyl heptyl diisopropylmalonate, mercaptoisoheptyl diisopropylmalonate, methyl diisopropylpropionate Octyl ester, decyl isooctyl diisopropylmalonate, ethyl propyl diisopropyl malonate, ethyl butyl diisopropyl malonate, ethyl diisopropyl malonate Butyl ester, ethyl isoamyldiisopropylmalonate, ethylhexyl diisopropylmalonate, ethyl isohexyl diisopropylmalonate, ethylglycol diisopropylpropionate Ester, ethyl iso-heptyl malonate, ethyl octyl diisopropylmalonate, ethyl isooctyl diisopropylmalonate, decyl diisobutylmalonate Ester, mercaptopropyl diisobutylmalonate, mercapto diisobutylmalonate , diisobutylmalonyl isopropyl isobutyl acrylate, diisobutylmalonyl decyl amyl phthalate, diisobutylmalonyl decyl neopentyl pentoxide, diisobutylmalonic acid 97111247 13 200909460 Hexyl hexyl ester, diisobutylmalonate methyl isohexyl ester, diisobutylmalonate methyl heptanoacetate, diisobutylmalonate methyl isoheptyl, diisobutylmalonate decyl Octyl ester, diisobutylmalonate methyl isooctyl ester, diisobutylmalonate ethyl propyl ester, diisobutylmalonate ethyl butyl ester, diisobutylmalonate ethyl Butyl ester, diisobutylmalonate ethyl amyl ester, diisobutylmalonate ethyl neopentazone, monoisobutylmalonate ethylhexyl, diisobutylmalonate ethyl Isohexyl ester, diisobutylmalonate ethylheptyl ester, diisobutylmalonate ethyl isoheptane, monoisobutylmalonate ethyloctylate, diisobutylmalonate ethyl Isooctyl ester, tert-butyl f-propyl malonyl malonate, tert-butyl methyl propyl methacrylate, second butyl methyl malonate methyl butyl vinegar, tert-butyl T-based Methyl isobutyl acrylate, tert-butyl decyl malonate methyl pentane , t-butyl methylmalonate methyl neopentyl ester, t-butyl methyl malonate methyl hexyl ester, t-butyl methyl malonate methyl iso-hexyl ester, t-butyl methyl malonate methyl heptyl ester, Tert-butylmethylmalonium decyl heptyl ester, second butyl methylmalonate methyloctyl ester, tert-butylmethylmalonate methylisooctyl sulfonate, second butylmercaptomalonate ethyl Propyl ester, tert-butyl decyl propyl sulfonate ethyl hydrazine, second butyl methyl malonate ethyl isobutyl vinegar, tert-butyl methyl propane 1-ethyl amyl ester, tert-butyl methyl propyl Acid ethyl neopentitcher first butyl methyl propionate ethyl hexyl, tert-butyl methyl malonate ethyl isohexyl ester, tert-butyl methyl malonate ethyl heptyl ester, third butyl methyl propane Acid ethyl isoheptyl ester, ethyl octyl butyl methyl malonate, ethyl isooctyl butyl methyl malonate, methyl ethyl s ate of t-butyl ethyl malonate, second butyl Methyl propyl malonate, methyl butyl tributylethyl malonate, methyl isobutyl tributylethyl malonate, third butyl 97111247 20 0909460 methyl amyl malonate, decyl neopentyl butyl ethanoate, decyl hexyl butyl methacrylate, butyl butyl triethyl acrylate Isohexyl ester, thiryl butyl ethyl malonate, decyl heptyl tert-butylethyl malonate, decyl octyl octyl acrylate, third butyl Methyl isopropionate methyl isooctyl ester, tert-butyl ethyl malonate ethyl propyl ester, tert-butyl ethyl malonate ethyl butyl ester, tert-butyl ethyl malonate B Isobutyl butyl ester, ethyl pentyl ethanoethyl malonate, ethyl pentoxide of tert-butyl ethyl acrylate, and ethyl butyl ethyl malonate First tributylethylmalonate ethyl isohexyl ester, tert-butylethylmalonate ethylheptyl ester, tert-butylethylmalonate ethylisoheptyl ester, tert-butylethyl Ethyl octyl malonate, ethyl isooctyl tributylethyl malonate, mercaptoethyl tert-butyl-n-propylmalonate, decyl-tert-butyl-n-propyl-propionate Propyl ester, tert-butyl-n-propyl-propylmalonate, tert-butyl-propyl propyl Isobutyl phthalate, decyl amyl propyl propyl malonate, decyl neopentyl methacrylate, tert-butyl propyl propyl malonate Mercaptohexyl ester, tert-butyl-n-propyl-propylmalonate, decyl heptyl t-butyl-n-propylmalonate, decyl-iso-glycolate , tert-butyl-n-propyl-propylmalonyl octyl octyl ester, tert-butyl-n-propyl-propionic acid methyl isooctyl ester, tert-butyl-n-propylmalonate ethyl propyl ester, third Butyl-n-propylmalonate ethyl butyl ester, t-butyl-n-propylmalonate ethyl isobutyl sulfonate, second butyl-n-propylmalonate ethyl amyl ester, and tert-butyl-positive Propylmalonate ethyl neopentyl ester, tert-butyl-n-propylmalonate ethylhexyl ester, tert-butyl-n-propylmalonate ethyl isohexyl ester, tert-butyl-n-propylpropane Acid ethyl heptyl ester, tert-butyl-n-propylmalonate ethyl isoheptyl ester, third butyl 97111247 15 200909460 propyl propyl malonate, ethyl octyl propyl malonate Ethyl isooctyl ester, tert-butyl isopropyl malonate methyl ethyl ester, third Mercaptopropyl propyl malonate, decyl butyl butyl isopropyl methacrylate, decyl isobutyl butyl isopropyl methacrylate, tert-butyl isopropyl Methyl pentyl malonate, methyl neopentyl butyl isopropyl malonate, decyl hexyl butyl isopropyl acrylate, tert-butyl isopropyl malonate Isohexyl ester, tert-butyl isopropyl malonyl heptyl heptyl ester, tert-butyl isopropyl malonyl isoheptyl ester, tert-butyl isopropyl malonyl octyl octyl ester, Tert-butyl isopropyl malonyl octyl isooctyl ester, tert-butyl isopropyl malonate ethyl propyl ester, tert-butyl isopropyl malonate ethyl butyl ester, tert-butyl Isopropyl malonate ethyl isobutyl ester, tert-butyl isopropyl malonate ethyl amyl ester, tert-butyl isopropyl malonate ethyl neopentyl ester, tert-butyl isopropyl Ethyl hexyl malonate, ethyl isobutyl hexyl butyl isopropyl malonate, ethyl heptyl butyl isopropyl malonate, ethyl butyl butyl isopropyl acrylate Isoheptyl ester, ethyl octyl butyl isopropyl malonate, tert-butyl isopropyl C malonate ethyl isooctyl ester, diisoamylmalonyl malonyl ethyl ester, diisoamylmalonate methyl propyl ester, diisoamylmalonate methyl butyl ester, diisoamyl Isobutyl isopropionate, decylpentane diisoamylmalonate, methyl neopentyl diisoamylmalonate, methylhexyl diisoamylmalonate, diisoamyl ** decyl isohexyl dicarboxylate, mercaptoheptyl diisoamylmalonate, decyl heptyl diisoamylmalonate, decyl octyl diisoamylmalonate, diisoamyl Isooctyl malonate, ethyl propyl diisoamylmalonate, ethyl butyl diisoamylmalonate, ethyl isobutyl diisoamylmalonate, diisoamyl Ethyl amyl malonate, ethyl neopentyl diisoamylmalonate, diisoamylpropion 97111247 16 200909460 ethylhexyl diacrylate, ethyl isohexyl diisoamylmalonate, diiso) Ethyl heptyl malonate, ethyl isoheptyl diisoamylmalonate, ethyl octyl diisoamylmalonate, ethyl isooctyl diisoamylmalonate, isopropyl Isobutyl butyl malonate, isopropyl isobutyl malonate Ester, methyl butyl isobutyl malonate, decyl isobutyl isopropyl isobutyl malonate, decyl amyl isopropyl isobutyl malonate, isopropyl isobutyl Mercapto-maleyl malonate, isopropylhexyl isopropyl isobutylmalonate, decyl isobutyl isopropyl isobutyl malonate, decyl isopropyl isopropyl isobutyl malonate Ester, iso-amp; propyl isobutyl malonate decyl heptyl ester, isopropyl isobutyl malonate methyl octyl ester, isopropyl isobutyl malonate decyl isooctyl ester, isopropyl Ethyl propyl malonate, ethyl butyl isopropyl isobutyl malonate, ethyl isobutyl isopropyl isobutyl malonate, isopropyl isobutyl malonate Ethyl amyl ester, isopropyl isobutyl malonate ethyl neopentyl ester, isopropyl isobutyl malonate ethylhexyl ester, isopropyl isobutyl malonate ethyl isohexyl ester, isopropyl Ethyl heptyl propyl malonate, ethyl iso-heptyl isopropyl isobutyl malonate, ethyl octyl isopropionate, isopropyl isobutyl propylene Acid ethyl isooctyl ester, isopropyl isoamylmalonyl malonyl ethyl ester, isopropyl isoamyl Methyl propyl dicarboxylate, methyl butyl isopropyl isoamylmalonate, methyl isobutyl isopropyl isoamylmalonate, methyl amyl isopropyl isoamylmalonate, Isopropylisoamylmalonate methyl neopentyl ester, isopropylisoamylmalonate methyl hexanoic acid, isopropylisoamylmalonate methylisohexyl vinegar, isopropyl isodecyl propyl Dimethyl vinegar diacetate, methyl iso-heptyl isopropyl isoamylmalonate, methyl octyl isopropyl isoamylmalonate, methyl isooctyl isopropyl isoamylmalonate , Isopropyl isoamylmalonate ethyl propyl ester, isopropylisoamylmalonate ethyl 97111247 17 200909460 Butyl ester, isopropyl isoamylmalonate ethyl isobutyl ester, isopropyl Isoamylmalonate ethyl amyl ester, isopropylisoamylmalonate ethyl neopentyl ester, isopropylisoamylmalonate ethylhexyl ester, isopropylisoamylmalonate B Isohexyl ester, isopropyl hesoamylmalonate ethyl heptyl ester, isopropylisoamylmalonate ethyl isoheptyl ester, isopropylisoamylmalonate ethyl octyl ester, isopropyl Isoamylmalonate ethyl isooctyl ester and the like. Specific examples of the halogenated alkyl-substituted malonic acid diester include bis(methylmethyl)malonate methylbutyl ester, bis(bromomethyl)malonate methylbutyl ester, and bis(chloroethyl) Methyl butyl acrylate, methyl butyl bis(bromoethyl)malonate, di(3-chloro-n-propyl)malonate methyl butylate, bis(3_bromo-n-propyl Base) methyl butyl acrylate. Among the above substituted malonic acid diesters, particularly preferred are methyl butyl bromomalonate, methyl butyl bromomalonate, ethyl butyl bromomalonate, Isobutyl bromide malonyl butyl acrylate, methyl butyl diisopropyl malonate, methyl butyl dibutyl malonate, ethyl butyl butyl diisopropionate, diisobutyl Methyl ethyl butyl malonate, ethyl isooctyl diisobutylmalonate, methyl butyl diisobutylmalonate, decyl butyl acetonate, isopropyl Isobutylmalonate methyl butyl, isopropyl isoamylmalonyl butyl butylate, tert-butylmercaptomalonate methyl butyl ester, bis(3' chloro-n-propyl) propyl Methyl butyl dicarboxylate, bis(3_in_-propyl)trimethyl butyl tricarboxylate. The above electron-donating compound (c) may be used alone or in combination of two or more. Further, in the above compound, the "butyl group" of the ester residue is n-butyl or isobutyl. Further, in the preparation of the solid catalyst component (A) of the present invention, the magnesium compound (4) 97111247 18 200909460 uses diethoxyanthracene ' as the electron-donating compound (6), and the alkyl group of the ester residue of R and r4 is an ethyl group. In the case of alkyl groups of different ester residues: in the process of preparing the solid catalyst component by contacting the components, the ethoxy group, the ethoxy group and the vinegar residue of the electron-donating compound (4) are produced. The exchange 'finally contains the compound (4) contained in the solid catalyst component, and the malonic acid diester compound becomes three or more types. For example, when diethoxymagnesium is used as the magnesium compound (4) and diisobutylmalonate methyl n-butyl ester is used as the electron-donating compound (C), the ester contained in the solid catalyst component is divalent. Dimethyl butyl malonate, methyl ethyl di-butyl malonate, methyl di-n-butylmalonate, methyl n-butyl acrylate, dibutyl butyl malonate, and diisobutyl acrylate Di-n-butyl butyl malonate: 5 kinds. Thus, the use of an electron-donating compound of a type in which the carboxylic acid residues of R3 and R4 are different from each other is finally produced in the solid catalyst component, whereby a solid catalyst component which is active for hydrogen can be obtained. In the solid catalyst component (A) of the present invention, the electron-donating compound used in the preparation of the solid catalyst component can be obtained in a high yield by using the substituted malonic acid represented by the general formula (1). A highly stereoregular polymer having high activity and goodness is obtained. The preparation of the solid catalyst component (1) in the present invention is preferably carried out by suspension contact in a hydrocarbon solvent (d) of 50 to 151 TC. For the solvent of 50 to 15 0 C, it is preferred to use indene, diterpene, acetaminophen, ',, hexane, hydrazine, octane, cyclohexane and the like. In addition, these may be used alone or in combination of two or more. If the boiling point is & 〇~15 灼, six doses, the solubility of the impurities increases during the reaction or cleaning, and the catalyst activity of the solid catalyst component of the solution = 97111247 19 200909460 or the obtained polymerization The improvement of the stereoscopicity of the object is not preferable in this respect. The following is a description of the contact method of each component. The solid catalyst component (A) of the present invention can be produced by bringing the above-mentioned sulfonate compound (4), dentate compound (b), and electron-donating compound (c) into contact. More specifically, 'the following method can be mentioned: the symbiotic compound (a) is suspended in the tetravalent titanium compound (b) or the hydrocarbon solvent (4), thereby contacting the electron-donating compound (6) and/or 4^ Titanium compound (8), and S is a solid catalyst. In the method of 'Hai', by using a spherical magnesium compound, a solid catalyst component having a spherical shape and a sharp particle size distribution can be obtained, and even if no spherical shape is used The smectic compound, for example, is formed by spray-drying a solution or a suspension by a spray device (so-called spray drying method) to form particles, whereby a spherical catalyst having a narrow particle size distribution can be obtained. The contact of each component is carried out while being removed in a container equipped with a mixer in an inert gas atmosphere under the condition of removing moisture or the like. In the case where only the contact and the lion are mixed, or the dispersion treatment is carried out by dispersing or suspending, the contact temperature may be a relatively low temperature region near the room temperature, and the reaction may be reacted after the contact to obtain a product. In the case of the object, it is a temperature range of 40 to 130 C. When the temperature at the time of the reaction is less than 4 Torr, the reaction of the solid catalyst component prepared is insufficient, and as a result, the evaporation of the solvent used becomes remarkable when the temperature exceeds 130 C, and it is difficult to control the reaction. . Further, the reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer. Hereinafter, the contact sequence of 97111247 20 200909460 when the solid catalyst component (A) of the present invention is not prepared is more specifically exemplified. Intermediate cleaning—(d)—(b)> Intermediate cleaning—(d)—(b)〉〉 (1)(4)~(4)-(b)-(c)s Final cleaning~Solid catalyst component U) (2)(a )~(4)-(c)-(b)s Final cleaning~Solid catalyst components (A) (4)-(b)-(c), "towel cleaning-(4)-(匕)-(eight))"--final cleaning- Solid catalyst component (a)

U)(ah⑷_(b)—(c)、《巾間清洗—⑷— (b) 》—最終清洗—固體觸媒成分（a) (:)(a)〜⑷一 (c)—(b)〜《中間清洗一⑷— (c) 》—最終清洗—固體觸媒成分（a) (c)4(b)〜《中間清洗—（d)— (b)》—最終清洗—固體觸媒成分（a) 再者’於上述各接觸方法中，關於雙括號（《》）内之步 驟，藉由視需要重複進行數次，可進一步提高活性。且《》 内之步驟中所使用之成分（b)或者成分⑷可為新加入 者，亦可為前步驟之殘留分。另外，了上述⑴〜⑻ 中所不之清洗步驟以外，亦可於常溫下利用液體之烴化人 物對各接觸階財所生成之生成物進行清洗。 ° 基於以上情況，本申請案中之固體觸媒成分（A)之特佳 衣備方法，係使作為紹b合物（a)之二炫氧基鎂懸浮於沸 =50〜15G C之作為烴溶劑⑷之甲苯中，接著使作為* 價之_化鈦化合物（b)之四氣化鈦接觸該懸浮液後，進行 反應處理。此時’使4價之S化鈦化合物（b)接觸該懸浮 97111247 21 200909460 液之前或接觸之後，於-20〜130 °C下使之接觸作為電子供 應性化合物（c)之二烷基取代丙二酸二酯之1種或者2種 以上’獲得固體反應生成物（1)。此時’較佳係於接觸電 子供應性化合物（c)之前或之後，於低溫下進行熟成反 應。將該固體反應生成物（1)於常溫下以液體之烴化合物 加以清洗（中間清洗）後，再次於芳香族烴化合物之存在 下，於-20〜l〇〇°C下使之接觸4價之鹵化鈦化合物（b)， (進行反應處理，獲得固體反應生成物（2)。再者，視需要 亦可進一步反覆進行數次中間清洗及反應處理。接著，於 常溫下利用液體之烴化合物對固體反應生成物（2)加以清 洗（最終清洗）’獲得固體觸媒成分（A)。 上述處理或者清洗之較佳條件如下所述。 •低溫熟成反應：_20〜70°C，較佳為-1〇〜6〇ΐ，更佳 為〇〜3(TC ’ 1分鐘〜6小時，較佳為5分鐘〜4小時，特 佳為10分鐘〜3小時。 G •反應處理：0〜130t：，較佳為40〜120t，特佳為5〇 〜115°C，0.5〜6小時，較佳為〇5〜5小時，特佳為^ •清洗：〇〜litre ’較佳為30〜10(rc，特佳為3〇〜9〇π， 1〜20次’較佳為1〜15次，特佳為1〜10次。再者，、、主 =所使用之烴化合物較佳為於常溫下為㈣之芳^ 舉==者飽和烴化合物，具體而言，芳香族烴化合物可 ;、二己；I本、乙基笨等，飽和烴化合物可舉出己烷、 庚说、％己料。較佳為中間清洗使用芳香族烴化合物， 97111247 22 200909460 最終清洗使用飽和烴化合物。 =固體觸媒成分（A)時之各成分之使用量比根據製備 斗人/斤不冋’故不能—概而論，例如相對於每1莫耳鎂 二勿（a) ’ 4 4貝之鹵化鈇化合物（b)為0.5〜100莫耳， Ί父it為〇·5〜50莫耳，更私故1 , Λ 人从r 更彳土為1〜丨〇莫耳，電子供應性化 〇口〇? Y、、G.G1〜1G莫耳’較佳〜1莫耳，更佳為 ;64耳，煙溶劑⑷為U01〜500莫耳，較佳為 (0·001〜1〇〇莫耳，更佳為0 005〜10莫耳。 另外，本發明中之固體觸媒成分⑴中之鈦、鎂、鹵素 =、電子供應性化合物之含有量並無特別較，較佳為 鈦為U〜8.0重量％，較佳為20〜U重量％，更佳為 U〜U重量％’鎮為10〜70重量％，更佳為1〇〜5〇重 ::特佳為15〜40重量％’更佳為15〜25請，齒素 原子為20〜9〇Μ%，更佳為30〜85重量％，特佳為4〇 〜80重量m為45〜75重量m卜電子供岸性化人 物為合計0.5〜30重量％，更佳為合計^重^，特二 Γ20重量%。為了更加平衡地發揮本發明之使用 電子供應性化合物與其他成分而成之固體觸媒成分⑴之 綜合性能’而較佳係鈦含有量為3〜8重量％ 15〜25重量％，齒素原子之含有量為扎〜”重量％，電^ 供應性化合物之含有量為2〜20重量％。 ° 作為形成本發明之稀煙類聚合用觸媒時所使用之有機 鋁化合物（B)，可使用以通式R5pA1Q3_p(式中，Rs表示碳數 1〜4之烷基，Q表示氫原子或者齒素原 :&amp; P 馬 0 &lt; p S d 97111247 23 200909460 之實數）表示之化合物。作為此種有機鋁化合物（B)之具體 例，可舉出三乙基鋁、二乙基氯化鋁、三異丁基鋁、^乙 基溴化鋁、二乙基氫化鋁，可使用丨種或者2種以上。較 佳為二乙基銘、三異丁基|呂。 作為形成本發明之烯烴類聚合用觸媒時所使用之外部 電子供應性化合物（c)(以下，有時稱為「成分（c)」），可 舉出自以通式（3)表示之有機矽化合物以及聚醚中選擇之 1種或2種以上： 〇 R6aSi(NR7R8)r(0R9)4_(q+r)(3) (式中’q為0或1〜4之整數’r為〇或卜4之整數，其 中，q+r為0〜4之整數，^、^或^為氫原子〜碳數^ 12之直鏈或支鏈狀烧基、經取代或未經取代之環烧基、 苯基、乙烯基、烯丙基、芳烷基之任一者，可含有雜原子， 可相同或不同。R9表示碳數丨〜4之烷基、環烷基、苯基、 =烯基、烯丙基、芳烷基，可含有雜原子，可相同或不同， R7與R8亦可鍵結而形成環狀）。 *通式（3)中，R6較佳為碳數丨〜^之直鏈或支鏈狀烷基、 石反數5〜8之裱烷基，特佳為碳數丨〜8之直鏈或支鏈狀烷 基、碳數5〜8之環烧基。另外^或R8較佳為碳數卜 10之直鏈或支鏈狀烷基、碳數5〜8之環烷基，特佳為碳 數1 8之直鍵或支鍵狀烧基、碳數5〜8之環烧基。另外， R7與R8鍵結而形成環狀之（nr7r8)較佳為全氫喹啉基、全氫 異°圭琳基。另外’ R9較佳為碳數j〜6之直鍵或支鍵狀烧 基’特佳為碳數1〜4之直鍵或支鍵狀燒基。 97111247 24 200909460 作為此種有機矽化合物，可舉出苯基烷氧基矽烷、烷基 烷氧基矽烷、苯基烷基烷氧基矽烷、環烷基烷氧基矽烷、 環烷基烷基烷氧基矽烷、（烷基胺基）烷氧基矽烷、烷基（烷 基胺基）烧氧基梦烧、烧基（烧基胺基）碎烧、烧基胺基石夕 烷等。 通式（3)中，於r為〇之情況下，q較佳為1〜3，Re較 佳為碳數1〜8之直鏈或支鏈狀烷基、碳數5〜7之環烷 基’ R9較佳為碳數1〜4之直鏈或支鏈狀院基。另外，尤 其是於r為〇之情況下，q較佳為1〜3，R6較佳為碳數j 〜8之直鏈或支鏈狀烷基、碳數5〜7之環烷基，R9較佳為 碳數1〜2之直鏈之烧基。 通式（3)中，於r為〇之情況下，特佳之化合物為二正 丙基二甲氧基矽烷、二異丙基二曱氧基矽烷、二正丁基二 甲氧基矽烷、二異丁基二甲氧基矽烷、二第三丁基二曱氧 基矽烷、二正丁基二乙氧基矽烷、第三丁基三曱氧基矽 烷、一％己基二甲氧基矽烷、二環己基二乙氧基矽烷、環 己基甲基=甲氧基石夕烧、ί裒己基曱基=乙氧基石夕烧、環己 基乙基二甲氧基矽烷、環己基乙基二乙氧基矽烷、二環戊 基二甲氧基矽烷、二環戊基二乙氧基矽烷、環戊基甲基二 曱氧基矽烷、環戊基曱基二乙氧基矽烷、環戊基乙基2乙 氧基矽烷、環己基環戊基二甲氧基矽烷、環己基環戊基二 乙氧基石夕烧、3-甲基環己基環戊基二甲氧基發烧、4_甲義 環己基環戊基=甲氧基料、3,5_二甲基環己基環戊基: 曱氧基矽烷。 97111247 25 200909460 通式（3)中，式中，作為r為1〜4之有機石夕化合物，可 舉出（烷基胺基）三烷基矽烷、（烷基胺基）二烷基環烷基矽 烷、（烷基胺基）烷基二環烷基矽烷、（烷基胺基）三環烷基 矽烷、（烷基胺基）（二烷基胺基）二烷基矽烷、（烷基胺 基）（二烷基胺基）二環烷基矽烷、雙（烷基胺基）二烷基矽 烷、雙（烷基胺基）烷基環烷基矽烷、雙（烷基胺基）二環烷 基矽烷、雙（烷基胺基）（二烷基胺基）烷基矽烷、雙（烷基 胺基）（二烷基胺基）環烷基矽烷、二（烷基胺基）二烷基矽 烷、二（烷基胺基）烷基環烷基矽烷、二（烷基胺基）二環烷 基矽烷、二（環烷基胺基）二烷基矽烷、二（環烷基胺基） 烷基環烷基矽烷、二（環烷基胺基）二環烷基矽烷、三（烷 基胺基）烷基矽烷、三（烷基胺基）環烷基矽烷、三（烷基胺 基）烷基矽烷、三（烷基胺基）環烷基矽烷、三（環烷基胺基） 烷基矽烷、三（環烷基胺基）環烷基矽烷、四（烷基胺基） 砍烧、三（烧基胺基）二烧基胺基砍烧、三（環烧基胺基） 二烷基胺基矽烷、雙（二烷基胺基）雙（烷基胺基）矽烷、二 烷基胺基三（烷基胺基）矽烷、雙（全氫異喹啉基）雙（烷基 胺基）矽烷、雙（全氩喹啉基）雙（烷基胺基）矽烷、雙（環烷 基胺基）雙（烷基胺基）矽烷、四（烷基胺基）矽烷、三（烷基 胺基）二烷基胺基矽烷、三（環烷基胺基）二烷基胺基矽 烷、二（二烷基胺基）二（烷基胺基）矽烷、二烷基胺基三（烷 基胺基）矽烷、二（烷基取代全氫異喹啉基）二（烷基胺基） 矽烷、二（烷基取代全氫喹啉基）二（烷基胺基）矽烷、二（環 烷基胺基）二（烷基胺基）矽烷、烷基（二烷基胺基）（烷基胺 97111247 26 200909460 基）烧乳基珍烧、環烧基（二烧基胺基）（烧基胺基）烧氧基 石夕烧、乙烯基（二烧基胺基）（烧基胺基）烧氧基石夕烧、烯丙 基（二烷基胺基）（烷基胺基）烷氧基矽烷、芳烷基（二烧基 胺基）（烷基胺基）烷氧基矽烷、二烷基（烷基胺基）烷氧基 矽烷（二烧基胺基）三烷氧基矽烷、烧基（二烷基胺基）烷氧 基矽烷、雙（全氫異喹啉基）二烷氧基矽烷等。該有機矽化 合物（C)可使用1種或者組合使用2種以上。聚趟之中， 較佳為1’3-二醚，更佳為9, 9 —雙（甲氧基甲基）第、2_異 丙基-2-異戊基-1，3-二甲氧基丙烷。該等外部電子供應性 化合物可使用1種或者組合使用2種以上。 L. 其次，本發明之烯烴類聚合用觸媒含有上述烯烴類聚合 用固體觸媒成分（A)、成分（B)及成分（c)，於該觸媒之存 在：進行烯烴類之聚合或共聚合。作為烯烴類，為乙稀、 :烯1 丁烯、1-戊烯、4一甲基_卜戊烯、乙烯基環己烷 專，該等烯烴類可使用丨種或者併用2種以上。尤其是可 較佳地使用乙烯、丙烯&amp;卜丁烯。特佳為丙烯。於丙烯 =時:亦可與其他_類進行共聚合。作為共聚合之稀 二二：烯、卜丁烯、卜戊烯、4_甲基+戊烯、乙烯 該等烯烴類可使用i種或者併用2種以上。 尤其疋可較佳地使用乙烯及1-丁烯。 =成刀之使用里比於不影響本發明之效果之範圍内為 i壬:耳特別限定，有機銘化合物⑻通常於相對於每 ;圭=固體觸媒成分⑴中之鈦原子為卜義莫耳、較 '' 1GGG莫耳之範圍内加以使用。有機魏合物（C) 97111247 27 200909460 於相對於每〗莫耳（β)成分 〜2莫耳、特佳為㈣〜G5^2；^耳、較佳為 各成分.5莫耳之乾圍内加以使用。 使之接觸烯埋H、用觸有機石夕化合物⑹，進而 頰♦。用固體觸媒成分（A)。 ::中之聚合方法可於有機溶劑 ===:用另外丙物烴單量體可於氣體及液： ' w 聚合溫度為戰以下，較佳為刚 另:二^力為1&quot;…，—…!^。 以1階合法、批次式聚合法之任-種。進而可 進而=，亦可以2階段以上進行聚合反應。 分⑴、成使用含她類聚合用固體觸媒成 式聚合）二了進-使稀煙聚合時（亦稱為正 ^ 改D觸媒活性、立體規則性及生成 2合體之粒子性狀等，而較佳係於正式聚合之前進行預 水&amp;。預聚合時，可传用盘 ' 乙烯等單體。 -正“ 口同樣之烯烴類或者苯 進：預：：時’各成分及單體之接觸順序為任意，較佳 二：肉Γ二為惰性氣體環境或者烯烴氣體環境之預聚 =、、刀其次使之接觸烯烴類聚合用固體觸 某成WA)，其後使之接觸丙烯等婦煙及/或i種或者^ 以上，其他烯烴類。於組合成分(c)進行預聚合之情況 叙佳係為々下方法’首先向設定為惰性氣體環境或者 細烴氣體環境之預聚合系内裝入成分⑻，其次使之接觸 97111247 28 200909460 成分（c)，進而使之接 其後使之接觸丙婦等烯烴及:或〜;觸媒成分(A) ’ 烯烴類。 種或者其他2種以上之 於藉由本發明所形成之婦煙類聚合 行烯烴類之聚合之情％ 觸媒之存在下，進 比，且有更高之^气、^ 與使用習知之觸媒之情況相 ”有更网之對虱活性，進而能夠 規則性之聚合物。 半&amp;付问立體 (實施例） 以下，將本發明之實施例與比較例加 明，但並不限制本發明。 和一。 兄 (實施例1) [固體觸媒成分（A)之製備] 於以氮氣加以充分置換、具備攪拌機之容量5〇〇 d之 圓底燒瓶中m〇g二乙氧基鎂及160ml ψ苯，形成 懸洋狀態。其次向該懸浮溶液中添加4〇 ml四氯化鈦，並 進行升溫，於達到60°C時添加4· 5 m 1二異丁基丙二酸乙 基正丁酯，進一步升溫使之達到9(rc。其後於保持9(rc 之皿度之狀態下，一邊擾拌2小時一邊使之反應。反應結 束後，將所獲得之反應生成物以200 ml之9(TC之甲苯清 洗4次，重新添加40 ml四氯化鈦及80 ml曱苯，升溫至 110°C ’ 一邊攪拌1小時一邊使之反應。反應結束後，以 200 ml之40°C之正庚烷清洗7次，獲得固體觸媒成分。 再者，分離該固體觸媒成分中之固液，測定固體分中之鈦 含有率’結果為4. 5重量％。另外，根據使用氣相層析法 97111247 29 200909460 之分析，觸媒中含有0.31重量％之二異丁基丙二酸二乙 酯、13. 34重量％之二異丁基丙二酸乙基正丁酯、〇. 11重 量％之二異丁基丙二酸二正丁酯。 [聚合觸媒之形成及聚合] 向以氮氣加以完全置換之内容積2.0公升之附有攪拌 機之高壓釜中’裝入1· 32 mmol三乙基鋁、〇. 13 mm〇i環 己基曱基二甲氧基矽烷及以鈦原子計為〇. 〇〇26 mm〇1之上 (述固體觸媒成分，形成聚合用觸媒。其後，裝入2 〇公升 氫氣、1. 4公升液化丙烯，於2(rc進行5分鐘預聚合後升 溫，於7(TC進行1小時聚合反應。此時之每丨g固體觸 媒成分之聚合活性、生成聚合體中之沸騰正庚烷不溶分之 比例（HI)、生成聚合體（a)之溶融流動速率之値（mfr ;表 示為「MI」）示於表1。 再者，每單位之此處使用之固體觸媒成分之聚合活性根 據下式算出。聚合活性=生成聚合體(g)/固體觸媒成分 (g) 另外，生成聚合體中之沸騰正庚院不溶分之比例⑻）， ，為將該生成聚合體以賴正庚料# 6小時時的不溶 解於正庚烧之聚合體之比例（重量％)。 (實施例2)U)(ah(4)_(b)-(c), "Washing between towels-(4)-(b)" - final cleaning - solid catalyst component (a) (:) (a) ~ (4) one (c) - (b) ~ "Intermediate cleaning one (4) - (c)" - final cleaning - solid catalyst components (a) (c) 4 (b) ~ "intermediate cleaning - (d) - (b) - final cleaning - solid catalyst components (a) In addition, in the above respective contact methods, the steps in the double brackets ("") can be further increased by repeating as many times as necessary, and the components used in the steps in "" ( b) or component (4) may be a new addition, or may be a residue of the previous step. In addition, in addition to the cleaning steps not mentioned in the above (1) to (8), it is also possible to use a liquid hydrocarbonized person at each room temperature to contact each contact step. The product produced by the money is cleaned. ° Based on the above, the method of preparing the solid catalyst component (A) in the present application is to suspend the bis-oxymagnesium as the compound (a). In the toluene of the hydrocarbon solvent (4) at a boiling point of 50 to 15 G C, the titanium tetrachloride which is a *valent titanium compound (b) is contacted with the suspension, and then reacted. At this time, 'contact the tetravalent S titanium compound (b) with the dioxane as an electron-donating compound (c) before or after contact with the suspension 97111247 21 200909460 liquid at -20 to 130 ° C. The solid reaction product (1) is obtained by one or two or more kinds of the malonic acid diester. At this time, it is preferred to carry out the ripening reaction at a low temperature before or after contacting the electron-donating compound (c). The solid reaction product (1) is washed with a liquid hydrocarbon compound at normal temperature (intermediate washing), and then contacted at a temperature of -20 to 10 ° C in the presence of an aromatic hydrocarbon compound. The titanium halide compound (b) is subjected to a reaction treatment to obtain a solid reaction product (2). Further, if necessary, the intermediate cleaning and the reaction treatment may be further repeated several times. Next, the liquid hydrocarbon compound is used at a normal temperature. The solid reaction product (2) is washed (final cleaning) to obtain a solid catalyst component (A). The preferred conditions for the above treatment or washing are as follows: • Low temperature ripening reaction: -20 to 70 ° C, preferably -1〇~6〇 ΐ, more preferably 〇~3 (TC '1 minute~6 hours, preferably 5 minutes~4 hours, especially good for 10 minutes~3 hours. G•Reaction treatment: 0~130t:, preferably 40~ 120t, especially good for 5〇~115°C, 0.5~6 hours, preferably 〇5~5 hours, especially good for ^•Cleaning: 〇~litre 'better 30~10(rc, especially good for 3 〇~9〇π, 1~20 times' is preferably 1~15 times, especially preferably 1~10 times. Furthermore, the hydrocarbon compound used in the main = is preferably (4) at room temperature ^ The saturated hydrocarbon compound may be, for example, an aromatic hydrocarbon compound; or a dihydrogen compound; and the like, and a saturated hydrocarbon compound may be exemplified by hexane, glycol or %. Preferably, the intermediate cleaning uses an aromatic hydrocarbon compound, 97111247 22 200909460. The final cleaning uses a saturated hydrocarbon compound. = The amount of each component in the case of the solid catalyst component (A) is not as large as that according to the preparation of the person (for example), for example, relative to 1 m of magnesium (2) The antimony halide compound (b) is 0.5 to 100 m, the uncle is 〇·5 to 50 m, and more privately, 1 Λ people from r more bauxite is 1 丨〇 丨〇 ,, electronic supply 〇 Mouth? Y, G.G1~1G Mo's better ~ 1 Mo, better; 64 ears, smoke solvent (4) is U01~500 Mo, preferably (0·001~1〇〇莫Further, the ear is more preferably 0 005 to 10 m. Further, the content of titanium, magnesium, halogen = and electron-donating compound in the solid catalyst component (1) of the present invention is not particularly preferable, and titanium is preferably U. ～8.0% by weight, preferably 20% by weight to U%, more preferably U~U% by weight, the town is 10 to 70% by weight, more preferably 1 〇 to 5 〇 by weight: more preferably 15 to 40% by weight 'More preferably 15~25, fangs atom is 20~9〇Μ%, more preferably 30~85wt%, especially good is 4〇~80 weight m is 45~75 weight mb electron supply shore The total number of people is 0.5 to 30% by weight, more preferably the total is ^^^, especially two to 20 weight %. In order to more balance the overall performance of the solid catalyst component (1) using the electron-donating compound and other components of the present invention, it is preferable that the titanium content is 3 to 8 wt% 15 to 25 wt%, and the tooth The content of the elemental atom is 3% to "% by weight, and the content of the compound is 2 to 20% by weight. ° The organoaluminum compound (B) used as a catalyst for forming a thin tobacco polymerization of the present invention. A compound represented by the formula R5pA1Q3_p (wherein Rs represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a dentinogen: &amp; P horse 0 &lt; p S d 97111247 23 200909460) can be used. Specific examples of such an organoaluminum compound (B) include triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminum, ethyl ethyl bromide, and diethyl aluminum hydride. The above-mentioned external electron-donating compound (c) is used as the catalyst for olefin polymerization of the present invention (hereinafter, it is preferably diethyl ester or triisobutyl). It is called "component (c)"), and it can be mentioned by the general formula (3). One or more selected from the group consisting of a ruthenium compound and a polyether: 〇R6aSi(NR7R8)r(0R9)4_(q+r)(3) (wherein 'q is 0 or an integer of 1 to 4' is 〇 Or an integer of 4, wherein q+r is an integer of 0 to 4, and ^, ^ or ^ is a linear or branched alkyl group having a hydrogen atom to a carbon number of 12, substituted or unsubstituted ring-burning Any of a group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may contain a hetero atom, may be the same or different. R9 represents an alkyl group having a carbon number of 丨4, a cycloalkyl group, a phenyl group, an ene group. The group, allyl group, and aralkyl group may contain a hetero atom, which may be the same or different, and R7 and R8 may also bond to form a ring. In the general formula (3), R6 is preferably a linear or branched alkyl group having a carbon number of 丨~^, a decyl group having an inverse number of 5 to 8, and particularly preferably a linear chain having a carbon number of 丨8 or A branched alkyl group or a cycloalkyl group having 5 to 8 carbon atoms. Further, ^ or R8 is preferably a linear or branched alkyl group having a carbon number of 10, a cycloalkyl group having a carbon number of 5 to 8, particularly preferably a direct bond or a branched bond group having a carbon number of 18 or a carbon number. 5 to 8 ring base. Further, R7 and R8 are bonded to each other to form a cyclic (nr7r8) group, preferably a perhydroquinolinyl group or a perhydrogen group. Further, 'R9 is preferably a straight bond or a branched bond group having a carbon number of j to 6', and particularly preferably a straight bond or a branched bond group having a carbon number of 1 to 4. 97111247 24 200909460 Examples of such an organic ruthenium compound include phenyl alkoxy decane, alkyl alkoxy decane, phenylalkyl alkoxy decane, cycloalkyl alkoxy decane, and cycloalkyl alkyl alkane. Oxydecane, (alkylamino) alkoxydecane, alkyl (alkylamino) alkoxylated, calcined (alkylamino) calcined, alkyl amine-based naphthene, and the like. In the formula (3), in the case where r is fluorene, q is preferably 1 to 3, and Re is preferably a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkane having 5 to 7 carbon atoms. The base 'R9 is preferably a linear or branched chain base having a carbon number of 1 to 4. Further, especially in the case where r is ruthenium, q is preferably 1 to 3, and R6 is preferably a linear or branched alkyl group having a carbon number of j 8 or a cycloalkyl group having 5 to 7 carbon atoms, R 9 A linear alkyl group having a carbon number of 1 to 2 is preferred. In the general formula (3), in the case where r is ruthenium, a particularly preferred compound is di-n-propyldimethoxydecane, diisopropyldimethoxy decane, di-n-butyldimethoxydecane, and Isobutyl dimethoxy decane, di-tert-butyl dimethoxy decane, di-n-butyl diethoxy decane, tert-butyl trimethoxy decane, mono-hexyl dimethoxy decane, two Cyclohexyldiethoxydecane, cyclohexylmethyl=methoxy methoxy sulfonium, 裒 裒 曱 曱 = ethoxy oxime, cyclohexylethyldimethoxydecane, cyclohexylethyldiethoxydecane , dicyclopentyldimethoxydecane, dicyclopentyldiethoxydecane, cyclopentylmethyldimethoxyoxydecane, cyclopentyldecyldiethoxydecane, cyclopentylethyl 2 Oxydecane, cyclohexylcyclopentyldimethoxydecane, cyclohexylcyclopentyldiethoxy zeoxime, 3-methylcyclohexylcyclopentyldimethoxy-fluorene, 4-methylcyclohexyl ring Pentyl = methoxylate, 3,5-dimethylcyclohexylcyclopentyl: decyloxydecane. 97111247 25 200909460 In the formula (3), in the formula, as the organic compound of R to 1 to 4, (alkylamino)trialkylnonane, (alkylamino)dialkylcycloalkane Alkane, (alkylamino)alkylbicycloalkylnonane, (alkylamino)tricycloalkylnonane, (alkylamino)(dialkylamino)dialkylnonane, (alkyl Amino)(dialkylamino)bicycloalkylnonane, bis(alkylamino)dialkylnonane, bis(alkylamino)alkylcycloalkylnonane, bis(alkylamino)di Cycloalkyl decane, bis(alkylamino)(dialkylamino)alkyl decane, bis(alkylamino)(dialkylamino)cycloalkylnonane, bis(alkylamino)di Alkyl decane, bis(alkylamino)alkylcycloalkylnonane, bis(alkylamino)bicycloalkylnonane, bis(cycloalkylamino)dialkylnonane, bis(cycloalkylamine) Alkyl cycloalkyl decane, bis(cycloalkylamino)bicycloalkylnonane, tris(alkylamino)alkylnonane, tris(alkylamino)cycloalkylnonane, tris(alkyl) Amino)alkyl Alkane, tris(alkylamino)cycloalkylnonane, tris(cycloalkylamino)alkylnonane, tris(cycloalkylamino)cycloalkylnonane, tetrakis(alkylamino) chopped, three (alkylamino) dialkylamino chopping, tris(cycloalkylamino)dialkylamino decane, bis(dialkylamino)bis(alkylamino)decane, dialkylamine Tris(alkylamino)decane, bis(perhydroisoquinolinyl)bis(alkylamino)decane, bis(all argonquinolyl)bis(alkylamino)decane, bis(cycloalkyl) Amino)bis(alkylamino)decane, tetrakis(alkylamino)decane, tris(alkylamino)dialkylaminodecane, tris(cycloalkylamino)dialkylaminodecane, Di(dialkylamino)bis(alkylamino)decane, dialkylaminotri(alkylamino)decane, di(alkyl substituted perhydroisoquinolyl) bis(alkylamino) Decane, di(alkyl substituted perhydroquinolyl) bis(alkylamino)decane, bis(cycloalkylamino)bis(alkylamino)decane, alkyl (dialkylamino) (alkane) Base amine 97111247 26 200909460 ) calcined base, calcined (dialkylamino) (alkylamino) alkoxylated, vinyl (dialkylamino) (alkylamino) azide, Allyl (dialkylamino)(alkylamino)alkoxydecane, aralkyl (dialkylamino)(alkylamino)alkoxydecane, dialkyl (alkylamino group) Alkoxydecane (dialkylamino) trialkoxydecane, alkyl (dialkylamino) alkoxydecane, bis(perhydroisoquinolinyl) dialkoxydecane, and the like. These organic hydrazine compounds (C) may be used alone or in combination of two or more. Among the polyfluorenes, preferred is 1'3-diether, more preferably 9,9-bis(methoxymethyl), 2-isopropyl-2-isopentyl-1,3-dimethyl Oxypropane. These external electron-donating compounds may be used alone or in combination of two or more. L. The olefin polymerization catalyst of the present invention contains the above-mentioned olefin polymerization solid catalyst component (A), component (B), and component (c), and the catalyst is used to carry out polymerization of olefins or Copolymerization. Examples of the olefins include ethylene, an alkene, a butene, a 1-pentene, a 4-methyl-p-pentene, and a vinylcyclohexane. These olefins may be used alone or in combination of two or more. In particular, ethylene, propylene &amp; butene can be preferably used. Particularly good for propylene. In the case of propylene = it can also be copolymerized with other _ classes. As a rare copolymer of the copolymerization: alkene, butene, pentene, 4-methyl pentene, and ethylene, the olefins may be used singly or in combination of two or more. In particular, ethylene and 1-butene are preferably used. = The use of the knives is in the range that does not affect the effects of the present invention: i 壬: the ear is particularly limited, and the organic compound (8) is usually used in relation to each of the titanium atoms in the solid catalyst component (1). Ears are used within the range of ''1GGG'. Organic Wei compound (C) 97111247 27 200909460 is about 2 molars per gram of moth (β) component, especially good (four) ~ G5^2; ^ ear, preferably each component. 5 moles of dry circumference Used internally. It is exposed to the olefin, and the organic compound (6) is touched, and then the buccal ♦. Use solid catalyst component (A). :: The polymerization method can be used in organic solvents ===: using another propane hydrocarbon monolith can be used in gases and liquids: ' w polymerization temperature is below war, preferably just another: two force is 1&quot;..., —...!^. Any one of the first-order legal and batch polymerization methods. Further, the polymerization reaction may be carried out in two or more stages. Sub-(1), using a solid catalyst containing a polymerization method for polymerization of the same type), when the dilute fumes are polymerized (also referred to as positive D-catalyst activity, stereoregularity, and particle traits which form a 2-complex), Preferably, it is pre-watered before the formal polymerization. In the pre-polymerization, the monomer such as ethylene can be transferred. - The same olefin or benzene: the:::: The order of contact is arbitrary, preferably two: the meat is the inert gas atmosphere or the prepolymerization of the olefin gas environment, and the second step is to contact the solids of the olefin polymerization to form a WA), and then contact the propylene, etc. Women's cigarettes and / or i or above, other olefins. In the case of prepolymerization of the component (c), it is a submerged method. First, the prepolymerization system is set to an inert gas atmosphere or a fine hydrocarbon gas environment. The component (8) is charged, and then it is brought into contact with the ingredients (c) of 97111247 28 200909460, and then it is brought into contact with the olefin such as propylene and the like: or the catalyst component (A) 'olefins. Species or other 2 More than the above-mentioned women's cigarettes formed by the present invention The polymerization of olefins in the presence of catalysts, the ratio of the catalyst, and the higher the gas, ^ and the use of the conventional catalyst" have a more network of antagonistic activity, which in turn can be a regular polymerization Things. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; And one. Brother (Example 1) [Preparation of solid catalyst component (A)] m〇g diethoxymagnesium and 160 ml of toluene in a round bottom flask which was sufficiently substituted with nitrogen and equipped with a stirrer capacity of 5 〇〇d. Forming a suspended state. Next, 4 〇ml of titanium tetrachloride was added to the suspension solution, and the temperature was raised. When the temperature reached 60 ° C, 4·5 m 1 of di-n-butylmalonate ethyl n-butyl acrylate was added, and the temperature was further increased to 9 (rc. Thereafter, the mixture was allowed to react for 2 hours while maintaining the state of 9 (r). After the reaction was completed, the obtained reaction product was washed 4 times with 200 ml of 9 (TC toluene 4 times). , re-add 40 ml of titanium tetrachloride and 80 ml of benzene, and raise the temperature to 110 ° C. While stirring for 1 hour, react with it. After the reaction, wash with 200 ml of 40 ° C n-heptane for 7 times. The solid catalyst component is further separated, and the solid content in the solid catalyst component is determined, and the titanium content in the solid fraction is determined to be 4.5% by weight. Further, according to the analysis using gas chromatography 9711247 29 200909460 The catalyst contains 0.31% by weight of diethyl diisobutylmalonate, 13.34% by weight of ethyl isobutyl butyl diisopropyl acrylate, 〇. 11% by weight of diisobutyl propyl Di-n-butyl diacidate [Formation and polymerization of polymerization catalyst] 2.0 liters of internal volume completely replaced by nitrogen In an autoclave with a stirrer, '1·32 mmol of triethylaluminum, 〇.13 mm〇i cyclohexyldecyldimethoxydecane and above titanium atom 〇〇26 mm〇1 are charged. The solid catalyst component is used to form a catalyst for polymerization. Thereafter, 2 liters of hydrogen gas and 1.4 liters of liquefied propylene are charged, and 2 (rc is prepolymerized for 5 minutes, then heated, and 7 (TC is subjected to polymerization for 1 hour). At this time, the polymerization activity of the solid catalyst component per gram of g, the ratio of boiling n-heptane insoluble fraction in the polymer (HI), and the melting flow rate of the polymer (a) (mfr; expressed as " The MI") is shown in Table 1. The polymerization activity of the solid catalyst component used per unit is calculated according to the following formula: polymerization activity = polymer (g) / solid catalyst component (g) The ratio (8)) of the boiling in the polymer to the insoluble fraction of the positive Gengyuan is the ratio (% by weight) of the polymer which is not dissolved in the n-gumene when the produced polymer is lyophilized #6 hours. (Example 2 )

ml 備H 果， 97111247 200909460 聚合結果示於表1。 (實施例3 ) 除了使用 Ο RU二異丁基 一 一 敗甲暴乙酯代替4. 5 ml -異丁基丙一 g曼乙基正丁 g旨以外，與實施例工同樣 體觸媒成分’進而進行聚合觸媒之形成及聚合。^ 所獲得之固體觸媒成分中之鈦含有㈣4 3 :二」 結果示於表1。 來5 (實施例4) 除了使用4.3 ml二異丁基丙二酸甲基正丁酯代替* 5 ml二異丁基丙二酸乙基正丁酯以外，與實施例工1 備固體觸媒成分，進而進行聚合觸媒之形成及聚合。其: 果’所獲得之固體觸媒成分中之鈦含有量為4 3重量；:M prepared H, 97111247 200909460 The polymerization results are shown in Table 1. (Example 3) The same physical catalyst component as the example work except that Ο RU diisobutyl ketone ethyl ester was used instead of 4. 5 ml -isobutyl propyl-g-mantyl butyl ketone 'The formation and polymerization of the polymerization catalyst are further carried out. ^ The titanium in the solid catalyst component obtained contains (4) 4 3 : 2". The results are shown in Table 1. 5 (Example 4) In addition to using 4.3 ml of methyl n-butyl diisobutylmalonate instead of * 5 ml of ethyl n-butyl diisobutylmalonate, the solid catalyst was prepared in the same manner as in Example 1. The component further forms and polymerizes the polymerization catalyst. It is: the amount of titanium in the solid catalyst component obtained is '43 weight;

另外，根據使用氣相層析法之分析，觸媒中，含有〇 U 重量％之二異丁基丙二酸二曱酯、〇19重量％之二異丁芙 丙二酸甲基乙醋、15.27重量%酷二異丁基丙二甲基： :酉旨、0.61重量%之二異丁基丙二酸乙基正丁醋、㈣重 里％之一異丁基丙二酸二正丁酯。聚合結果示於表工。 (實施例5) ' 除了使用4.9 ml雙（3-氯-正丙基）丙二酸甲基正丁醋代 替4. 5 ml二異丁基丙二酸乙基正丁酯以外，與實施例i 同樣製備固體觸媒成分，進而進行聚合觸媒之形成及聚 合。其結果，所獲得之固體觸媒成分中之鈦含有量為3.g 重量％。聚合結果示於表1。 (實施例6) 97111247 31 200909460 除了使用3. 7 ml 丁基溴代丙_ m基丙二酸乙基正丁以：甲基正丁基代替4·5 備固體觸媒成分，進而進行聚合，與實施例1同樣製 果固體觸媒成分中之鈦含有量 ^之形成及聚合。其結 於表1。 ‘ .4重量％。聚合結果示 (實施例7) 除了使用4.3 ml 丁基溴代丙二酸 ml二異丁基丙二酸乙基正丁酯以 土 丁知代替4.5 備固體觸媒成分，進而進行聚合’與實施#&quot;同樣製 果固體觸媒成分中之鈦含有量;觸3媒= 形成及聚合。其結 於表卜 *里為3.3重量％。聚合結果示 (實施例8 ) “除了使用…第三丁基甲基丙二酸曱基正丁酉旨代替 m 一異丁基丙一酸乙基正丁酯以外，盥實施例 樣製備固體觸媒成分，進而進〃同 甘处A 逆订1合觸媒之形成及聚合。 m果固體觸媒成分中之鈦含有 果示於表卜 _置為3.3重買％。聚合結 (實施例9) 除了使用4·5 ml二異丁基丙二酸乙基異丁醋代替u 備固體、酸乙基正了酉旨以外，與實施例1同樣製 =體觸媒成》’進而進行聚合觸媒之形成及聚合。其处 觸媒成分中之鈦含有量為U重量％。聚合結果示 (實施例10) 97111247 32 200909460 除了使用4.3 ml二異丁基丙二酸曱基異丁 d二異丁基丙二酸乙基正丁醋以外，與實施例ι 備固體觸媒成分，進而進行聚合觸媒之形成及聚人门^ 果固體觸媒成分中之鈦含有量為44重量％。Μ結^ 於表1。 不 (實施例11) 除了使用5.4 ml第三丁基甲基丙二酸甲基異丁醋代替 ('·5 ml 一異丁基丙二酸乙基正丁酯以外’與實施例1同 樣製備固體觸媒成分，進而進行聚合觸媒之形成及聚人。 其結果固體觸媒成分中之鈦含有量為46重量％。聚合口結 果示於表1。 (比較例1) 除了使4.0 ml #苯二曱酸二正丁醋代帛45 二異 丁基丙一酸乙基正丁酯以外，與實施例丨同樣製備固體觸 媒成刀，進而進行聚合觸媒之形成及聚合。其結果固體觸 〇媒成分中之鈦含有量為3· 5重量％。聚合結果示於表2。 (比較例2) 除了使用4. 1 ml二異丁基丙二酸二乙酯代替4. 5 ml二 異丁基丙二酸乙基正丁酯以外，與實施例丨同樣製備固體 觸媒成分，進而進行聚合觸媒之形成及聚合。其结果固體 觸媒成分中之鈦含有量為4. 5重量％。聚合結果示於表2。 (實施例12) [固體觸媒成分（A)之製備] 於以氮氣加以充分置換、具備攪拌機之容量5〇〇 ml之 97111247 33 200909460 圓底燒瓶中，裝入20 g無水氯化鎂（東邦鈦製）、ι〇6 μ 癸烷及102 ml之2-乙基己基醇，一邊攪拌一邊升溫至 °C，處理2小時而使之溶解無水氯化鎂，製成均勾溶液。 其後添加4.4 g鄰笨二甲酸酐，進而於13〇t： 一邊攪拌工 小時一邊使之反應。另外於以氮氣加以充分置換、具見備擾 拌機之容量11之圓底燒瓶中，裝入17〇ml四氣化欽，冷 卻至-2(TC，向其中滴加上述均勻溶液。其後升溫至ιι〇 ί、\添加4.〇ml二異丁基丙二酸甲基正丁醋。其後於110 C處理2小時。除去上清液後’重新導入n〇mi四氣化 鈦，於UOt-邊㈣2小時—邊使之反應。反應結束後， 以200 ml之40 C之正庚燒清洗7次，獲得固體觸媒成分。 再者，分離該固體觸媒成分中之固液，測定固體分中之鈦 含有率’結果為3. 0重量％。 [聚合觸媒之形成及聚合] 除了使用上述固體觸媒成分以外，與實施例丨同樣進行 〇聚合觸媒之形成及聚合。所得結果示於表 (實施例13) [固體觸媒成分（A)之製備] • 於以氮氣加以充分置換、具備攪拌機之容量5〇〇 U之 圓底燒瓶中’裝入20 g二乙氧基鎂、4〇 ml二異丁基丙 ?夂曱基正丁酯及100 ml二氯甲烷，製成懸浮狀態，1 後升溫，於回流狀態下-邊授拌i小時一邊使之反應^ 外於以氮氣加以充分置換、具備攪拌機之容量2000 ml之 圓底燒瓶中，裝入800 ral室溫之四氣化欽，向其中滴加 97111247 34 200909460 上述懸浮液。其後升溫至110°C，一邊攪拌2小時—邊使 之反應。除去上清液後，以8 0 0 m 1癸烧清洗3 ：：欠，重新 導入800 ml四氯化鈦，於120°C —邊攪拌2小時—邊使 之反應。反應結束後，以800 ml之40°C之正庚烷清洗7 次，獲得固體觸媒成分。再者，分離固體觸媒成分中之固 液，測定固體分中之鈦含有率，結果為3. 3重量％。 [聚合觸媒之形成及聚合] 除了使用上述固體觸媒成分以外，與實施例1同樣進行 聚合觸媒之形成及聚合。所得結果示於表1。 (實施例14) 除了使用0.13 mmol之9,9-雙（曱氧基曱基）第代替 〇· 13 mmol環己基甲基二曱氧基矽烷以外，與實施例4同 樣進行聚合觸媒之形成及聚合。聚合結果示於表1。 (貫施例1 5 ) 除了使用0.13 mmol二環戊基雙（乙基胺基）矽烷代替 0.13随〇1環己基甲基二甲氧基矽烷以外，與實施例4同 樣進仃聚合觸媒之形成及聚合。聚合結果示於表i。 (比較例3) 4，了使用4.1 mi之2一異丙基丙二酸乙基異丁酯代替 样制ml 一異丁基丙二酸乙基正丁醋以外，與實施例1同 2備固體觸媒成分，進而進行聚合觸媒之形成及聚合。 果、:果固體觸媒成分中之鈦含有量為45重量％。聚合結 严不於表2。 (比較例4) 97111247 35 200909460 除了使用4·1 ml之2-異丙基丙二酸乙基新戊酯代替 4.5 ml二異丁基丙二酸乙基正丁酯以外，與實施例 樣製備固體觸媒成分，進而進行聚合觸媒之形成及聚合°。 其結果固體觸媒成分中之鈦含有量為4 5 &quot; 果示於表2。 · 合結 (比較例5) [固體觸媒成分（A)之製備] ，，除了使用4·〇 鄰本一甲酸二正丁酯代替4 〇 mi 酸甲基正丁酯以外’與實施例12同樣製備2 :蜀媒成分。其結果固體觸媒成分中之鈦含有量為w重： [聚合觸媒之形成及聚合] ，了使用上述固體觸媒成分以外，與實施例 “觸媒之形成及聚合。所得結果示於表2。羡進仃 (比較例6) ;[固體觸媒成分（A)之製備] 除了使用4. 0 ml鄰苯二甲酸二 正丁酯代替4.〇 ml二異 [聚合觸媒之形成及聚合] 除了使用上述固體觸媒成分以外，與 (聚比成及聚合。所得結果示於表2。]1同樣進行 97111247 36 200909460 除了使用4. 5 ml二異丁基丙二酸二正丁酯代替45… 一異丁基丙二酸乙基正丁酯以外，與實施例丨同樣製備固 體觸媒成分，進而進行聚合觸媒之形成及聚合。其結果固 體觸媒成分中之鈦含有量為4 6重量％。聚合結果：於表 2 ° (比較例8) 除了使用4.1 ml &lt; 2_異丙基丙二酸乙基正丁酯代替 4. 5 ml 一異丁基丙二酸乙基正丁醋以外，與實施例1同 樣製備固體觸媒成分，*而進行聚合觸媒之形成及聚合。 其結果固體觸媒成分中之鈦含有量為4. 3重量％。聚二士 果示於表2。 乂 口、口 (比較例9) 除了使用5. “1二異丁基丙二酸二辛酯代替4. 5…二 丙二酸乙基正丁醋以外’與實施例1同樣製備固體 觸媒成为，進而進行聚合觸媒之形成及聚合。其結果固體 觸媒成分中之鈦含有量為4. 8重量%。聚合結果 (比較例10) 、 ，了使帛4.1 ml t 2_異丙基丙二酸乙基異辛酯代替 媒制L 一異丁基丙二酸乙基正丁酉1以外’與實施例1同 ，衣備固體觸媒成分，進而進行聚合觸媒之形成及 。 :結果固體觸媒成分中之鈦含有量為4. 5重量%。聚：结 果示於表2。 (比較例11) 除了使用4.5 ml二異丁基丙二酸二曱酯代替4·5以二 97111247 37 200909460 異丁基丙二酸乙基正丁酯以外’與實施例1同揭制&amp; u水敁備固體 觸媒成分’進而進行聚合觸媒之形成及聚合。复έ士田 丹結果固體 觸媒成分中之鈦含有量為4.3重量％。聚合結果示 、於表2。 (比較例12 ) 除了使用4.1 ml之2-異丙基丙二酸甲基乙酯代替* $ ml二異丁基丙二酸乙基正丁酯以外，與實施例1同樣製 備固體觸媒成分，進而進行聚合觸媒之形成及聚合。其鈐 果固體觸媒成分中之鈦含有量為4· 6重量％。聚合結果= 於表2。 (比較例13)In addition, according to the analysis by gas chromatography, the catalyst contains bismuth 8% by weight of diisobutylmalonate dinonyl ester, 〇19% by weight of diisoflufenic acid methyl vinegar, 15.27% by weight of diisobutyl propyl dimethyl group: : 0.61% by weight of diisobutylmalonate ethyl n-butyl vinegar, (iv) 3% by weight of di-n-butylmalonate. The results of the polymerization are shown in the table. (Example 5) 'Except that 4.9 ml of bis(3-chloro-n-propyl)malonate methyl n-butyl vinegar was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate, and Examples i The solid catalyst component is also prepared, and the formation and polymerization of the polymerization catalyst are carried out. As a result, the titanium content in the obtained solid catalyst component was 3. g% by weight. The polymerization results are shown in Table 1. (Example 6) 97111247 31 200909460 In addition to the use of 3.7 ml of butyl bromide-methyl-malonic acid ethyl-n-butyl group: methyl n-butyl group instead of 4·5 of the solid catalyst component, and further polymerization, In the same manner as in Example 1, the formation and polymerization of the titanium content in the solid catalyst component were determined. It is shown in Table 1. ‘ .4% by weight. The polymerization results are shown (Example 7) except that 4.3 ml of butylbromomalonic acid ml diisobutylmalonate ethyl-n-butyl ester was used in place of the sulphate component instead of 4.5, and the polymerization was carried out. #&quot;The same titanium content in the solid catalyst component; contact 3 media = formation and polymerization. It is 3.3% by weight in the table. The polymerization results are shown (Example 8) "In addition to the use of ... tert-butylmethylmalonium decyl n-butyl phthalate instead of m-isobutylpropionate ethyl n-butyl ester, the ruthenium example was prepared to prepare a solid catalyst component, Further, the formation and polymerization of the catalyzed by the stagnation of the stagnation of the sorghum A. The titanium contained in the solid catalyst component of the fruit is shown in Table _ set to 3.3 repurchase %. Polymerization knot (Example 9) 4·5 ml of diisobutylmalonate ethyl isobutyl vinegar was prepared in the same manner as in Example 1 except that the solid was prepared in the same manner as in Example 1, and the formation of a polymerization catalyst was further carried out. And polymerization, wherein the titanium content in the catalyst component is U% by weight. The polymerization result is shown (Example 10) 97111247 32 200909460 In addition to using 4.3 ml of diisobutylmalonate decyl diisobutyl bis diisobutyl propyl In addition to the diacid n-butyl vinegar, the solid catalyst component was prepared in the same manner as in Example 1, and the formation of the polymerization catalyst and the titanium content in the solid catalyst component were 44% by weight. Table 1. No (Example 11) except that 5.4 ml of tributylmethylmalonate methyl isobutyl vinegar was used instead ('·5 ml The solid catalyst component was prepared in the same manner as in Example 1 except for ethyl isobutyl butyl acrylate, and the polymerization catalyst was formed and aggregated. As a result, the titanium content of the solid catalyst component was 46% by weight. %. The results of the polymerization port are shown in Table 1. (Comparative Example 1) The same procedure as in Example 除了 except that 4.0 ml of di-n-butyl phthalate was used, and ethyl n-butyl butyl diisobutyl acrylate was used. The formation of a solid catalyst was carried out, and the formation and polymerization of a polymerization catalyst were carried out. As a result, the content of titanium in the solid contact vehicle component was 3.5% by weight. The polymerization results are shown in Table 2. (Comparative Example 2) 4. The solid catalyst component was prepared in the same manner as in Example 以外 except that 1 ml of diethyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl butyl diisobutylmalonate. The result of the formation and the polymerization was as follows: The titanium content of the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2. (Example 12) [Preparation of solid catalyst component (A)] Replacement, with a mixer capacity of 5 〇〇 ml of 97111247 33 200909460 round bottom flask, loaded 20 g of anhydrous magnesium chloride (made of Toho Titanium), 〇 6 μ decane and 102 ml of 2-ethylhexyl alcohol, and the mixture was heated to ° C while stirring, and treated to dissolve anhydrous magnesium chloride for 2 hours to prepare a homologous solution. Thereafter, 4.4 g of o-dicarboxylic anhydride was added, and the reaction was carried out at 13 Torr while stirring for a while, and in a round bottom flask which was sufficiently substituted with nitrogen and had a capacity of 11 for the scrambler. Load 17 〇ml of four gasification, cool to -2 (TC, add the above homogeneous solution to it. Then warm up to ιι〇ί, \ add 4. 〇ml diisobutylmalonate methyl-n-butyl vinegar. Thereafter, it was treated at 110 C for 2 hours. After removing the supernatant, 're-introducing n〇mi four-vaporized titanium and reacting it on the UOt-side (four) for 2 hours. After completion of the reaction, the mixture was washed 7 times with 200 ml of 40 C of n-gum to obtain a solid catalyst component. 0重量百分比。 The solid content of the solid content of the solid content was determined to be 3. 0% by weight. [Formation and Polymerization of Polymerization Catalyst] The formation and polymerization of a ruthenium polymerization catalyst were carried out in the same manner as in Example 除了 except that the above solid catalyst component was used. The results obtained are shown in the table (Example 13) [Preparation of solid catalyst component (A)] • 20 g of diethoxygen was placed in a round bottom flask equipped with a capacity of 5 〇〇U, which was sufficiently substituted with nitrogen. Base magnesium, 4 〇ml diisobutyl propyl fluorenyl n-butyl acrylate and 100 ml of methylene chloride, made into a suspension state, 1 temperature rise, under reflux state - while mixing for 1 hour to make it react In a round bottom flask which was sufficiently substituted with nitrogen and equipped with a volume of 2000 ml of a stirrer, it was charged with 800 ral at room temperature, and the above suspension was added dropwise to 97111247 34 200909460. Thereafter, the temperature was raised to 110 ° C, and the mixture was stirred for 2 hours to cause a reaction. After removing the supernatant, it was washed with 8000 m 1 Torr 3:: owed, and re-introduced with 800 ml of titanium tetrachloride and stirred at 120 ° C for 2 hours while allowing to react. After completion of the reaction, it was washed 7 times with 800 ml of 40 ° C n-heptane to obtain a solid catalyst component. 3%重量。 The solid content of the solid content of the solid content of the solid content of the solid content was 3.3% by weight. [Formation and Polymerization of Polymerization Catalyst] The formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 1 except that the above solid catalyst component was used. The results obtained are shown in Table 1. (Example 14) Polymerization catalyst formation was carried out in the same manner as in Example 4, except that 0.13 mmol of 9,9-bis(decyloxyfluorenyl) was used instead of 〇·13 mmol of cyclohexylmethyldimethoxy decane. And polymerization. The polymerization results are shown in Table 1. (Example 15) A polymerization catalyst was introduced in the same manner as in Example 4, except that 0.13 mmol of dicyclopentyl bis(ethylamino) decane was used instead of 0.13 with 环1 cyclohexylmethyl dimethoxy decane. Formation and polymerization. The polymerization results are shown in Table i. (Comparative Example 3) 4. The same procedure as in Example 1 was carried out except that 4.1 mmol of 2-isopropyl isopropyl malonate ethyl isobutyl ester was used instead of the sample ml isobutyl butyl malonate ethyl n-butyl vinegar. The solid catalyst component further forms and polymerizes the polymerization catalyst. Fruit: The titanium content of the fruit solid catalyst component was 45% by weight. The aggregation is not as shown in Table 2. (Comparative Example 4) 97111247 35 200909460 Prepared in the same manner as in the Example except that 4.1 ml of 2-isopropylpropionic acid ethyl neopentyl ester was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. The solid catalyst component further forms and polymerizes the polymerization catalyst. As a result, the titanium content in the solid catalyst component was 4 5 &quot; · Coupling (Comparative Example 5) [Preparation of solid catalyst component (A)], except that 4: phthalic acid di-n-butyl methacrylate was used instead of 4 〇mi acid methyl n-butyl ester, and Example 12 The same preparation 2: oxime component. As a result, the titanium content in the solid catalyst component was w weight: [formation and polymerization of a polymerization catalyst], and the formation and polymerization of the catalyst were carried out in addition to the above solid catalyst component. The results are shown in the table. 2. 羡进仃 (Comparative Example 6); [Preparation of solid catalyst component (A)] In addition to using 4. 0 ml of di-n-butyl phthalate instead of 4. 〇ml diiso[polymerization and formation of a polymerization catalyst Polymerization] In addition to the above-mentioned solid catalyst component, it was mixed with (polymerization and polymerization. The results obtained are shown in Table 2.) 1 was carried out in the same manner as 9711247 36 200909460 except that 4.5 ml of di-n-butyl diisobutylmalonate was used. In the same manner as in Example 丨, a solid catalyst component was prepared in the same manner as in Example 45 except for ethyl isobutyl butyl acrylate, and the polymerization catalyst was formed and polymerized. As a result, the titanium content in the solid catalyst component was 4重量%。 Polymerization results: in Table 2 ° (Comparative Example 8) except that 4.1 ml &lt; 2 - isopropylmalonate ethyl n - butyl ester was used instead of 4. 5 ml of isobutyl butyl acrylate A solid catalyst component was prepared in the same manner as in Example 1 except for n-butyl vinegar, and the formation of a polymerization catalyst was carried out. As a result, the content of titanium in the solid catalyst component was 4.3% by weight. The polyglycoside was shown in Table 2. Mouthwash and mouth (Comparative Example 9) In addition to the use of 5. "1 diisobutylpropane In the same manner as in Example 1 except that ethyl dioctyl acid was replaced by ethyl dioctyl acrylate, a solid catalyst was prepared in the same manner as in Example 1, and further, polymerization and formation of a polymerization catalyst were carried out. As a result, titanium in the solid catalyst component was obtained. The content of the mixture was 4.8 wt%. The polymerization result (Comparative Example 10), 帛 4.1 ml t 2_isopropylmalonate ethyl isooctyl ester was substituted for the medium L-isobutylmalonate ethyl 5重量%。 The results are shown in the same as in the first embodiment, the same as in the first embodiment, the solid catalyst component, and the formation of the polymerization catalyst. Table 2. (Comparative Example 11) Same as Example 1 except that 4.5 ml of diisobutylmalonate di-decyl ester was used instead of 4·5 to two 97111247 37 200909460 isobutylmalonate ethyl n-butyl ester The system &amp; u water prepares the solid catalyst component 'and further forms the polymerization catalyst and polymerizes it. The titanium content was 4.3% by weight. The polymerization results are shown in Table 2. (Comparative Example 12) Except that 4.1 ml of 2-isopropylpropionic acid methyl ethyl ester was used instead of *$ ml diisobutylmalonate B. The solid catalyst component was prepared in the same manner as in Example 1 except that the n-butyl acrylate was used, and the polymerization catalyst was further formed and polymerized. The titanium content of the capsule solid component was 4.6 wt%. Table 2. (Comparative Example 13)

Τ! · X 除了使用 ，、· V /土、η 一吸T丞正丁酯代替 4.5 ml二異丁基丙二酸乙基正丁 t 止丁自曰以外，與實施例1同 樣製備固體觸媒成分’進而谁钚取人雜w 史阳進仃聚合觸媒之形成及聚合。 其結果固體觸媒成分中之鈦合右呈炎1r 3有里為4. 5重量％。聚合結 果示於表2。X! · X In addition to the use, · V / soil, η a T-n-butyl ester instead of 4.5 ml diisobutylmalonate ethyl n-butyl t-butyrene, the same as in Example 1 to prepare a solid touch The media component 'and then who draws people's miscellaneous w Shiyang Jinyu polymerization catalyst formation and polymerization. 5重量百分比。 The result of the solid catalyst composition of the right side of the sulphate. The polymerization results are shown in Table 2.

97111247 38 200909460 表1 供電子化合物 聚合活性 (g-PP/g-cat.) HI (wt%) MI (g/10 min.) 實施例 1 二異丁基丙二酸乙基 正丁酯 49, 200 96.6 42 實施例 2 二異丁基丙二酸乙基 異辛酯 34, 300 95. 5 49 實施例 3 二異丁基丙二酸甲基 乙酯 34,300 96. 1 72 實施例 4 二異丁基丙二酸正丁 酯 45,500 96.5 85 實施例 5 雙（3-正丙基）丙二酸 曱基正丁酯 33,600 96.2 90 實施例 6 丁基溴代丙二酸甲基 正丁醋 33,700 97. 2 76 實施例 7 丁基溴代丙二酸乙基 正丁酯 29,900 96. 5 64 實施例 8 第三丁基甲基丙二酸 甲基正丁酯 29,400 96. 1 75 實施例 9 二異丁基丙二酸乙基 異丁酯 47,600 96. 2 50 實施例 10 二異丁基丙二酸曱基 異丁酯 43,300 96. 0 81 實施例 11 第三丁基曱基丙二酸 曱基異丁酯 30,300 95. 9 83 實施例 12 二異丁基丙二酸曱基 正丁醋 34,100 95.3 74 實施例 13 二異丁基丙二酸甲基 正丁醋 36,600 96.0 71 實施例 14 二異丁基丙二酸曱基 正丁醋 47,300 96.5 88 實施例 15 二異丁基丙二酸甲基 正丁酯 43,300 95. 9 140 97111247 39 200909460 表2 Ο97111247 38 200909460 Table 1 Electropolymer compounding activity (g-PP/g-cat.) HI (wt%) MI (g/10 min.) Example 1 Diisobutylmalonate ethyl n-butyl ester 49, 200 96.6 42 Example 2 Diisobutylmalonate ethyl isooctyl ester 34, 300 95. 5 49 Example 3 Diisobutylmalonate methyl ethyl ester 34,300 96. 1 72 Example 4 Diisobutyl N-butyl malonate 45,500 96.5 85 Example 5 Bis-butyl 3-(3-n-propyl)malonate 33,600 96.2 90 Example 6 Butylbromomalonate methyl n-butyl vinegar 33,700 97. 2 76 Example 7 ethyl n-butyl butyl bromomalonate 29,900 96. 5 64 Example 8 methyl n-butyl methyl butyl methyl malonate 29,400 96. 1 75 Example 9 Diisobutyl butyl Ethyl isobutyl ester diacid 47,600 96. 2 50 Example 10 Indyl isobutyl butyl isobutyl acrylate 43,300 96. 0 81 Example 11 Tert-butyl isobutyl butyl methacrylate 30,300 95. 9 83 Example 12 Diisobutylmalonate decyl n-butyl vinegar 34,100 95.3 74 Example 13 Diisobutylmalonate methyl-n-butyl vinegar 36,600 96.0 71 Example 14 Butyl propyl malonate n-butyl vinegar 47,300 96.5 88 Example 15 Diisobutylmalonate methyl n-butyl ester 43,300 95. 9 140 97111247 39 200909460 Table 2 Ο

由表1及表2之纟士果 成分及觸媒進行丙；之=’：:使用本發明之固體觸媒 而能夠以高產率來二’可顯示更高之對氫活性，進 (產業上之可利用:Γ 則性之婦煙類聚合體。 使用本發明之烯烴類聚合用觸 南且對氫活性良好，㈣以高產样彳;活性 物。 座手彳又侍间立體規則性聚合 97111247 40 200909460 【圖式簡單說明】 圖1為表示製備本發明之聚合觸媒之步驟之流程圖。The custard component and the catalyst of Tables 1 and 2 are used for C; and = ':: using the solid catalyst of the present invention, the high activity can be used to display a higher hydrogen activity, and the industry is industrially It can be used: 妇 之 之 妇 。 。 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用40 200909460 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the steps of preparing the polymerization catalyst of the present invention.

97111247 4197111247 41

Claims (1)

200909460 十、申請專利範圍： 1. 一種烯烴類聚合用固體觸媒成分’其係使鎂化合物 (a)、4價之鹵化鈦化合物及以下述通式（1)表示之電 子供應性化合物（c )相接觸而製備： RVCCCOOfXCOOR4) (!) (式中，R及R為鹵素原子、碳數】至2〇之直鏈狀或支鏈 狀烷基、€烷基、苯基、乙烯基、烯丙基、芳烷基及取代 有1個或2個鹵素原子之碳數j纟1〇之直鏈狀或支鏈狀 烷基之任一者，可相同或不同；R3表示碳數丨〜3之烷基、 環烧基、乙稀基、烯丙基，R4為碳數2〜2〇之烧基、環烧 基、苯基、乙烯基、烯丙基、芳烧基之任一者，尺3與r4 不同）。 2. 如申請專利範圍第1項之烯烴類聚合用固體觸媒成 分’其中’於上述通式⑴中，RI為甲基或異丁基。 3. 二：°月專利範圍第1項之烯烴類聚合用固體觸媒成 υ分’其中，於上述通式⑴中，R1為甲基且反2為第三丁基， 或者R為異丁基且R2為異丁基。 分之婦烴類聚合用固體觸媒成 ⑴中’R3為陶乙基。 八圍第1項之歸烴類聚合用固體觸媒成 :乙Ln 供應性化合物(c)為自二異丁基丙二 二乙—異丁基丙二酸甲基乙醋、二異丁基丙二 酉文乙基異辛g曰、二異丁基丙二醆 二酸甲基異丁酯、-異丁美丙土丁酯、二異丁基丙 一異丁基丙—酸乙基異丁醋、雙（3-氯- 97111247 42 200909460 正丙基）丙二酸曱基正丁酯、丁基溴代丙二酸曱基正丁 酯、丁基溴代丙二酸乙基正丁酯、第三丁基曱基丙二酸甲 基正丁s曰、第三丁基曱基丙二酸曱基異丁酯中選擇之化合 物。 6.如申請專利範圍帛}項之烯烴類聚合用固體觸媒成 分，其中，上述鎂化合物為二烷氧基鎂，上 鈦化合物為四氣化鈦。 &quot; 7· —種烯烴類聚合用觸媒，其特徵在於係藉由下述所形 成： (A)申請專利範圍帛！項之烯烴類聚合用固體觸媒成 分； (B)以通式（2)表示之有機鋁化合物： R5pA1Q3-p (2) 表示虱原子或者鹵200909460 X. Patent Application Range: 1. A solid catalyst component for olefin polymerization, which is a magnesium compound (a), a tetravalent titanium halide compound, and an electron-donating compound represented by the following formula (1) Prepared by contact: RVCCCOOfXCOOR4) (!) (wherein R and R are halogen atoms, carbon number) to 2〇 linear or branched alkyl, alkyl, phenyl, vinyl, alkenyl The propyl group, the aralkyl group, and any of the linear or branched alkyl groups having one or two halogen atoms and having a carbon number of J 纟 1 , may be the same or different; R 3 represents a carbon number 丨 〜 3 An alkyl group, a cycloalkyl group, an ethylene group, an allyl group, and R4 is a carbon group having 2 to 2 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aryl group. Ruler 3 is different from r4). 2. The solid catalyst component for olefin polymerization according to the first aspect of the patent application, wherein 'in' is in the above formula (1), and RI is a methyl group or an isobutyl group. 3. Two: The solid catalyst for olefin polymerization in the first paragraph of the patent range is in the above formula (1), wherein R1 is a methyl group and the reverse 2 is a third butyl group, or R is an isobutyl group. And R2 is an isobutyl group. The solid catalyst used for the polymerization of the hydrocarbons in the group is (1) where 'R3 is a ceramic ethyl group. The solid catalyst for the polymerization of hydrocarbons in the first item of the eight divisions is: B. Ln The supply compound (c) is self-diisobutyl propylene di-diethylammonium malonate, diisobutyl Propionate ethyl isooctyl g曰, diisobutyl propylene dimercapto methyl isobutyl ester, butylbutabutin, diisobutyl propyl isobutyl propyl acrylate Butyl vinegar, bis(3-chloro-97111247 42 200909460 n-propyl) decyl butyl acrylate, n-butyl butyl bromomalonate, ethyl n-butyl butyl bromomalonate A compound selected from the group consisting of methyl butyl decyl malonate and n-butyl butyl butyl methacrylate. 6. The solid catalyst component for olefin polymerization according to the scope of the patent application, wherein the magnesium compound is dialkoxymagnesium and the upper titanium compound is titanium tetrahydride. &quot; 7·—A catalyst for olefin polymerization, which is characterized by the following: (A) Patent application scope! a solid catalyst component for olefin polymerization; (B) an organoaluminum compound represented by the formula (2): R5pA1Q3-p (2) represents a ruthenium atom or a halogen (式中，R表示碳數1〜4之烧基，q 素原子’ P為0&lt;p$3之實數）；以及 (C)外部電子供應性化合物。 8. —種烯烴類聚合用觸媒 ， 且 ，、狩徵在於，上述（C)外3 電子供應性化合物為⑹自以通式（3)表示之有 二 物及聚醚中選擇之1種或2種以上： σ R6qSi(NR7R8)r(〇R9)4_(q+r)(3) (式中’q為0或1〜4之整數，r為〇或卜4之整數 q+r為0〜4之整數m “氫原子、碳數^旦 之直鏈或支鏈狀烷基、經取代或未經取代之環烷美、^ 基、乙烯基、烯丙基、芳烷基之任一者， ^ 苯 ^ 』含有雜原子， 97111247 43 200909460 可相同或不同表示碳數1〜4之烷基、環院基、苯基、 乙烯基、烯丙基、芳烷基，可含有鉍 …亦可鍵結而形成環狀)。有雜原子，可相同或不同’ 專聚合體之製造方、去1 專㈣圍第7或8項 去，其特徵在於，於申請 烯烴類之聚合。貞之私類聚合用觸媒之存在下(wherein R represents a carbon group of 1 to 4, a hydroxyl group 'P is 0 &lt; real number of p$3); and (C) an external electron-donating compound. 8. A catalyst for olefin polymerization, wherein the (C) external 3 electron-donating compound is (6) one selected from the two compounds represented by the general formula (3) and a polyether. Or two or more types: σ R6qSi(NR7R8)r(〇R9)4_(q+r)(3) (wherein q is an integer of 0 or 1 to 4, r is an integer of 〇 or Bu, q+r is An integer m of 0 to 4 "a hydrogen atom, a linear or branched alkyl group having a carbon number, a substituted or unsubstituted cycloalkane, a group, a vinyl group, an allyl group, an aralkyl group One, ^ benzene ^ 』 contains a hetero atom, 97111247 43 200909460 can be the same or different to represent a carbon number of 1 to 4 alkyl, ring-based, phenyl, vinyl, allyl, aralkyl, can contain ... It can also be bonded to form a ring.) There are heteroatoms, which can be the same or different. The manufacturer of the specific polymer, go to the 1st or 8th item of the special (4), which is characterized by the application of the polymerization of olefins. In the presence of a private polymerization catalyst 97111247 4497111247 44