TW200302235A - Metal complex compositions and their use as catalysts for olefin polymerization and copolymerization - Google Patents
Metal complex compositions and their use as catalysts for olefin polymerization and copolymerization Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
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- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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200302235 玖、發明說明 (發明說明應敘明:發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明) 【發明所屬之技術領域】 本發明係有關金屬錯合物組成物,其製備及其用作為 催化劑之用途,俾用以經由共軛二烯單體之聚合而製造共 5 軛二烯聚合物、以及共軛二烯與芳香族或非芳香族α婦烴 、或與非共輛一細之共聚物。使用的金屬錯合物組成物包 含鈷錯合物組成物組合第1型活化劑化合物及第2型活化劑 化合物以及催化劑改性劑。特別本發明係關於含有至少一 個鈷-氧鍵之鈷錯合物,以及該催化劑之製備以及製備得 10之催化劑之用途,供用以製造共軛二烯均聚物,或共輕二 烯與芳香族或非芳香族α烯烴、或與非共軛二烯之共聚物 ,較佳係供用於1,3-丁二烯或異戊間二烯之共聚物,較佳 係供用於1,3-丁二烯或異戊間二烯之聚合,或丨,夂丁二婦 或異戊間二烯與苯乙烯或二乙烯基苯之共聚合。 15 【先前技術】 由共輊一稀單體製造聚合物之金屬錯合物催化劑為已 知。 ΕΡ 816,386說明包含過渡金屬化合物之烯烴聚合催化 刮’較佳為選自ΙΙΙΑ、IVA、VA、VIA、VIIA或VIII族過渡 2〇金屬或鑭系元素較佳為鈦、锆、或铪與烷二烯基配位子組 成之化合物。 催化劑進一步包含輔助烷基鋁氧烷催化劑,可用於婦 煙之聚合及共聚合。 基於鈷錯合物及有機鋁活化劑之丨,3 _ 丁二烯聚合用催 200302235 玖、發明說明 化劑係述於專利案以及公開的參考文獻。特別有兩大類基 於始錯合物之催化劑較為經過徹底研究·· A)典型鈷催化劑 ’其係由至少一種魏酸姑(有機缓酸始鹽)組合一或多種烧 基鋁化合物組成,B)鈷化合物或錯合物,其包含鈷化合物 5 或組合至少一種鋁氧烷成分之錯合物。 傳統上,羧酸鈷係與適當有機鋁活化劑成分組合用於 共軛二烯(如1,3_丁二烯及異戊間二烯)之聚合反應。 A)典型鈷催化劑 一種聚丁二烯之製法述於EP 0106596。由至少一種鈷 10化合物,有機齒化鋁(至少一種三烷基鋁化合物與水之反 應產物組成之)成分,以及二氟化碳或/及異氰酸苯酯化合 物組成之催化劑用於1,3-丁二烯之聚合。例如,丁二烯於 苯溶劑暴露於二乙基一氯化鋁以及三乙基鋁與水(比例j : 0.87)之反應產物。隨後藉加入辛酸鈷及二硫化碳開始聚合 15反應。聚合反應結果,回收高比例順-1,3-聚丁二烯(順含 量為 95%至 97.1%)。 專利案EP 770631 B1說明高順l,4-聚丁二烯之製備, 忒製備方法係使用至少一種鈷化合物,至少一種有機鋁化 合物,水,以及除了環烷做為主要溶劑外,使用經取代之 20苯做為式(C6H5_n)R1+n[其中11為3至5之整數,以及其中各個 R表不含1至4個碳原子之低碳烷氧基]之聚合調節劑。較佳 R基表不烧氧基。例如乙醯基丙酮酸鈷(11)組合二乙基氯化 鋁用於1,4- 丁二烯於聚合溶劑之聚合反應,該聚合溶劑係 由%己烷、水、丁烯以及各種濃度之甲氧基取代苯組成。 200302235 玖、發明說明 、須才曰出則述所謂之典型聚合系統結果導致獲得相對低 刀:里艰口物,且仍然要求水組合二垸基鹵化紹來活化録 錯口物用於丁二烯聚合反應。銘錯合物/二有機_化銘/水 系統之水中溶解度低,經常導致製程不穩定。 多考文獻P. Cass等人,聚合物科學期刊:A部聚合 物化子,39 2001 2244-2255」言兒明以調節劑替代苯用於 丁二烯之催化聚合反應,聚合成為高順-1,4-聚丁二烯 典型辛酸姑/二乙基氯化銘/水系統使用1,3,5-三甲氧苯或 甲笨女疋化,且用作為込弘丁二烯於環己烷/丁烯溶劑之 10催化劑。U,5-三甲氧苯推定係透過鍵結至活性催化劑中 〜配位而用作4聚合調節劑。發現加入三甲氧苯可提高活 性催化鈷粒子百分比至約原先數值的200%。但同時形成 的聚丁二烯之轉化率以及順含量降低。例如於1,3,5-三甲 氧苯存在下未曾報告丁二烯之轉化率高於45%。雖然溶劑 5不含於裱保上有特殊限制的苯,但無法避免使用水,仍然 而要使用水來活化辛酸鈷組合二烷基鹵化鋁。如前文所述 ’水於铦錯合物/二有機氯化鋁/水系統之溶解度低,結果 導致製程不穩定。 B)銘化合物或包含至少一種鈷化合物之錯合物或 2〇 鈷錯合物組合鋁氧烷活化劑成分 WO 0004064說明使用姑化合物組合有機鋁化合物及 改性劑’於芳香族乙烯基化合物如苯乙烯存在下,共軛二 歸之聚合反應。鈷化合物例如為有機酸鹽,有機鋁化合物 之必須為紹氧烧。此外,另一種有機紹化合物為由有機 200302235 玖、發明說明 鹵化鋁(A1Ud,R為烷基、環烷基或芳基)與式 HYR’e(Y為元素週期表Vb或VIb族元素,R,為氫、烧基、 裒烧基或芳基)之施體化合物反應所得產物。雖然羧酸鈷 排它地為本發明之目的,溴化鈷膦加合物催化劑 5 C〇Br2(PPh3)2遠用以驗證本發明。例如丁二稀及苯乙稀無 需額外聚合溶劑,使用C〇Br2(PPh3)2,艾歐諾(I〇n〇l)[(2,6_ 一-第二丁基甲基)紛]及甲基鋁氧烷(MAO)組成的催化 劑系統進行共聚合。專利案DE 19832455 A1類似前述專利 案 WO 0004064。 10 根據US 5,879,805,姑化合物如鹵化姑、有機酸有機 鹽之鈷化合物等組合有機鋁化合物以及一種[選自膦、黃 素原(xanthogen)或硫異氰化物組成的組群之]化合物,用 於氣相反應器聚合1,3-丁二烯。有機鋁化合物係以選自三 有機铭AIR3、有機_化鋁AlR'X^m、或鋁氧烷 15 A1Rn2(0R3)34之化合物之一表示。例如二鹵化鈷膦加合物200302235 发明 Description of the invention (The description of the invention should state: the technical field, prior art, content, embodiments, and drawings of the invention are briefly explained.) [Technical field to which the invention belongs] The present invention relates to a metal complex composition. Preparation and its use as a catalyst for the production of conjugated diene polymers by polymerization of conjugated diene monomers, and conjugated diene and aromatic or non-aromatic alpha-hydrocarbons, or A total of one fine copolymer. The metal complex composition used includes a cobalt complex composition combination of a type 1 activator compound and a type 2 activator compound and a catalyst modifier. In particular, the present invention relates to a cobalt complex containing at least one cobalt-oxygen bond, as well as the preparation of the catalyst and the use of a catalyst to obtain 10 for the manufacture of conjugated diene homopolymers, or co-diene and aromatics. Family or non-aromatic alpha olefins, or copolymers with non-conjugated dienes, preferably for copolymers of 1,3-butadiene or isoprene, more preferably for copolymers of 1,3- Polymerization of butadiene or isoprene, or copolymerization of butadiene or isoprene with styrene or divinylbenzene. 15 [Prior art] Metal complex catalysts for producing polymers from a dilute monomer are known. EP 816,386 states that olefin polymerization catalysts containing transition metal compounds are preferably selected from the group consisting of IIIA, IVA, VA, VIA, VIIA or VIII transitions. 20 metals or lanthanides are preferably titanium, zirconium, or hafnium and alkanes. A compound consisting of an alkenyl ligand. The catalyst further includes an auxiliary alkylaluminoxane catalyst, which can be used for the polymerization and copolymerization of tobacco. Based on cobalt complexes and organoaluminum activators, 3_butadiene polymerization catalyst 200302235 发明, description of invention Chemical agents are described in patent cases and published references. In particular, there are two major types of catalysts based on incipient complexes that have been thoroughly studied. A) Typical cobalt catalysts' are composed of at least one Wei acid (organic slow acid starting salt) combined with one or more aluminum-based compounds, B) A cobalt compound or complex comprising a complex of cobalt compound 5 or a combination of at least one alumoxane component. Traditionally, cobalt carboxylates have been used in combination with appropriate organoaluminum activator ingredients for the polymerization of conjugated diene (such as 1,3-butadiene and isoprene). A) Typical cobalt catalyst A process for the preparation of polybutadiene is described in EP 0106596. A catalyst composed of at least one cobalt 10 compound, organic toothed aluminum (composed of at least one trialkyl aluminum compound and water reaction product), and carbon difluoride or / and phenyl isocyanate compounds, Polymerization of 3-butadiene. For example, butadiene is exposed to a benzene solvent to diethylaluminum monochloride and the reaction product of triethylaluminum and water (ratio j: 0.87). The polymerization was then started by adding cobalt octoate and carbon disulfide. As a result of the polymerization reaction, a high proportion of cis-1,3-polybutadiene was recovered (cis content was 95% to 97.1%). Patent case EP 770631 B1 describes the preparation of Gao Shun 1,4-polybutadiene. The preparation method of rhenium uses at least one cobalt compound, at least one organoaluminum compound, water, and in addition to naphthenes as the main solvent, substituted 20 benzene is used as a polymerization regulator of the formula (C6H5_n) R1 + n [wherein 11 is an integer of 3 to 5, and each R table does not contain a low-carbon alkoxy group of 1 to 4 carbon atoms]. Preferably, R is oxy. For example, cobalt ethylacetonate (11) combined with diethylaluminum chloride is used for the polymerization of 1,4-butadiene in a polymerization solvent. The polymerization solvent consists of hexane, water, butene, and various concentrations. Composition of methoxy substituted benzene. 200302235 Rhenium, description of inventions, and descriptions of the requirements of the so-called typical polymerization system lead to relatively low-profile results, and still require water to combine difluorenyl halides to activate misregistrations for butadiene Polymerization. Ming complex / two organic _ chemical Ming / water system solubility in water is low, often leading to process instability. P. Cass et al., Polymer Science Journal: Part A Polymer Chemist, 39 2001 2244-2255 "Yan Erming replaced the benzene with a regulator for the catalytic polymerization of butadiene, and the polymerization became Gao Shun-1 , 4-Polybutadiene is a typical octanoic acid / diethyl chloride / water system using 1,3,5-trimethoxybenzene or methylbenzidine, and is used as a cyclobutadiene in cyclohexane / 10 catalysts for butene solvents. U, 5-trimethoxybenzene is presumed to be used as a 4 polymerization regulator by bonding to the active catalyst through coordination. The addition of trimethoxybenzene was found to increase the percentage of active catalytic cobalt particles to approximately 200% of the original value. However, the conversion rate and cis content of the polybutadiene formed at the same time are reduced. For example, the conversion of butadiene has not been reported to be higher than 45% in the presence of 1,3,5-trimethoxybenzene. Although solvent 5 does not contain benzene with special restrictions on the mounting substrate, the use of water is unavoidable, and it is still necessary to use water to activate the cobalt octylate combination dialkyl aluminum halide. As mentioned above, the solubility of the water in the amidine complex / diorganoaluminum chloride / water system is low, resulting in unstable process. B) Ming compound or complex containing at least one cobalt compound or 20 cobalt complex combination alumoxane activator component WO 0004064 illustrates the use of a combination of organoaluminum compounds and modifiers in aromatic vinyl compounds such as Polymerization of conjugated dimerization in the presence of styrene. The cobalt compound is, for example, an organic acid salt, and the organic aluminum compound must be sintered. In addition, another organic compound is aluminum halide (A1Ud, R is alkyl, cycloalkyl, or aryl) and organic formula HYR'e (Y is Vb or VIb group element of the periodic table, R Is a product obtained by reacting a donor compound such as hydrogen, alkyl, sulfanyl or aryl). Although cobalt carboxylate is exclusively for the purpose of the present invention, cobalt bromide phosphine adduct catalyst 5 CoBr2 (PPh3) 2 is far from validating the present invention. For example, butadiene and styrene need no additional polymerization solvent, use CoBr2 (PPh3) 2, Ionol (Ionol) [(2,6_ mono-second butylmethyl)] and methyl aluminum A catalyst system consisting of oxane (MAO) was copolymerized. Patent DE 19832455 A1 is similar to the aforementioned patent WO 0004064. 10 According to US 5,879,805, a compound such as a halogenated compound, a cobalt compound of an organic acid organic salt, and the like is a combination of an organoaluminum compound and a compound [selected from the group consisting of phosphine, xanthogen, or sulfur isocyanide] for gas Reverse reactor polymerizes 1,3-butadiene. The organoaluminum compound is represented by one of the compounds selected from the group consisting of triorganic AIR3, organo-aluminum AlR'X ^ m, or alumoxane 15 A1Rn2 (0R3) 34. Cobalt dihalide phosphine adduct
CoBr2(PPh3)2、乙醯基丙酮酸鈷Co(acac)3或甲基_卜丙烯 基)(丁-1,3-二烯)三苯基膦鈷單獨借助於甲基鋁氧烷活化, 或於適當撐體材料存在下活化,隨後用於丁二烯聚合反應 。以乙醯基丙酮酸鈷為主之催化劑為例,未曾述及有關聚 20 合物之顯微結構或分子量。 1^6,001,478說明類似專利案1)8 5,879,805之實施例, 但申請專利範圍係有關氣相聚合所需惰性粒狀材料。 於EP 0816398及JP 10-7717,至少一種鈷成分,至少 一種三烷基鋁化合物,以及式AlR2mX3-m(X為鹵陰離子, 200302235 玖、發明說明 R2表示烴基,m為0至2之數目)之烷基鹵化鋁化合物或/及 式R X(R表示經基)之烧基鹵化合物,及水組成之催化劑 系統,用以1,3- 丁二烯之聚合。最佳鋁氧烷成分係經由三 烷基鋁化合物混合水而預先製備。如此,由至少一種姑化 5合物,鋁氧烷成分,烷基函化鋁化合物及/或烷基函化合 物組成之催化劑系統也被請求專利用作為丨,3_丁二烯聚合 催化劑。舉例言之,辛酸鈷、甲基鋁氧烷、乙基倍半氣化 鋁(EASC)組合1,5-環辛二烯用作為分子量改性劑。結果所 得聚合物於所述實施例包含大於97%順聚丁二稀,平均分 10 子量為 390,000 及 450,000 克 / 莫耳。慕尼值(M〇〇ney values) (ML 1+4)為29至34。須指出各實施例中,ι,3_丁二稀之轉化 率不超過50%。 JP 10-158333請求1,2-聚丁二豨之製備程序。ι,2_聚丁 二婦係使用催化劑經由1,3-丁二烯之聚合反應製備,該催 15化劑係由鈷化合物、膦化合物、甲基鋁氧烷、或三甲基鋁 與水之反應產物、以及含矽原子化合物製成。 JP 11-140118請求專利使用催化劑製備聚丁二烯之程 序,該催化劑係由鈷化合物、以及鋁氧烷成分以及有機齒 素化合物組成。鋁氧烷成分及有機_素化合物於使用前必 20 須老化。 根據JP 114817引進一種由共軛二烯製備聚合物之程序 。應用於二烯聚合之催化劑含有鈷化合物,至少一種鋁氧 烧成分’以及含有函素原子之化合物。含自素原子化合物 為金屬南素化合物與路易士鹼之反應產物。 10 200302235 玖、發明說明 專利案JP 8-325331說明聚丁二烯之製備程序。L3-丁 一細係使用結化合物組合通式AIR3之三烧基链化合物、氧 化鋁化合物,以及一種(選自二氧化碳、異氰酸苯酯以及 黃素原酸鹽化合物組成的組群之)化合物組合進行聚合反 5 應。 JP 6-116316及JP 128301請求含高含量乙烯鍵之丁二 烯聚合物。聚丁二烯含量達至少50莫耳百分比。用於製備 共聚物之催化劑係由鈷鹽、含鋁氧烷之有機鋁化合物、及 膦化合物組成。聚合反應係於無活性有機溶劑且使用氫氣 10進行。專利案JP 6-128301額外請求使用連續及非連續聚合 法製備前述聚合物。 專利案JP 6-1163 15類似前述專利案jp 6-116316,但供 丁二稀聚合物製備用之催化劑額外含有_化有機鋁化合物。 JP 6-116342也類似前述專利案jP 6-116316,請求含高 15含量乙烯鍵之丁二烯共聚物。第二單體(1至30莫耳%共聚 物)也包含共軛雙鍵。共聚物之丁二烯部分含有8〇%或以上 乙烯鍵。供共聚物製備用之催化劑例如含有鈷化合物、甲 基鋁氧烷(MAO)及三苯基膦(pph3)。 專利案JP 7-102014敘述含至少5〇莫耳%聚丁二烯之聚 20合物之製備程序。所得聚合物係使用鈷化合物組合含鋁氧 烷成分之有機鋁化合物以及如下通式烷基苯氧化鋁化合物 製備 200302235 玖、發明說明CoBr2 (PPh3) 2, Cobalt acetamylpyruvate Co (acac) 3 or methyl_bupropenyl) (but-1,3-diene) triphenylphosphine cobalt is activated by methylalumoxane alone, Alternatively, it can be activated in the presence of a suitable support material and subsequently used for butadiene polymerization. Taking the catalyst based on cobalt acetopyruvate as an example, the microstructure or molecular weight of the polymer has not been mentioned. 1 ^ 6,001,478 describes an example similar to patent case 1) 8 5,879,805, but the scope of the patent application is related to inert granular materials required for gas phase polymerization. In EP 0816398 and JP 10-7717, at least one cobalt component, at least one trialkylaluminum compound, and the formula AlR2mX3-m (X is a halogen anion, 200302235 玖, description of the invention R2 represents a hydrocarbon group, and m is a number from 0 to 2) A catalyst system consisting of an alkylaluminum halide compound or / and a halogenated halogen compound of the formula RX (R represents a radical) and water is used for the polymerization of 1,3-butadiene. The optimum aluminoxane component is prepared in advance by mixing water with a trialkylaluminum compound. In this way, a catalyst system composed of at least one pentad compound, alumoxane component, aluminum alkyl compound, and / or alkyl functional compound has also been patented as a catalyst for the polymerization of 3-butadiene. By way of example, cobalt octoate, methylalumoxane, and ethyl sesquicarbonate (EASC) in combination with 1,5-cyclooctadiene are used as molecular weight modifiers. As a result, the obtained polymer contained more than 97% cis-polybutadiene in the examples, and the average molecular weight was 390,000 and 450,000 g / mole. Mooney values (ML 1 + 4) are 29 to 34. It should be noted that the conversion rate of ι, 3-dioxane in each of the examples is not more than 50%. JP 10-158333 requests a procedure for the preparation of 1,2-polybutadiene. ι, 2_ polybutadiene is prepared through the polymerization of 1,3-butadiene using a catalyst. The catalyst is a cobalt compound, a phosphine compound, methylalumoxane, or trimethylaluminum and water. Reaction products and silicon atom-containing compounds. JP 11-140118 claims a process for preparing polybutadiene using a catalyst, which is composed of a cobalt compound, an alumoxane component, and an organic halide compound. The aluminoxane and organic compounds must be aged before use. A procedure for preparing a polymer from a conjugated diene was introduced according to JP 114817. The catalyst used for the polymerization of diene contains a cobalt compound, at least one aluminizing component ', and a compound containing a halide atom. The compounds containing autogen atoms are the reaction products of metal south compounds and Lewis bases. 10 200302235 (ii) Description of the invention Patent JP 8-325331 describes the preparation procedure of polybutadiene. The L3-butadiene system is a combination of a compound consisting of a trialkyl group compound of the general formula AIR3, an alumina compound, and a compound selected from the group consisting of carbon dioxide, phenyl isocyanate, and a flavin orthoate compound. Aggregation reaction. JP 6-116316 and JP 128301 request a butadiene polymer having a high content of ethylene bonds. The polybutadiene content is at least 50 mole percent. The catalyst used to prepare the copolymer is composed of a cobalt salt, an aluminoxane-containing organoaluminum compound, and a phosphine compound. The polymerization was carried out in an inert organic solvent and using hydrogen 10. Patent JP 6-128301 additionally requests the preparation of the aforementioned polymers using continuous and discontinuous polymerization processes. The patent JP 6-1163 15 is similar to the aforementioned patent jp 6-116316, but the catalyst for the production of succinic polymers additionally contains an organic aluminum compound. JP 6-116342 is also similar to the aforementioned patent jP 6-116316 and claims a butadiene copolymer having a high content of 15 ethylene bonds. The second monomer (1 to 30 mole% copolymer) also contains a conjugated double bond. The butadiene portion of the copolymer contains 80% or more of ethylene bonds. The catalyst for the preparation of the copolymer contains, for example, a cobalt compound, methylalumoxane (MAO) and triphenylphosphine (pph3). Patent JP 7-102014 describes the procedure for preparing a poly 20 compound containing at least 50 mole% polybutadiene. The obtained polymer is prepared by using a cobalt compound in combination with an organoaluminum compound containing an alumoxane component and an alkyl benzene alumina compound of the following general formula.
(R1為烷基,R2-R6為氫原子、鹵原子、烷基、烷氧基 或芳基,η為1或2)於無活性有機溶劑。 專利案RU 21255778 C1說明一種與芳香族溶劑合成 5順-1,‘聚丁二烯之程序。共軛二烯(特別1,3-丁二烯)之聚 合反應係於可溶解之鈷鹽、(一)氯化鋁或倍半氣化鋁以及 聚鋁氧烷(R)2Al-[OAlR]n-〇-Al(R)2 或胺基鋁氧烷(r)2A1-〇_ cH2_n(r’)(r”)[其中r表示乙基或異丁基,R,為a1(R2),r,, 為氫或A1(R2)以及η為〇、1或2]存在下進行。鈷化合物例如 10 為〗衣烧酸姑、辛酸敍或乙酿基丙酮酸姑。 專利案RU 2082721 C1說明一種於烴溶劑(如甲苯)使 用催化劑系統合成順-1,4-聚丁二烯之程序,該催化劑系統 係由鈷化合物、烷基氣化鋁化合物、水及下式聚鋁氧烷化 合物組成:(R)2Al-[0AlR]n-0-Al(R)2,其中R表示乙基或異 15 丁基以及η至少為2。鈷化合物例如為環烷酸鈷、辛酸鈷、 硬脂酸鈷、2-乙基己酸鈷或乙醯基丙酮酸鈷。烷基氯化鋁 化合物係選自二異丁基氣化鋁、二乙基氯化鋁、異丁基氯 化紹及乙基倍半氯化紹組成的組群。 一種於催化劑存在下製造聚丁二烯之方法述於Ερ 20 0511015 Β1,該催化劑係由姑膦錯合物以及大致包含鋁 氧烷之有機鋁化合物組成。例如,貳(三苯基膦)二溴化鈷 、甲基鋁氧烷(ΜΑΟ)、甲苯溶劑及ι,3-丁二烯置於不銹鋼 12 200302235 玖、發明說明 高壓銷。分子量為101000至384000。丁二烯轉化率低,經 4小時後不超過40%。結果所得聚丁二烯之微結構(順_u_/ 反-1,3-/1,2-聚丁二烯比)並未提供於該專利案。 EP 0511015 B1說明一種聚丁二烯之製法。根據本專 5利案,U·丁二烯係於催化劑存在下聚合,該催化劑係由 鈷-膦錯合物以及有機鋁化合物(較佳表示鋁氧烷成分)組成 。例如三苯基膦)二漠化鈷使用甲基鋁氧烷於曱苯處理 形成催化劑。聚合反應結果導致大於6〇%之高比例之1,2_ 聚丁二烯。但該專利案報告之聚合物轉化率於全部實施例 10 皆係低於24%。 15 20 BP 0433943 A2請求催化劑成分八之料,該催化劑成 分A係由通式M(R)1(0R,)mXn(i+m)表示之過渡金屬化合物, 其中Μ表示過渡金屬原子,尺及尺,分別表示烴基,以及X表 示函原子。較佳過渡金屬化合物之金料表示鈦或錯。催 化劑成分Β為有機鋁化合物,其可為鋁氧烷、三烴基鋁化 合物或烴基鹵化鋁。催化劑成分。為帶有至少兩羥基之有 機化合物(如烧二醇)或帶有兩個或兩個以上經基之芳香族 化合物。有機化合物之組群例如為混合二甲笨。前述催化 :主要係用於製備反_聚丁二烯。典型例包括四氣化鈦與 芳香族二醇(如2,2,-二經基_3,3,_二_第三丁基_5,5,·二甲基 二苯基硫化物)反應,接著與甲基銘氧烷反應。所得催: 劑用於U-丁二烯之聚合。本專利案並未涵括第二種以鋁 為主的成分於催化劑形成過程,基本上限於以鈦及錯為主 之催化心15物。表示成分C之有機化合物用於形成所需 13 200302235 玖、發明說明 催化劑前驅物,但非做為進行中之聚合方法之改性劑。 辛酸鈷用作為催化劑’組合甲基銘氧院以及第三丁基 氯,用於使用溶劑混合物製備高順聚丁二稀,該溶 物含有廳環己烧’15%苯,35%τ烯及篇u.丁二稀單 體(參考P. Cass等人’聚合物科學期刊:A部分··聚合物化 學,W277-遍)。於3〇%u_丁二稀轉化率,達到 最高動噴-M-聚丁二烯含量。比較典型辛⑽/二乙基氣 ㈣m㈣之辛酸氧燒/第三丁基氯催化劑就 ίο 15 20 聚丁二烯品質而言並未顯示顯著差異,但聚合物之線性程 度略微提升。效果為芳香族苯溶劑含量顯著減少。 此外’對使用辛酸姑/鋁氧烷/笛__^ ^ 乳沉/第二丁基氣催化劑系統 之U-丁二稀聚合反應進行動態研究,述於p. Cass等人(聚 合物科學期刊:A部分:聚合物化學,39讀2256_2叫。 希望有一種姑催化劑系統,其無需使用水即可活化, 俾保證容易做製程㈣。此外’所需催化劑系統必須於不 含苯及/或甚至實質上不含芳香族化合物之溶劑系統進行 。此種催化㈣統比至今維持已知之絲烧含㈣化劑系 統更具有活性。此外希望有催化劑成分,該催化劑成分可 直接注入聚合反應而益需「丰儿 …、而老化」(攪拌、振搖或儲存)催 化劑或催化劑成分經歷一段長時間。此外,若所需姑催化 劑系統可共聚合共輛二烯與α烯烴,較佳為㈣細缚煙列 更有利。例如丁二稀-苯乙稀共聚物用於多項用途令人感 興趣。 之备、-烤均聚物、 只有一類共軛二烯單體聚合法製造 14 200302235 玖、發明說明 或於共聚合法製造之共聚物、及該等聚合方法為本發明之 目的,該共聚合法為-類共轭二婦單體與另_類共輕 單體共聚合、或與-或二類非芳香族⑽煙或非 5 、,純化合物或錯合物使用下組合活化劑及催化劑改性劑 進行共聚合。特別用於合成共輛二婦單體之均聚物或共聚 物之姑化合物或錯合物含有至少_個姑_氧鍵。更特別二 烯單體例如為U·丁二稀,異戊間二婦為均聚合;或二: 單體(例如但非限於U-丁二烯及異戊間二稀)係與芳香族 10 或非芳香族4煙或非芳香族非共輕二烯(例如但非限於笨 乙稀、二乙婦基苯或二乙烯基甲苯、1-己烯、1·辛婦、卜 癸烯、1,5-己二烯、u-辛二烯或u癸二婦),使用前述 始化合物或錯合物組合活化劑,且組合一或多種芳香族化 物U為改jt劑進行共聚合反應。特別紹氧烧類活化劑或 非配位陰離子成形劑(例如但非限於有機硼酸鹽或有機硼 15 -物)X及種统基齒化銘類活化劑,組合姑錯合物以 及組合-或多種芳香族化合物用於合成均聚物或共聚物。 更特別一種1呂氧炫類活化劑以及-種烧基鹵化紹類活化劑 組合始錯合物以及組合一種芳香族化合物用於合成均聚物 20 或共聚物。特別芳香族改性劑係以類似活化劑用量或小於 活化劑用量施用。 【發明内容】 本發明目的為錯錯合物,其可供形成烯烴單體特別二 烯單體’更特別共軛二烯單體聚合用催化劑組成物。本發 月之另一目的為録錯合物,其可用於形成烯烴單體,特別 15 玖、發明說明 二稀單體,二料 體如共輛二料體,师工早體’特別二稀單(R1 is an alkyl group, R2-R6 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and η is 1 or 2) in an inert organic solvent. Patent RU 21255778 C1 describes a procedure for the synthesis of 5cis-1, 'polybutadiene with an aromatic solvent. The polymerization of conjugated diene (especially 1,3-butadiene) is based on soluble cobalt salts, (a) aluminum chloride or sesquigas, and polyalumoxane (R) 2Al- [OAlR] n-〇-Al (R) 2 or amine aluminoxane (r) 2A1-〇_ cH2_n (r ') (r ”) [where r is ethyl or isobutyl, R is a1 (R2), r, is hydrogen or A1 (R2) and η is 0, 1 or 2]. The cobalt compound, for example, 10 is ignite, octanoate, or ethylpyruvate. Patent Case RU 2082721 C1 Description A process for synthesizing cis-1,4-polybutadiene in a hydrocarbon solvent (such as toluene) using a catalyst system consisting of a cobalt compound, an alkyl aluminum oxide compound, water, and a polyalumoxane compound of the following formula : (R) 2Al- [0AlR] n-0-Al (R) 2, where R represents ethyl or iso 15 butyl and η is at least 2. The cobalt compound is, for example, cobalt naphthenate, cobalt octoate, stearic acid Cobalt, cobalt 2-ethylhexanoate or cobalt acetopyruvate. The alkylaluminum chloride compound is selected from the group consisting of diisobutylaluminum gaseous, diethylaluminum chloride, isobutylaluminum chloride, and ethyl A group consisting of sesquichloride. One exists in the catalyst The method for making polybutadiene is described in Ερ 20 0511015 B1. The catalyst is composed of a phosphine complex and an organoaluminum compound that roughly contains alumoxane. For example, osmium (triphenylphosphine) cobalt dibromide, formazan Aluminoxane (ΜΑΟ), toluene solvent and ι, 3-butadiene are placed on stainless steel 12 200302235 玖, invention description high pressure pin. Molecular weight is 101,000 to 384000. Butadiene conversion is low, not more than 40 after 4 hours %. The microstructure of the obtained polybutadiene (cis_u_ / trans-1,3- / 1,2-polybutadiene ratio) was not provided in the patent case. EP 0511015 B1 describes a polybutadiene Production method. According to the 5 patents of this patent, U · butadiene is polymerized in the presence of a catalyst, which is composed of a cobalt-phosphine complex and an organoaluminum compound (preferably an alumoxane component). For example, triphenyl Cobalt phosphine) Cobalt di-molybdenum is treated with methylaluminoxane in toluene to form a catalyst. The polymerization reaction results in a high proportion of polybutadiene greater than 60%. However, the polymer conversion rate reported in this patent case In all the examples 10, it is lower than 24%. 15 20 BP 0433943 A2 request for reminder The catalyst component A is a transition metal compound represented by the general formula M (R) 1 (0R,) mXn (i + m), where M represents a transition metal atom, a ruler and a ruler each represent a hydrocarbon group, And X represents a function atom. The preferred gold material of the transition metal compound represents titanium or copper. The catalyst component B is an organoaluminum compound, which may be an alumoxane, a trihydrocarbyl aluminum compound, or a hydrocarbyl aluminum halide. The catalyst component. Two hydroxy organic compounds (such as burned glycol) or aromatic compounds with two or more warp groups. The group of organic compounds is, for example, mixed dimethylbenzyl. The aforementioned catalysis is mainly used for preparing trans-polybutadiene. Typical examples include the reaction of titanium tetragas with an aromatic diol (such as 2,2, -diacryl_3,3, _di_thirdbutyl_5,5, · dimethyldiphenylsulfide) , And then react with methyl alumoxane. The obtained catalyst is used for the polymerization of U-butadiene. This patent does not cover the second aluminum-based component in the catalyst formation process, which is basically limited to the catalytic core 15 mainly composed of titanium and tungsten. The organic compound representing component C is used to form the desired 13 200302235 玖, description of the invention The catalyst precursor, but not as a modifier for the ongoing polymerization process. Cobalt octoate is used as a catalyst 'combined with Methyl Oxygen Institute and a third butyl chloride, used to prepare a high cis polybutadiene using a solvent mixture. The solution contains cyclohexyl'15% benzene, 35% τene and articles Dibutene monomers (see P. Cass et al. 'Journal of Polymer Science: Part A. Polymer Chemistry, W277-pass). At 30% u_butadiene conversion, the highest dynamic spray-M-polybutadiene content was reached. Comparing the typical octane / diethyl ㈣m㈣ octanoic acid / third butyl chloride catalysts did not show significant differences in terms of the quality of 15 20 polybutadiene, but the linearity of the polymer improved slightly. The effect is a significant reduction in aromatic benzene solvent content. In addition, a dynamic study of U-butadiene polymerization using octanoic acid / alumoxane / di __ ^^ ^ milk precipitation / second butyl gas catalyst system is described in p. Cass et al. (Journal of Polymer Science : Part A: Polymer Chemistry, 39 read 2256_2. I hope there is a catalyst system that can be activated without the use of water, which guarantees easy process. In addition, the required catalyst system must be free of benzene and / or even A solvent system containing substantially no aromatic compounds is carried out. Such a catalytic system is more active than the known silk-fired amidine-containing system which has been known so far. In addition, it is desirable to have a catalyst component, which can be directly injected into the polymerization reaction. "Fenger ..., and aging" (stirring, shaking or storage) catalysts or catalyst components undergo a long period of time. In addition, if the required catalyst system can copolymerize diene and alpha olefins, it is preferable to bind them. Smoke is more advantageous. For example, butadiene-styrene copolymers are interesting for many purposes. Preparation, roasting homopolymer, only one type of conjugated diene monomer polymerization method 14 200302235 玖, Description of the invention or a copolymer produced by a copolymerization method, and such polymerization methods are the purpose of the present invention, the copolymerization method is-a conjugated dimer monomer and another _ -type light monomer copolymerization, or with-or The second class of non-aromatic soot or non-5, pure compounds or complexes are used in combination with activators and catalyst modifiers for copolymerization. It is especially used for the synthesis of homopolymers or copolymers of dimer monomers. The compound or complex contains at least one oxygen bond. More particularly, the diene monomer is, for example, U.butadiene, and the isoprene is homopolymerization; or the monomer (for example, but not limited to U- Butadiene and isoprene) are aromatic 10 or non-aromatic 4 smoke or non-aromatic non-co-light diene (such as, but not limited to, stilbene, diethenylbenzene or divinyltoluene, 1-hexene, 1. succinyl, decadiene, 1,5-hexadiene, u-octadiene or u decadiene), use the aforementioned starting compound or complex to combine an activator, and combine one or A variety of aromatic compounds U are changed to jt agent for copolymerization reaction. In particular, sintering activators or non-coordinating anion forming agents (such as but not In organic borate or organic boron 15-ite) X and germ-based denatured activators, combined complexes and combined-or multiple aromatic compounds are used to synthesize homopolymers or copolymers. More specifically a 1 Lu Xuanxuan type activator and a kind of burn-based halogenated Shao type activator combined initial complex and combined with an aromatic compound for the synthesis of homopolymer 20 or copolymer. Special aromatic modifier is used in a similar amount of activator Or less than the amount of activator to be applied. [Summary of the invention] The object of the present invention is a complex complex, which can be used to form a catalyst composition for the polymerization of olefin monomers, especially diene monomers, and more particularly conjugated diene monomers. Another purpose is to record the wrong compound, which can be used to form olefin monomers, especially 15 玖, invention description two dilute monomers, two materials such as a total of two materials, the engineer early body 'special two dilute monomers
„ tr 或人方香族或非芳香族CC婦烴乒聚A 用之催化劑組成物。 八\口 ,催t:二又1的為,備催化劑組成物之方法, 成物可用於稀烴單體,特別二婦單體,更特別 /、尼一烯早體之聚合,·或該催化劑組成物可 : 單體與稀烴單體特別0 0 〜、軛一烯 乂 、 /、一烯單體或芳香族α烯烴或非芳 香烴之共聚合反應。 10 本!X明之又-目的為催化劑組成物其可用於稀烴單體 寺別彳早體’更特別共輛二稀單體之聚合;或該催化 I组,物可用於共輕二烯單體與烯烴單體特別共輛二婦單 體或芳香知α㈣或非芳香族α稀烴之共聚合反應。 15 本發明之又一目的為一種聚合烯烴單體特別二稀單體 ’更特別共輛二婦單體之方法,該方法使用該催化劑組成 物用於共轭二稀單體與稀煙單體,特別共輕二婦單體或芳 香無α烯烴或非芳香族以烯烴之共聚合反應。 本^月之又-目的為使用該催化劑組成物製造之聚合 物’特別聚二稀更特別共輛二嫦聚合物。 20 本务明之又一目的為催化劑組成物,該催化劑組成物 、^a έ共幸厄未飽和碳-碳雙鍵之單體,特別共輛二 婦單體類別之一,獲得聚二稀,該聚二烤包含a)姑化合物 或鈷錯合物,b)金屬錯合物活化劑化合物以及c)至少一種 催化劑改性劑’較佳為芳香族化合物。此外,本發明之目 的為兩種或兩種以上鈷錯合物/活化劑成分第1型/活化劑成 16 200302235 玖、發明說明 分第2型/含催化劑改性劑之催化劑組成物之組合。 較佳鈷錯合物含有至少一個鈷_氧鍵。 鈷錯合物之式量係低於2〇〇〇,更佳係低於8〇〇。 較佳根據本發明之鈷錯合物含有羧酸根配位子。 5 更佳根據本發明之鈷錯合物含有辛酸根、新癸酸根、 環烧酸根、維沙酸根(versatate)、乙醯基丙酮酸根、2_乙 基己酸根或硬脂酸配位子。 根據本發明之鈷錯合物例如包括辛酸鈷、新癸酸鈷、 環烷酸鈷、維沙酸鈷、乙醯基丙酮酸鈷、2-乙基己酸鈷及 1〇 硬脂酸鈷。 本發明之金屬錯合物可使用活化劑化合物活化(至少 一種第1型活化劑組合至少一種第2型活化劑)。活化可於 分開反應步驟期間,視需要地包含分離活化化合物進行, 或可於原位進行。活化較佳於金屬錯合物活化後,若無需 15 分離及/或純化活化後之錯合物,則原位進行活化。 較佳本發明之金屬錯合物經由組合至少一種第1型活 化劑化合物、至少一種第2型活化劑化合物以及至少一種 催化劑改性劑而變成具有催化活性。 根據本發明之金屬錯合物可使用適當活化劑(第丨型活 20化劑及第2型活化劑)以及適當催化劑改性劑活化。例如第 1型活化劑可為有機金屬化合物,其中至少一個芳香族炉 基係直接鍵結至金屬,而獲得至少一種(芳香族)碳_金屬鍵 。直接鍵結至有機金屬化合物至金屬之烴基較佳含有 ,及更佳1-10碳原子。有機金屬化合物之金屬可選自元素 17 200302235 玖、發明說明 週期表11、12、13或14族。適當金屬例如為銘及删。 用於此處之適當第】型活化劑化合物包括_化芳香族 硼化合物,特別氟化或全氟化三(芳基)硼化合物例如參(五 氟苯基)硼、參(鄰-九氟聯苯基)硼、參[3,5_武(三氣甲基)苯 5基]删、氟化或全氟化三(芳基)銘化合物如參(五i苯基)紹 、參(鄰-九氟聯苯基)紹、參[3,5_底(三氟甲基)苯基]紹;聚 合物或寡聚物is氧院特別甲基紹氧烧(ΜΑ〇)、三異丁基銘 改性之甲基鋁氧烷或異丁基鋁氧烷;非聚合物、相容性、 非配位、離子生成性化合物(包括將此等化合物用於氧化 條件),特別使用相容性非配價陰離子之録鹽、鱗鹽、氧 鑕鹽、碳錄鹽、石夕院錄鹽、續鐵鹽或鐵茂鐵鹽;及前述活 化化合物的組合。前述第1型活化化合物先前就不同金屬 錯合物教示於下列參考案:^國專利案“Μ·, 5,153,157 . 5,064,802,5,321,106 . 5,721,185,5,350,723 ,及WO-97/04234,相當於美國第〇8/818,53()號中請案, 申請曰1997年3月14曰。 離子生成性化合物可用作為根據本發明之第】型活化 劑化合物。 作為第1型活化劑化 個陽離子(其為可施 本發明之一具體實施例中,可用 合物之適當離子生成性化合物包含一 個相容非配位陰離子。 種陰離子或物質,其未 予一個質子之布朗司德酸)以及一 用於此處’「非配位」一詞表示一 配位至含金屬前驅物錯合物以及由該前驅物錯合物衍生而 得之催化_生物,或該陰離子只微弱配位至此種 18 20 玖、發明說明 錯合物,因而維持充八丁,—、 體)所置拖 刀不穩定而可被路易士鹼(如烯烴單 陽離;、卩配位陰離子特別係指-種陰離子,其當於 = 物用作為電荷平衡陰離子時,不會移轉 。「相容 物分解時^分解陰離子,其當好形成的錯合 成為中性,也*會干擾該錯合物之期望 鼓後聚合反應或其它用途。 較佳陰離子合古g — 早一配位錯合物,其包含一個載有電 10 15 k金屬或類金屬中心,該陰離子可平衡活性催化劑物種 (金屬陽離子’可能於兩個成分組合時形成)的電荷。此外 ,該陰離子充分不穩定,而可由烯H屬及㈣未飽 Η 。物或其匕中性路易士鹼如醚或腈置換。適當酸包括 但非限於鋁、金及鉑。適當類金屬包括但非限於硼、磷及 石夕3陰離子化合物其包含含單一金屬或類金屬原子之配 位錯t物當然為眾所周知,多種錯合物特別為陰 離子部分 含有單一硼原子之化合物為市面上可得。 較佳此種第1型活化劑化合物以下式表示: (L*-H)/Ad- 其中: 20 L*為中性路易士驗; (L*-H)+為布朗司德酸;„The catalyst composition for tr or fragrant aromatic or non-aromatic CC women's hydrocarbon ping poly A. Eight, mouth, t: two and one, the method of preparing the catalyst composition, the product can be used for dilute hydrocarbon monomer Polymer, especially dimer monomer, more special /, polymerization of nidene early body, or the catalyst composition may: monomer and dilute hydrocarbon monomer in particular 0 0 ~, conjugated monoene, /, monoene Copolymerization of aromatic or aromatic alpha olefins or non-aromatic hydrocarbons. 10 Ben! X Mingzhi-The purpose is a catalyst composition which can be used for the polymerization of dilute monomers, more specifically, dilute monomers. Or the group I of the catalyst can be used for the copolymerization of a co-light diene monomer and an olefin monomer, particularly a diene monomer or an aromatic α㈣ or a non-aromatic α dilute hydrocarbon. 15 Another object of the present invention It is a method for polymerizing olefin monomers, particularly dilute monomers, and more particularly divinyl monomers. The method uses the catalyst composition for conjugated dilute monomers and dilute monomers, and particularly dilute diethyl monomers. Copolymerization reaction of aromatic or non-aromatic alpha olefins or non-aromatic olefins. This month-purpose is to use the The polymer made from the chemical composition is a special polymer and a more special polymer. 20 Another purpose of the present invention is a catalyst composition. The catalyst composition, ^ a, coexists with unsaturated carbon-carbon. Monomers of double bonds, especially one of the two types of dimer monomers, obtain polydiene, which comprises a) a quaternary compound or a cobalt complex, b) a metal complex activator compound, and c) at least A catalyst modifier is preferably an aromatic compound. In addition, the object of the present invention is two or more cobalt complexes / activator component type 1 / activator 16 200302235 玖, the second part of the description of the invention Type / catalyst composition containing catalyst modifier. Preferably the cobalt complex contains at least one cobalt-oxygen bond. The formula of the cobalt complex is less than 2000, more preferably less than 80. 〇 It is preferable that the cobalt complex according to the present invention contains a carboxylate ligand. 5 More preferably, the cobalt complex according to the present invention contains octanoate, neodecanoate, cyclamate, versatate, ethyl Amidinopyruvate, 2-ethylhexanoate or stearic acid ligands. The cobalt complexes of the invention include, for example, cobalt octoate, cobalt neodecanoate, cobalt naphthenate, cobalt vesartate, cobalt acetopyruvate, cobalt 2-ethylhexanoate, and 10 cobalt stearate. The metal complex can be activated using an activator compound (at least one type 1 activator combined with at least one type 2 activator). Activation can be performed during a separate reaction step, optionally including isolation of the activating compound, or can be The activation is preferably after the activation of the metal complex, if the isolation and / or purification of the activated complex is not required, the activation is performed in situ. Preferably, the metal complex of the present invention is combined with at least one first Type activator compound, at least one type 2 activator compound, and at least one catalyst modifier to become catalytically active. The metal complex according to the present invention may use an appropriate activator (type activator 20 and type 2 Type activator) and appropriate catalyst modifiers. For example, the type 1 activator may be an organometallic compound, in which at least one aromatic radical is directly bonded to the metal, and at least one (aromatic) carbon-metal bond is obtained. The hydrocarbyl group directly bonded to the organometallic compound to the metal preferably contains and more preferably 1 to 10 carbon atoms. The metal of the organometallic compound may be selected from element 17 200302235 rhenium, description of the invention Groups 11, 12, 13 or 14 of the periodic table. Suitable metals are, for example, inscriptions and deletions. Suitable type activator compounds for use herein include fluorinated aromatic boron compounds, in particular fluorinated or perfluorinated tri (aryl) boron compounds such as gins (pentafluorophenyl) boron, ginseno (o-ninefluoro) Biphenyl) boron, ginseng [3,5_wu (trifluoromethyl) benzene 5yl], fluorinated or perfluorinated tri (aryl) ming compounds such as ginsyl (pentaphenyl), ginseng ( O-Nine fluorobiphenyl), ginseng [3,5_ bottom (trifluoromethyl) phenyl], and polymers or oligomers Butylming modified methylalumoxane or isobutylalumoxane; non-polymer, compatible, non-coordinating, ion-generating compounds (including using these compounds for oxidation conditions), especially using compatibility Non-valent anion recorded salt, scale salt, oxo salt, carbon recorded salt, Shi Xiyuan recorded salt, continued iron salt or ferrocene salt; and a combination of the foregoing activating compounds. The aforementioned type 1 activating compound has previously been taught in the following references for different metal complexes: National Patent Case "M., 5,153,157. 5,064,802, 5,321,106. 5,721,185, 5,350,723, and WO-97 / 04234, which is equivalent to U.S. 08 / 818,53 (), the application date is March 14, 1997. Ion-generating compounds can be used as the activator compounds of the first type according to the present invention. The cations (which are In one embodiment of the present invention, suitable ionogenic compounds of useful compounds include a compatible non-coordinating anion (an anion or substance that does not have a protonic Bronsted acid) and one for use herein "The term" non-coordinating "means a coordination to a metal-containing precursor complex and a catalyzed derivative derived from the precursor complex, or the anion is only weakly coordinated to such 18 20 发明, invention Explain that the complex compound, therefore, maintains the stability of the drag knife placed by octabutadiene, which can be unstable by Lewis base (such as alkene monocation; 卩 complex anion refers specifically to an anion, which is equivalent to = Use as When the anion is balanced, it will not transfer. "When the compatibilities are decomposed, the anions will be decomposed, and the misformation that is well formed is neutral, and it will also interfere with the desired post-drum polymerization or other uses of the complex. Good anion Hegu g — an early coordination complex containing an electric 10 15 k metal or metalloid center, the anion balances the active catalyst species (the metal cation 'may form when the two components are combined) In addition, the anion is sufficiently unstable and can be substituted by olefins and saturates. Substances or neutral Lewis bases such as ethers or nitriles. Suitable acids include, but are not limited to, aluminum, gold, and platinum. Suitable classes Metals include, but are not limited to, boron, phosphorus, and stone. Anionic compounds that contain coordination dislocations containing a single metal or metal-like atom are, of course, well-known. A variety of complexes, particularly compounds containing a single boron atom in the anion portion, are commercially available. Available. The preferred type 1 activator compound is represented by the following formula: (L * -H) / Ad- where: 20 L * is neutral Lewis test; (L * -H) + is Bronsted acid ;
Ad為帶有電荷d·之非配位相容性陰離子,以及 d為1至3之整數。 更佳Ad_對應式: 19 200302235 玖、發明說明 [M*Q4]; 其中: M*為+3克式量氧化態之硼或鋁;以及 Q各自出現時分別係選自氫陰離子、二烷基醯胺基、 5 _陰離子、烴基、烴基、鹵碳基、烴基氧陰離子、烴氧 基取代之烴基、有機金屬取代之烴基、有機類金屬取代之 基、烴氧基、!I烴氧基取代之烴基、函碳基取代之烴 基、以及鹵取代之矽烷基烴基(包括全_化烴基、全鹵化 經氧基、以及全鹵化矽烷基烴基),該Q含至多2〇個碳,但 10不多於一次為Q鹵陰離子。適當烴基氧陰離子Q基例如揭 示於美國專利第5,296,433號。 更佳具體實施例中,d為1,亦即抗衡離子含有單一負 電荷且為A·。特別可用於製備本發明之催化劑之活化劑化 合物係以如下通式表示: 15 (L*-H)+(BQ4)-; 其中: L*定義如前; B為克式量氧化鈦3之删;以及 、烴氧基、氟化烴基 但Q為烴基不多於一 ’特別五氟苯基或九 20 Q為含至多20個非氫原子之烴基 、氟化烴氧基、或氟化矽烷基烴基, 次。最佳Q於各次出現時為氟化芳基 氟聯苯基。 明之改良催化劑 取代之銨鹽例如 可用作為活化劑化合物用於製備本發 之·化合物之說明性但非限制性範例為 20 200302235 玖、發明說明 :四苯基硼酸三曱基銨、四苯基硼酸三(正丁基)銨、四苯 基硼酸甲基二_十八烷基銨、四苯基硼酸三乙基銨、四苯 基硼酸三丙基銨、四苯基硼酸三(正丁基)銨、四笨基硼酸 甲基-十四烷基-十八烷基銨、四苯基硼酸N,N-二甲基苯銨 5 、四本基蝴酸N,N-二乙基苯銨、四苯基棚酸n,n_二甲基 (2,4,6-二甲基苯銨)、貳(7,8·二甲醯十一硼酸)鈷酸 (III)N,N-二甲基苯銨、肆(五氟苯基)硼酸三甲基銨、肆(五 氟苯基)硼酸甲基二(十四烷基)銨、肆(五氟苯基)硼酸甲基 二(十八烷基)銨、肆(五氟苯基)硼酸三乙基銨、肆(五氟苯 10基)硼酸三丙基銨、肆(五氟苯基)硼酸三(正丁基)銨、肆(五 氟苯基)硼酸三(第二丁基)銨、肆(五氟苯基)硼酸N,N_二甲 基苯銨、肆(五氟苯基)硼酸N,N_二乙基笨銨、肆(五氟苯基 )蝴酸N,N_二甲基(2,4,6-三甲基苯銨)、肆(2,3,4,卜四氣苯基 )硼酸三f基銨、肆(2,3,4,6-四氟苯基)硼酸三乙基銨、肆 15 (2,3,4,6-四氟苯基)硼酸三丙基銨、肆(2,3,4,6_四氟苯基)硼 酸二(正丁基)銨、肆(2,3,4,6-四氟苯基)硼酸二甲基(第三丁 基)銨、肆(2,3,4,6-四氟苯基)硼酸N,N-二甲基苯銨、肆 (2,3,4,6-四氟苯基)硼酸N,N_二乙基苯銨、以及肆(2,3,4,6_ 四氟苯基)硼酸N,N.H(2,Mg f基隸);二烧基銨 20鹽如:肆(五氟苯基)硼酸二(十八烧基)錢、肆(五氧苯基)领 酸二(十四烷基)銨、以及肆(五氟苯基)硼酸二環己基銨; 三取代之鐫鹽例如··肆(五氟苯基)硼酸三苯基鱗、肆(五氟 本基)硼酸甲基二(十八烧基)鱗、以及肆(五氟苯基)娜酸三 (2,6-二甲基笨基)鱗。 21 200302235 玖、發明說明 較佳為長鏈烧基一取代及二取代之銨錯合物之肆(五 氟本基)蝴酸鹽,特別Ci4_C2〇烧基錢錯合物,特別肆(五氣 本基)爛酸甲基二(十八烧基)銨以及肆(五氟苯基)棚酸曱基 一(十四烧基)銨,或其混合物。此種混合物包括衍生自含 5兩個Cm、8烷基以及一個甲基之胺之質子化銨陽離 子。此等胺可以商品名克馬明(Kemamine)丁9701得自惠可 (Witco)公司以及以商品名亞明(Armeen)M2HT得自艾克左 諾貝爾(Akzo-Nobel)公司。 用於此處之最佳第1型催化劑活化劑例如包括前述三 10 烴基銨鹽,特別下列甲基貳(十四烷基)銨鹽或甲基貳(十八 烧基)銨鹽··貳(參(五氟苯基)硼烷)咪唑化物, 系(參(五氟苯基)侧烧)-2-十一烧基咪唾化物, Λ(參(五氟苯基)蝴院)-2-十七烧基咪唾化物, 貳(參(五氟苯基)硼烷)-4,5-貳(十一烷基)咪唑化物, 15 貳(參(五氟苯基)硼烷)-4,5-貳(十七烷基)咪唑化物, 貳(參(五氟苯基)硼烷)咪唑噍化物, 貳(參(五氟苯基)硼烷)-2-十一烷基咪唑嘬化物, 氛(參(五氟苯基)棚烧)-2-十七烧基味唾喉化物, 貳(參(五氟苯基)硼烷)-4,5-貳(十一烷基)咪唑嗫化物, 2〇 貳(參(五氟苯基)硼烷)-4,5-貳(十七烷基)咪唑。辰化物, 家(參(五氟苯基)硼烷)-5,6-二曱基笨并咪唑化物, 戴(參(五I苯基)鄉烧)-5,6-武(十一烧基)苯并味嗤化物, 貳(參(五氟苯基)鋁烷)咪唑化物, 家(參(五氟苯基)|g烧)-2-十一烧基咪哇化物, 22 200302235 玖、發明說明 貳(參(五氟苯基)紹烧)-2-十七烧基咪唾化物, 貳(參(五氟苯基)鋁烷)-4,5-貳(十一烷基)咪唑化物, 貳(參(五氟苯基)鋁烷)-4,5-貳(十七烷基)咪唑化物, 貳(參(五氟苯基)鋁烷)咪唑嘬化物, 5 貳(參(五氟苯基)鋁烷)-2-十一烷基咪唑嘬化物, 篆(參(五氣苯基)紹烧)-2 -十七烧基味嗤喉化物, 貳(參(五氟苯基)鋁烷)-4,5·貳(十一烷基)咪唑噍化物, 貳(參(五氟苯基)鋁烷)-4,5·貳(十七烷基)咪唑噍化物, 武(參(五氟苯基)鋁烷)-5,6-二甲基苯并咪唑化物,以 10 及 貳(參(五氟苯基)铭院)-5,6-貳(十一烧基)笨并咪σ坐化物 。前述活化劑化合物先前已經就不同的金屬錯合物教示於 下列參考案:ΕΡ 1 560 752 Α1。 另一種適當銨鹽特別係用於非同質催化劑系統係由有 15機金屬化合物(特別三(Cw烷基)鋁化合物)與羥基芳基參( 氟芳基)硼酸化合物銨鹽反應生成。所得化合物為通常不 可溶於脂肪族液體之有機金屬氧基芳基參(氟芳基)硼酸鹽 化合物。適當化合物包括三(Cw烷基)鋁化合物與羥芳基 參(芳基)硼酸銨鹽之反應產物。適當羥芳基參(芳基)硼酸 2〇鹽包括銨鹽,特別下列之前述長鏈烷基銨鹽·· (4 一甲基鋁氧基-1-苯基)參(五氟苯基)硼酸鹽, 斤(4-二甲基!呂氧基_3,5-二(三甲基石夕烧基)小苯基⑷五 氟苯基)删酸鹽, ⑷二曱基ί呂氧基_3,5_二(第三丁基)小苯基)參(五氣苯 23 200302235 玖、發明說明 基)硼酸鹽, (4-二甲基鋁氧基-1-嶋基)參(五氟苯基)硼酸鹽, (4-二甲基铭氧基-3-曱基-1-苯基)參(五氣苯基)獨酸鹽’ (4-二甲基紹氧基-四亂-1-苯基)參(五亂苯基)删酸鹽5 5 (5-二甲基鋁氧基-2-毡基)參(五氟苯基)硼酸鹽, 4-(4-二曱基鋁氧基-1-苯基)苯基參(五氟苯基)硼酸鹽, 4-(2-(4-(二甲基鋁氧基苯基)丙烷-2-基)苯氧基)參(五 氟苯基)硼酸鹽, (4-二乙基鋁氧基-1·苯基)參(五氟苯基)硼酸鹽, 10 (4-二乙基鋁氧基-3,5-二(三曱基矽烷基)-1-苯基)參(五 氟苯基)硼酸鹽, (4-二乙基鋁氧基-3,5-二(第三丁基)-1-苯基)參(五氟苯 基)硼酸鹽, (4-二乙基鋁氧基-1-嶋基)參(五氟苯基)硼酸鹽, 15 (4-二乙基鋁氧基-3-甲基-1-苯基)參(五氟苯基)硼酸鹽, (4-二乙基鋁氧基-四氟-1-苯基)參(五氟苯基)硼酸鹽, (5-二乙基鋁氧基-2-毡基)參(五氟苯基)硼酸鹽, 4-(4-二乙基鋁氧基-1-苯基)苯基參(五氟苯基)硼酸鹽, 4-(2-(4-(二乙基銘氧基苯基)丙烧-2 -基)苯氧基)參(五 20 氟苯基)硼酸鹽, (4-二異丙基鋁氧基-1-笨基)參(五氟苯基)硼酸鹽, (4 -二異丙基紹氧基-3,5 -二(二曱基碎烧基)-1-笨基)參( 五氟苯基)硼酸鹽, (4 -二異丙基紹氧基-3,5-二(第二丁基)-1-苯基)參(五氟 24 200302235 玖、發明說明 苯基)硼酸鹽, (4_二異丙基鋁氧基-1-嶋基)參(五氟苯基)硼酸鹽, (4-二異丙基鋁氧基τ基—丨―苯基)參(五氟苯基)硼酸 鹽, 5 (4-二異丙基鋁氧基-四氟-1-苯基)參(五氟苯基)硼酸鹽, (5_二異丙基鋁氧基-2-毡基)參(五氟苯基)硼酸鹽, 4-(4-二異丙基鋁氧基_丨_苯基)苯基參(五氟苯基)硼酸 鹽,以及 4-(2_(4-(二異丙基鋁氧基苯基)丙烷基)苯氧基)參( 10 五氟苯基)硼酸鹽。 特佳銨化合物為(4_二乙基鋁氧基_丨_苯基)參(五氟苯基 )硼酸甲基二(十四烷基)銨、(4-二乙基鋁氧基-1-苯基)參(五 氟苯基)硼酸甲基二(十六烷基)銨、(‘二乙基紹氧基苯 基)參(五氟苯基)硼酸甲基二(十八烷基)銨及其混合物。前 15述錯合物揭示於美國專利案5,834,393及5,783,512。 另一種適當離子生成性第丨型活化劑化合物包含陽離 子性氧化劑與下式表示之非配位相容性陰離子生成之鹽: (〇xe+)d(AdJe,其中 〇xe+為帶有電荷e+之陽離子性氧化劑; d為1至3之整數; e為1至3之整數;以及 Ad定義如前。 陽離子性氧化劑例如包括··鐵茂鑽、 鑽、Pb + 2+ Λ + η 丞取代之鐵茂 或Ag。較佳,具體實施例為先前就含布朗司德 25 200302235 软、發明說明 酸之活化劑化合物定義之陰離子,特別為肆(五氣苯細 酸根。 一另:種適當離子生成性第1型活化劑化合物包含下式 表π之碳烯鑽離子與非配位相容性陰離子生成之鹽: 5 @+Α· 其中: @為匸】^碳稀鑕離子;以及 Α-為具有價數-1之非配位相容性陰離子。較佳碳烯鑕 離子為三苯甲基陽離子,特別三苯甲基鑽。 10 較佳第1型碳烯鑕鹽活化劑化合物為肆(五氟苯基)硼酸 三苯甲基鑕、肆(九氟聯苯基)硼酸三苯甲基鑕、肆(五氟苯 基)卿酸二甲苯甲基鑕及其它經取代之加合物。 另一種適當之離子生成性第丨型活化劑化合物包含一 種化合物其為下式表示之矽烷鍇離子與非配位相容性陰離 15子之鹽·· R3Si+A_ 其中: R為C 1.1 〇烴基;以及 A定義如前。 2〇 較佳第1型矽烷鑕鹽活化劑化合物為肆(五氟苯基)硼酸 三甲基矽烷鑕、肆(九氟聯苯基)硼酸三甲基矽烷鑽、肆(五 氟苯基)硼酸三乙基矽烷鑽及其它經取代之加合物。 矽烷鏘鹽先前概略揭示於化學會化學通訊期刊,1993 ,383-384,以及 Lambert, J. B·等人,有機金屬,1994,13 26 200302235 玖、發明說明 ,2430-2443。使用前述矽烷鏘鹽做為供加成聚合催化劑用之 活化劑化合物係於美國專利案第5,625,〇87號申請專利。 某些醇類、硫醇類、矽烷醇類及肟類與參(五氟苯基) 硼烷之錯合物也為有效第1型催化劑活化劑,而可用於本 5發明。此等催化劑化合物係揭示於美國專利第5,296,433號。 第1型活化劑化合物也可組合使用。特佳組合為三(烴 基)鋁或三(烴基)硼烷化合物(各個烴基含有丨至4個碳)與寡 聚物或聚合物鋁氧烧化合物之混合物。 催化劑/辅催化劑之莫耳比較佳為i : 1〇,〇〇〇至1〇 : 1, 10更佳為1 : 5000至10 : 1,及最佳為! : 25〇〇至i : i。鋁氧 烷當本身用作為第1型活化劑化合物時較佳係以大莫耳比 使用,通常以莫耳為基準,至少為金屬錯合物用量之50倍 。參(五氟苯基)硼烷若用作為第丨型活化劑化合物,較佳使 用參(五氟苯基)硼烷對金屬錯合物之莫耳比〇5:丨至…:! 15 ,更佳為! ··:[至6 ·· !及最佳為! : j至5 ·· i。其餘活化劑化 合物通常較佳係以約略等莫耳量而與金屬錯合物使用。 若前述非配位或不良配位陰離子用作為第丨型活化劑 化合物,則較佳為根據本發明欲烷化之金屬錯合物(換言 之,金屬錯合物之R,基之一為烷基或芳基)。以含硼活化 2〇劑化合物為[最佳活化劑化合物包含肆(五^苯基㈣酸 鹽、參(五氟苯基)硼烷、參(鄰-九氟聯苯基)硼烷、肆(3,5_ 貳(三氟甲基)苯基)蝴酸鹽、參(五氟苯基)無烧 '參(鄰-九 氟聯笨基)鋁烷。 若選用有機金屬化合物做為活化劑化合⑯,則金屬錯 27 200302235 玖、發明說明 合物中第1型活化劑化合物相對於金屬中心之莫耳比,通 ¥係於1 : 10至10,000 : 1 ,更佳為i : 10至5000 : i及最佳 為1 · 1至2,500 ·· 1之範圍。若含有或可獲得非配位或不良 配位陰離子之化合物選用做為活化劑化合物,則莫耳比通 5 常為1 : 10至M00 : 1,及較佳1 : 2至250 : 1之範圍。 根據本發明之催化劑之形成係經由鈷錯合物組合至少 一種第1型活化劑、至少一種第2型活化劑以及至少一種催 化劑改性劑之組合而完成。 例如第2型活化劑可為有機金屬化合物,其中至少一 10個或多於一個函原子或烴基係直接鍵結至金屬而提供金 屬素鍵或碳-金屬鍵。烴基為非芳香族,烴基直接鍵結 至有機金屬化合物之金屬,且較佳含卜…及更佳卜碳原 子。有機金屬化合物之金屬係選自元素週期表丨、2、3、4 、5、6、7、12、13 或 14 族。 15 此處使用之適當第2型活化劑包括烴基鈉、_化鈉、 烴基鋰、齒化鋰、烴基鋅、二_化鋅、二_化鎂、烴基函 化鎂、二烴基鎂,特別烷基鈉、烷基鋰、烷基鋅、烷基鹵 化鎂、二烷基鎂,例如正辛基鈉、丁基鋰、新戊基鋰、甲 基經、乙基鐘、二乙基鋅、二丁基辞、丁基氯化鎮、乙基 2〇氯化鎮、辛基氣化鎮、二丁基鎮、二辛基鎮、丁基辛基鎮 。用於此處之適當第2型催化劑活化劑也包括中性路易士 酸,例如非芳香族Cu烴基取代之13族化合物取代基,特 另|J(烴基)鋁化合物或(烴基)硼化合物及其_化(包括全齒化) 衍生物,於各個烴基或鹵化烴基含】至20個碳,·更特別二 28 200302235 玖、發明說明 烷基鋁化合物,例如三乙基鋁及三異丁基鋁;二烷基鋁氫 化物例如二異丁基氫化铭;烧基烧氧基紹化合物如二丁基 乙氧基鋁;_化鋁化合物如二乙基氯化鋁、乙基氣化鋁、 二異丁基氯化銘、異丁基氯化铭、乙基辛基氯化|呂、乙基 5倍半氯化鋁、乙基環己基氯化鋁、二環己基氯化鋁、二辛 基氯化鋁。 用於此處之適當第2型催化劑活化劑也包括銘三鹵化 物及硼三_化物例如三氯化鋁、三氟化鋁、三氟化硼、以 及二函化銘與二齒化侧與路易士驗之加合物。 0 適當用於此處之視需要使用的第2型催化劑活化劑也 包括中性路易士酸例如烴基取代之3族或7族化合物, 特別(烴基)航-、(烴基)鈦、(烴基)結_、(烴基)飢-或(烴基) 銦化合物及其_化(包括全鹵化)衍生物,各個烴基或_化 烴基含1至20個碳。 5 用於此處之適當第2型催化劑活化劑也包括3族至7族 金屬鹵化物特別銃-、鈦-、錯-、飢-或|目鹵化物,例如二 氣化鈦、三氯化鈦、四氯化鈦、二氯化鍅、三氯化錯、四 氣化錯、二氯化釩、三氯化釩、五氯化鉬。 較佳i化鋁化合物例如二乙基氯化鋁、乙基氯化铭、 〇 二異丁基氯化鋁、乙基辛基氯化鋁、乙基倍半氯化鋁、曱 基倍半氯化鋁、乙基環己基氯化鋁、二環己基氯化鋁、二 辛基氣化鋁為第2型活化劑。 第2型催化劑活化劑相對於鈷錯合物金屬中心之莫耳 比其特徵為該莫耳比通常係於1 : 1 〇至丨,〇〇〇·· 1,更佳i ·· 29 200302235 玖、發明說明 10至500 : 1及最佳1 : 1至250 : 1之範圍。 特別期望用於此處之活化劑化合物為第2型活化劑化 合物之組合,例如中性視需要使用之路易士酸,特別各個 烷基含1至4個碳原子之二烷基鋁鹵化物化合物(例如乙基 5倍半氯化鋁、乙基辛基氯化鋁及二乙基氯化鋁)與第1型活 化劑化合物(例如Cu烴基取代之13族路易士酸化合物, 特別各個烴基含1至20個碳之函化三(烴基)硼或_鋁化合物 ,特別參(五氟苯基)硼烷或參(五氟苯基)鋁烷)之組合;第 2型活化劑(如中性路易士 g《混合物)與聚合物或寡聚物紹氧 1〇烷(第1型活化劑)之組合;以及單一中性路易士酸(第2型活 化劑)特別與參(五敦苯基)蝴烧或參(五氣苯基)減以及聚 合物或寡聚物鋁氧烷(第丨型活化劑)之組合。 如剛述,根據本發明之催化劑可經由鈷錯合物組合至 少-種第㈣活化劑、至少—種第2型活化劑、以極至少一 15種催化劑改性劑完成。 添⑴催化別改性劑為芳香族化合物。較佳催化劑改性 ^為含有至少兩個或多於兩個qh基鍵結至芳香族化合物 之芳香族化合物。 車交佳含有至少兩個經基之芳香族化合物係以下式之一 表示:Ad is a non-coordinating compatible anion with a charge d ·, and d is an integer from 1 to 3. Better Ad_ Correspondence: 19 200302235 发明, description of the invention [M * Q4]; where: M * is +3 grams of boron or aluminum in the oxidation state; and each Q is selected from the group consisting of hydrogen anion and dioxane. Hydrazone, 5 anion, hydrocarbyl, hydrocarbyl, halocarbon, hydrocarbyloxy anion, hydrocarbyloxy substituted hydrocarbyl, organometal substituted hydrocarbyl, organic metal substituted hydrocarbyl, hydrocarbyl, etc. I hydrocarbyl-substituted hydrocarbyl, alkano-substituted hydrocarbyl, and halogen-substituted silane-based hydrocarbyls (including fully halogenated hydrocarbyls, fully-halogenated via oxygen radicals, and fully-halogenated silyl hydrocarbon radicals), the Q contains up to 20 Carbon, but no more than 10 is a Q halide anion. Suitable hydrocarbyloxyanion Q groups are disclosed, for example, in U.S. Patent No. 5,296,433. In a more specific embodiment, d is 1, that is, the counter ion contains a single negative charge and is A ·. The activator compounds that are particularly useful in preparing the catalysts of the present invention are represented by the following formula: 15 (L * -H) + (BQ4)-; where: L * is as defined above; B is the deletion of grams of titanium oxide 3. ; And alkoxy, fluorinated hydrocarbyl, but Q is a hydrocarbyl group of not more than one, especially pentafluorophenyl or nine 20 Q is a hydrocarbyl group containing up to 20 non-hydrogen atoms, fluorinated alkoxy, or fluorinated silyl Hydrocarbyl, times. The best Q at each occurrence is a fluorinated aryl fluorobiphenyl. The modified ammonium salt of the improved catalyst can be used, for example, as an activator compound for the preparation of the present invention. An illustrative but non-limiting example of the compound is 20 200302235. 发明, Description of the invention: Triphenylammonium tetraphenylborate, tetraphenylborate Tris (n-butyl) ammonium, methyl di-octadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tris (n-butyl) tetraphenylborate Ammonium, tetrabenzyl borate methyl-tetradecyl-octadecyl ammonium, tetraphenyl borate N, N-dimethylaniline 5, tetrabenthoate N, N-diethylaniline, Tetraphenylheptanoic acid n, n_dimethyl (2,4,6-dimethylaniline), osmium (7,8 · dimethylformadecylboronic acid) cobalt acid (III) N, N-dimethyl Methylbenzyl ammonium, trimethylammonium (pentafluorophenyl) borate, methyldi (tetradecyl) ammonium (pentafluorophenyl) borate, methyldi (18-pentafluorophenyl) borate Alkyl) ammonium, triethylammonium (pentafluorophenyl) borate, tripropylammonium (pentafluorophenyl 10yl) borate, tri (n-butyl) ammonium (pentafluorophenyl) borate, Pentafluorophenyl) borate Methyl) ammonium, methyl (pentafluorophenyl) borate N, N_dimethylaniline, methyl (pentafluorophenyl) borate N, N_diethylbenzyl ammonium, methyl (pentafluorophenyl) butter , N_dimethyl (2,4,6-trimethylaniline), tris (2,3,4, tetrakiphenyl) trifluoroammonium borate, (2,3,4,6- Tetrafluorophenyl) triethylammonium borate, 15 (2,3,4,6-tetrafluorophenyl) tripropylammonium borate, (2,3,4,6_tetrafluorophenyl) borate di (N-butyl) ammonium, methane (2,3,4,6-tetrafluorophenyl) borate dimethyl (third butyl) ammonium, methane (2,3,4,6-tetrafluorophenyl) borate N, N-dimethylaniline, N- (2,3,4,6-tetrafluorophenyl) borate N, N_diethylaniline, and (2,3,4,6_tetrafluorophenyl) ) Boric acid N, NH (2, Mg f based); Dialkyl ammonium 20 salts such as: (pentafluorophenyl) boric acid di (octadecyl), di (pentaoxyphenyl) terephthalic acid ( Tetradecyl) ammonium, and dicyclohexylammonium (pentafluorophenyl) borate; tri-substituted phosphonium salts such as ·· (pentafluorophenyl) borate triphenyl scale, and (pentafluorobenzyl) borate Methyl bis (octadecyl) scale and tris (pentafluorophenyl) naphthalene tris (2, 6-dimethylbenzyl) scale. 21 200302235 发明, description of the invention is preferably a long-chain alkyl mono- and di-substituted ammonium complex (pentafluorobenzyl) phosphonate, especially Ci4_C20 alkyl radical complex, especially This group) methyl bis (octadecyl) ammonium rotten acid and ammonium (pentadecyl) ammonium (pentafluorophenyl) pentanoate, or mixtures thereof. Such mixtures include protonated ammonium cations derived from amines containing two Cm, 8 alkyl groups, and one methyl group. These amines are available from the company Witco under the trade name Kemamine Ding 9701 and from Akzo-Nobel under the trade name Armeen M2HT. The preferred type 1 catalyst activators used herein include, for example, the aforementioned tri-10 alkylammonium salts, in particular the following methylphosphonium (tetradecyl) ammonium salts or methylphosphonium (octadecyl) ammonium salts ·· 贰(Shen (pentafluorophenyl) borane) imidazolium, (Shen (pentafluorophenyl) side burning) -2-undecyl Imidosal, Λ (shen (pentafluorophenyl) butterfly house)- 2-Heptadecanyl imide salivate, osmium (reference (pentafluorophenyl) borane) -4,5-fluorene (undecyl) imidazolium, 15 hydrazone (reference (pentafluorophenyl) borane) -4,5-fluorene (heptadecyl) imidazolium, hydrazone (gins (pentafluorophenyl) borane) imidazolium, hydrazone (gins (pentafluorophenyl) borane) -2-undecyl Imidazolium sulfonate, Ambient (referred to (pentafluorophenyl) greenhouse) 2-Seventhyl-based salivary salivary compounds, fluorene (referred to (pentafluorophenyl) borane) -4,5-fluorene (undecane Group) imidazolium phosphonium compound, 20% (reference (pentafluorophenyl) borane) -4,5-fluorene (heptadecyl) imidazole. Cinnamate, Home (Ginseng (pentafluorophenyl) borane) -5,6-difluorenylbenzimidazole, Dai (Ginseng (pentaphenyl) township) -5,6-wu Benzyl miso compound, hydrazone (ginseng (pentafluorophenyl) alumino) imidazolium, home (ginseng (pentafluorophenyl) | g roast) -2-undecyl imidazolate, 22 200302235 pyrene 2. Description of the invention Thallium (Ginseng (pentafluorophenyl) Shaoyao) -2-heptadecanyl imidyl salivate, Thallium (Ginseng (pentafluorophenyl) alumane) -4,5-fluorene (undecyl) Imidazolium, osmium (reference (pentafluorophenyl) alane) -4,5-hydrazone (heptadecyl) imidazide, osmium (reference (pentafluorophenyl) alane) imidazolium, 5 osmium (reference (Pentafluorophenyl) alkane) -2-undecylimidazolium halide, osmium (referred to (pentaphenyl) Shaoyao)-2-heptadecyl miso throat, osmium (referenced to (pentafluoro) Phenyl) alane) -4,5 · fluorene (undecyl) imidazolium phosphonium, hydrazone (gins (pentafluorophenyl) alkane) -4,5 · fluorene (heptadecyl) imidazolium hydrazone, Wu (Shen (pentafluorophenyl) alane) -5,6-dimethylbenzimidazolium, with 10 and osmium (Shen (pentafluorobenzene) ) Ming Institute) -5,6-II (xi burn-yl) imidazole and σ Zuohua was stupid. The aforementioned activator compounds have previously been taught in the following references for different metal complexes: EP 1 560 752 A1. Another suitable ammonium salt is particularly used in non-homogeneous catalyst systems. It is formed by the reaction of 15 organic metal compounds (especially tri (Cw alkyl) aluminum compounds) with hydroxyl ammonium (fluoroaryl) borate compounds. The resulting compound is an organometallic oxyaryl ginseng (fluoroaryl) borate compound which is generally insoluble in aliphatic liquids. Suitable compounds include the reaction product of a tri (Cw alkyl) aluminum compound and a hydroxyaryl para (aryl) borate ammonium salt. Suitable hydroxyaryl ginseng (aryl) boronic acid 20 salts include ammonium salts, in particular the aforementioned long-chain alkylammonium salts ... (4-methylaluminumoxy-1-phenyl) ginseng (pentafluorophenyl) Borate, Phenyl (4-dimethyl! Lvoxy_3,5-bis (trimethylcarboxanyl) small phenyl⑷pentafluorophenyl) phosphonate, Pyridoxyl_3 , 5-Di (third butyl) small phenyl) ginseng (pentabenzene 23 200302235 玖, description of the invention) borate, (4-dimethylaluminumoxy-1-fluorenyl) ginseng (pentafluorobenzene) ) Borate, (4-dimethylammoxy-3-fluorenyl-1-phenyl) ginseng (pentaphenyl) mono ('pentafluorophenyl) monotetramide -Phenyl) Shen (pentanylphenyl) delete salt 5 5 (5-dimethylaluminumoxy-2-feltyl) shen (pentafluorophenyl) borate, 4- (4-difluorenyl aluminum) Oxy-1-phenyl) phenyl phenyl (pentafluorophenyl) borate, 4- (2- (4- (dimethylaluminumoxyphenyl) propane-2-yl) phenoxy) Pentafluorophenyl) borate, (4-diethylaluminumoxy-1 · phenyl) ginseng (pentafluorophenyl) borate, 10 (4-diethylaluminumoxy-3,5-bis ( Trimethylsilyl) -1-phenyl) ginseng ( Pentafluorophenyl) borate, (4-diethylaluminumoxy-3,5-bis (thirdbutyl) -1-phenyl) ginseng (pentafluorophenyl) borate, (4-diethyl Aluminooxy-1-fluorenyl) gins (pentafluorophenyl) borate, 15 (4-diethylaluminumoxy-3-methyl-1-phenyl) span (pentafluorophenyl) borate , (4-diethylaluminumoxy-tetrafluoro-1-phenyl) ginseng (pentafluorophenyl) borate, (5-diethylaluminumoxy-2-fetyl) ginseng (pentafluorophenyl) ) Borate, 4- (4-diethylaluminumoxy-1-phenyl) phenyl phenyl (pentafluorophenyl) borate, 4- (2- (4- (diethylamyloxyphenyl) ) Propane-2-yl) phenoxy) ginseng (penta-20 fluorophenyl) borate, (4-diisopropylaluminumoxy-1-benzyl) ginseng (pentafluorophenyl) borate, ( 4-diisopropylstiloxy-3,5-di (difluorenyl crushed alkyl) -1-benzyl) shen (pentafluorophenyl) borate, (4-diisopropylstiloxy)- 3,5-bis (second butyl) -1-phenyl) ginseng (pentafluoro 24 200302235 玖, description of the invention phenyl) borate, (4-diisopropylaluminumoxy-1-fluorenyl) ginseng (Pentafluorophenyl) borate, (4-diisopropylaluminumoxyτyl — 丨 benzene ) Ginseng (pentafluorophenyl) borate, 5 (4-diisopropylaluminumoxy-tetrafluoro-1-phenyl) ginseng (pentafluorophenyl) borate, (5-diisopropylaluminumoxy) 2-Pentyl) ginseng (pentafluorophenyl) borate, 4- (4-diisopropylaluminumoxy_ 丨 _phenyl) phenyl (pentafluorophenyl) borate, and 4- (2- (4- (diisopropylaluminumoxyphenyl) propalkyl) phenoxy) ginseng (10 pentafluorophenyl) borate. Particularly preferred ammonium compounds are (4-diethylaluminumoxy_ 丨 _phenyl) ginseng (pentafluorophenyl) borate methyldi (tetradecyl) ammonium, (4-diethylaluminumoxy-1 -Phenyl) Phenyl (pentafluorophenyl) borate methyldi (hexadecyl) ammonium, ('diethylsulphoxyphenyl) Phen (pentafluorophenyl) borate methyldi (octadecyl) ) Ammonium and its mixtures. The first 15 complexes are disclosed in U.S. Patent Nos. 5,834,393 and 5,783,512. Another suitable ion-generating type activator compound includes a salt formed by a cationic oxidant and a non-coordinating compatible anion represented by the formula: (〇xe +) d (AdJe, where 〇xe + is a cation with a charge e + D is an integer from 1 to 3; e is an integer from 1 to 3; and Ad is as defined above. Cationic oxidants include, for example, ferrocene diamonds, diamonds, Pb + 2+ Λ + η 丞 substituted ferrocene Or Ag. Preferably, the specific examples are the anions previously defined for the activator compounds containing Bronsted 25 200302235 soft, invention-explaining acids, especially pentacene benzoate. Another: a suitable ion generating property The type 1 activator compound includes a salt formed by a carbene diamond ion and a non-coordinating compatible anion of the following formula π: 5 @ + Α · Wherein: @ 为 匸】 ^ Carbene sulfonium ion; and A- Non-coordinating compatible anions of number -1. The preferred carbenesulfonium ion is a trityl cation, especially a trityl diamond. 10 The preferred type 1 carbenesulfonium salt activator compound is pentamidine (pentafluoro Phenyl) trityl hydrazone borate, Nine (nonafluorobiphenyl) boron Tritylpyrene, pentyl (pentafluorophenyl) acetate and other substituted adducts. Another suitable ion-generating type activator compound includes a compound which is represented by the formula The salt of silanium ions and non-coordination-compatible anions 15 R3Si + A_ where: R is a C 1.1 〇 hydrocarbyl group; and A has the same definition as above. 2 The preferred type 1 silane sulfonium salt activator compound Trimethylsilyl (pentafluorophenyl) borate, trimethylsilyl (pentafluorobiphenyl) borate, triethylsilyl (pentafluorophenyl) borate, and other substituted additions Silane sulfonium salts were previously outlined in the Journal of Chemical Communications of the Chemical Society, 1993, 383-384, and Lambert, J. B. et al., Organometals, 1994, 13 26 200302235 玖, Description of Inventions, 2430-2443. Silane phosphonium salts as activator compounds for addition polymerization catalysts are patented in US Patent No. 5,625,087. Certain alcohols, thiols, silanols, oximes and ginseng (pentafluorobenzene) Radical) Borane complex is also effective for Type 1 catalyst activation And can be used in the present invention 5. These catalyst compounds are disclosed in US Patent No. 5,296,433. Type 1 activator compounds can also be used in combination. A particularly preferred combination is a tri (hydrocarbyl) aluminum or tri (hydrocarbyl) borane compound ( Each hydrocarbon group contains from 1 to 4 carbons) and a mixture of an oligomer or a polymer aluminocarbon compound. The molar ratio of the catalyst / co-catalyst is preferably i: 10,000 to 10: 1, 10 It is 1: 5000 to 10: 1, and most preferably !: 2500 to i: i. When alumoxane itself is used as the type 1 activator compound, it is preferably used in a large mole ratio, usually in a molar ratio. Ear-based, at least 50 times the amount of metal complex. If ginseng (pentafluorophenyl) borane is used as the first type activator compound, it is preferable to use the molar ratio of ginseng (pentafluorophenyl) borane to metal complexes: 05: to ...:! 15 is even better! ··: [to 6 ··! And best for! : J to 5 ·· i. The remaining activator compounds are usually preferably used with metal complexes in approximately equimolar amounts. If the aforesaid non-coordinating or poorly coordinating anion is used as the type Ⅰ activator compound, the metal complex to be alkylated according to the present invention (in other words, one of R of the metal complex is an alkyl group Or aryl). Boron-activated 20-agent compounds were used as the [best activator compounds including pentamidine, pentafluorophenyl) borane, ginseng (o-ninefluorobiphenyl) borane, and (3,5_ hydrazone (trifluoromethyl) phenyl) phytate, ginseng (pentafluorophenyl) non-burned ginseng (o-nonafluorobibenzyl) alane Compound rhenium, then the metal is 27 200302235 玖, the molar ratio of the type 1 activator compound to the metal center in the invention description compound is generally between 1: 10 to 10,000: 1, more preferably i: 10 to 5000 : i and optimally in the range of 1 · 1 to 2,500 · · 1. If a compound containing or obtaining a non-coordinating or poorly coordinating anion is selected as the activator compound, Mormolitone 5 is usually 1: 10 To M00: 1, and preferably 1: 2 to 250: 1. The formation of the catalyst according to the present invention is a combination of at least one type 1 activator, at least one type 2 activator, and at least one via a cobalt complex. The combination of catalyst modifiers is completed. For example, the type 2 activator may be an organometallic compound, of which at least one or ten A metal atom or a hydrocarbon group is directly bonded to the metal to provide a metalloid bond or a carbon-metal bond. The hydrocarbon group is non-aromatic, and the hydrocarbon group is directly bonded to the metal of the organometallic compound, and preferably contains ... and more preferably Carbon atom. The metal of the organometallic compound is selected from Groups 2, 3, 4, 5, 6, 7, 12, 13, or 14 of the Periodic Table of Elements. 15 Suitable type 2 activators for use herein include sodium hydrocarbyl, _ Sodium hydride, lithium hydrocarbyl, lithium dentate, hydrocarbyl zinc, zinc dioxide, magnesium dihydrate, hydrocarbyl magnesium, dihydrocarbyl magnesium, especially sodium alkyl, lithium alkyl, alkyl zinc, alkyl magnesium halide , Dialkyl magnesium, such as n-octyl sodium, butyl lithium, neopentyl lithium, methyl chloride, ethyl bell, diethyl zinc, dibutyl chloride, butyl chloride, ethyl 20 chloride Chemical towns, octyl gas towns, dibutyl towns, dioctyl towns, butyl octyl towns. Suitable type 2 catalyst activators for use herein also include neutral Lewis acids, such as non-aromatic Cu Hydrocarbyl-substituted Group 13 compound substituents, especially | J (hydrocarbyl) aluminum compounds or (hydrocarbyl) boron compounds, Derivatives, containing up to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more particularly 28 200302235 玖, description of the invention alkyl aluminum compounds, such as triethyl aluminum and triisobutyl aluminum; dialkyl aluminum hydrides such as Diisobutyl hydrogenated compounds; Alkyl compounds such as dibutylethoxyaluminum; Aluminium compounds such as diethylaluminum chloride, ethyl gasified aluminum, diisobutylchloride, isopropyl Butyl chloride, ethyloctyl chloride | Lu, ethyl 5 times aluminum chloride, ethylcyclohexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride. Used here Suitable type 2 catalyst activators also include trihalides and boron trioxides such as aluminum trichloride, aluminum trifluoride, boron trifluoride, and Erhanium and bidentate sides and Louis Vuitton. Adduct. 0 Type 2 catalyst activators suitable for use here as needed also include neutral Lewis acids such as hydrocarbyl-substituted Group 3 or 7 compounds, especially (hydrocarbyl) aeronautics, (hydrocarbyl) titanium, (hydrocarbyl) In the case of (hydrocarbyl), or (hydrocarbyl) indium compounds and their (including fully halogenated) derivatives, each hydrocarbon or alkoxylated group contains 1 to 20 carbons. 5 Suitable type 2 catalyst activators for use herein also include Group 3 to Group 7 metal halides, particularly hafnium-, titanium-, meta-, starvation- or | mesh halides, such as titanium dioxide, trichloride Titanium, titanium tetrachloride, osmium dichloride, trichloride, four gasification, vanadium dichloride, vanadium trichloride, molybdenum pentachloride. Preferred aluminum compounds are e.g. diethylaluminum chloride, ethyl chloride, chlorodiisobutylaluminum chloride, ethyloctyl aluminum chloride, ethyl sesquichloro aluminum, and fluorenyl sesquichloride. Aluminum sulfide, ethylcyclohexylaluminum chloride, dicyclohexylaluminum chloride, and dioctyl aluminum hydride are the second type activators. The molar ratio of the type 2 catalyst activator relative to the metal complex of the cobalt complex is characterized in that the molar ratio is usually in the range of 1: 1 to 〇, 〇〇〇 ·· 1, better i ·· 29 200302235 玖The invention description ranges from 10 to 500: 1 and optimally 1: 1 to 250: 1. It is particularly desirable that the activator compound used herein is a combination of type 2 activator compounds, such as neutral Lewis acid used as needed, especially dialkyl aluminum halide compounds having 1 to 4 carbon atoms in each alkyl group (Such as ethyl 5 times aluminum semichloride, ethyloctyl aluminum chloride, and diethyl aluminum chloride) and type 1 activator compounds (such as Cu hydrocarbyl-substituted Group 13 Lewis acid compounds, especially each hydrocarbyl group contains 1 to 20 carbon functional tris (hydrocarbyl) boron or aluminum compounds, especially a combination of (pentafluorophenyl) borane or (pentafluorophenyl) alane); type 2 activator (as in The combination of natural Louise g "mixture" and polymer or oligomer oxoalkane (type 1 activator); and a single neutral Lewis acid (type 2 activator) is especially used with ginseng (pentabenzene Base) butterfly or ginseng (pentaphenyl) minus and polymer or oligomer alumoxane (type activator) combination. As just mentioned, the catalyst according to the present invention can be completed by combining at least one thorium activator, at least one type 2 activator, and at least one 15 catalyst modifiers via a cobalt complex. Timo's catalytic other modifiers are aromatic compounds. A preferred catalyst modification is an aromatic compound containing at least two or more qh groups bonded to an aromatic compound. Che Jiaojia's aromatic compounds containing at least two groups are represented by one of the following formulas:
OHOH
30 200302235 玖、發明說明30 200302235 发明, description of invention
IIIIII
(R9)s (RU)r(R9) s (RU) r
其中 R’及R”分別表示含1-20個碳原子之烴基; R1、R2、R3、R4、R5、R6、R7、R8、R9、Rl〇、rU、 R12可為相同或相異,且分別表示1-20個碳原子之烴基、經 基、硝基、烴氧基或ii原子; Z表示含1 -20個碳原子之烴基、氧原子、琉原子、_ (C=0)-基、-(NR13)基-或-(SiR142)-基,其中 R13及R14可相同 或相異且分別表示1-20個碳原子之烴基; 31 200302235 玖、發明說明 d為0、1或2 ; ο、p為0、1、2、3或4 ; m+n<4 ; 5 o+p<4 ; r+q<4 ; s+t<4> 較佳催化劑改性劑為芳香族化 口初其中至少兩個 0H基各自直接鍵結至芳香族化合物之芳香環之一 10 更特別催化劑改性劑係選自式I。 又更佳下列催化劑改性劑之—係組合姑錯合物、第! 型活化劑化合物及第2型活化劑化合物使用··Where R 'and R "respectively represent a hydrocarbon group containing 1-20 carbon atoms; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, rU, R12 may be the same or different, and Represents a hydrocarbyl, meridian, nitro, hydrocarbyloxy or ii atom of 1-20 carbon atoms, respectively; Z represents a hydrocarbyl, oxygen atom, Rau atom, _ (C = 0) -group containing 1-20 carbon atoms ,-(NR13) group- or-(SiR142)-group, in which R13 and R14 may be the same or different and each represents a hydrocarbon group of 1-20 carbon atoms; 31 200302235 玖, invention description d is 0, 1 or 2; ο, p is 0, 1, 2, 3, or 4; m + n <4; 5 o + p <4; r + q <4; s + t < 4 > A preferred catalyst modifier is an aromatic port In the beginning, at least two 0H groups are each directly bonded to one of the aromatic rings of the aromatic compound. 10 More particularly, the catalyst modifier is selected from Formula I. Still more preferably, the following catalyst modifiers are combinations of complex compounds, Use of type 2 activator compounds and type 2 activator compounds ...
又更佳催化劑改性劑含有三個羥基。 當選用有機金屬化合物做為催化劑改性劑時。催化劑 改性劑相對於鈷錯合物之金屬中心之莫耳比通常係於1 : 10至 1,000 : 1,更佳 1 : 1〇 至 500 : 1 及最佳 1 ·· 1 至 250 : 1 之範圍。 出乎意外地根據本發明有效使用催化劑改性劑組合鈷 20 錯合物、第1型活化劑化合物及第2型活化劑化合物,允許 以相當高催化效率製造二烯聚合物。此外,當小量催化劑 32 200302235 玖、發明說明 改性劑應用於聚合反應時,使用較小量昂貴的鋁氧烷活化 劑化合物’可達成可相媲美的催化劑效率。此外,可獲得 具有較低鋁殘餘物因而較高澄清度之聚合物。 5 10 除了根據本發明之金屬錯合物及活化劑化合物外,催 化劑組成物也含有小量其它有機金屬化合物,其可用作為 所謂之清除劑。添加清除劑,用以於反應混合物之雜質反 應。可隨時添加,但通常係於金屬錯合物及活化劑化合物 添加前’添加清除劑至反應混合物。通常使时機銘化合 物做為清除劑。清除劑例如為三辛基銘、三乙基紹及三異 丁基鋁。熟諳技藝人士了解金屬錯合物、第i型活化劑化 :物、第2型活化劑化合物以及催化劑改性劑可呈單一成 ::呈數種成分混合物存在於催化劑組成物。例如若需要 2聚合物之分子性料(例如分子量分布)則需要使用混 20 妓^據本發明之金屬錯合物可用於稀屬單體之均聚合及 特…特別包合之—型烯煙為二婦,較佳為共輛二浠。 發明二=聚單體為芳香族或非芳香族_烴。根據本 ::屬:物特別適合用於-或多種共一聚合 "、異戊—J::成:群’包含:1,3-丁二 烯、1,3H ,丁一烯)、2,3-二甲基-1,3· 丁二 1丄庚—、2,心己二烯、π己二婦、己二烯、 二=:二稀、〜戊二蝉、環戊4 场 ,%辛一烯、原冰片二烯、亞乙 〜、—或環戊二烯 33 200302235 玖、發明說明 嫦。較佳芳香族α烯烴為苯乙烯、對甲基苯乙烯、二乙烯 苯例如丨,2-二乙烯苯、1,3-二乙烯苯、1,4-二乙烯苯以及二 乙烯基甲苯例如2,3-二乙烯基甲苯、2,4-二乙烯基甲苯、 2,5-二乙烯基甲苯、2,6_二乙烯基甲笨、3,4·二乙烯基甲苯 5 、3,5-二乙烯基甲苯單體。更佳使用苯乙烯做為芳香族α 烯烴。較佳非芳香族α烯烴為乙烯以及烷基鏈含1-35個碳 原子之^烯(如丙烯、丁烯、1-己烯、1-辛烯、1-癸烯)。 欲用於此種產物及方法之單體為熟諳技藝人士已知。 使用根據本發明之金屬錯合物,非晶形或橡膠狀或橡 10膠聚合物可依據使用之單體而製備。 -烯早體之聚合可以已知方式,於氣相進行以及於液 體^應介f進行。後述情況下以溶絲合及料液聚合為 適合。金屬用量通常為金屬於分散劑之濃度達ι〇.8_ι〇·3莫 15 20 耳/升且幸X佳1GMG、耳/升。聚合方法可呈氣相聚合(例 如於流化床反應器)、呈懸浮液/衆液聚合、呈固相粉末聚 或所《月之本體聚合方法進行,其中使用過量稀煙單體 做為反應介質。分散劑適合用於聚合反應,分散劑可選自 下述旦群包合但非限於環烧類如環己烧;飽和、直鏈或 分支脂肪族烴類如丁烧、戍院、己燒、餘、辛燒、五甲 基庚烷或礦油餾分例如輕質或常規石油、石腦油、毕油或 化煙流體或類似之液體也適合用於該項… 方香族溶劑如甲笨也適合用於該項用途。若干芳香 $㈣❹,㈣安純考量,巍 製造時去除料溶劑。於技術«之μ方法中== 34 200302235 玖、發明說明 5 10 用㈣本脂肪族烴或其混合物,例如石化蓋業出售用作為 溶劑、或使用低成本脂肪族烴組合芳香族溶劑、或使用芳 香族溶劑。若使用脂肪族煙做為溶劑,則溶劑可視需要地 含有小量芳香族煙如”。如此若例如使”基銘氧炫 (MA〇)做為活化劑化合物,則可使用甲苯做為MAO溶劑, 俾以溶解形式供應MA〇至聚合反應器。當使用此等溶劑時 需要脫水或純化溶劑;可毫無_地由熟諳技藝人士達成。 於聚口方法中’金屬錯合物、活化劑化合物(第1及2 型)以及催化劑改性劑係以催化有效量使用,換古之,任 何可成功地生成聚合物之數量使用。此種用量方便由熟諳 技藝人士藉例行實驗決定。 、、技云人士谷易了解根據本發明使用之催化劑組成 物也可於原位製備。 若欲使用溶液聚合或本體聚合,則較佳典型係於〇t Μ至2貌且較佳至⑽。c之溫度進行反應,但非限制性。 聚口方法也可於懸浮液或氣相聚合條件下進行,並型 係於低於15〇°C之溫度進行,但非限制性。 ^ 由聚合所得聚合物可藉已知方法後續處理。通常催化 劑係於聚合物處理期間之某一點去活化。去活化也可以已 方式例4 用7]C或醇進行。由於使用本發明催化劑系統 ’均聚物或共聚物中之催化劑含量,特別_素及金屬含量 極低,故可刪除催化劑殘餘物之去除。但若有所需,聚合 物中催化背J殘餘物含量可以已知方式例如藉洗蘇減少。去 /舌化步驟之後可接著為汽提步驟[由(均)聚合物中去除有機 35 200302235 玖、發明說明 溶劑]。 聚合可於大氣壓、於低於大氣壓、或於高達5〇〇 MPa 之升高壓力下連續或非連續進行。較佳聚合反應係於〇.〇i 至500 MPa,最佳0.01至1〇 MPa,特別〇1·2 Mpa之壓力進 5行。可施加較高壓力。於此種高壓處理中,根據本發明之 金屬錯合物也可使用而獲得良好結果。漿液聚合及溶液聚 合通常係於較低壓力較佳低於10 MPa壓力進行。 聚合也可以若干步驟串聯及/或並聯進行。若有所需 ,催化劑組成物、單體組成物、溫度、氫氣濃度、壓力、 10停駐時間等可因各步驟而異。藉此方式也可獲得性質分布 寬廣例如分子量分布寬廣之產物。經由使用根據本發明之 金屬錯合物用於烯烴之聚合,可獲得具有多分散性 (Mw/Mn)=l.〇-50之聚合物。 t實施方式3 15 實施例 20 須了解本發明可於無任何未特別揭示之成分存在下操 作。下列實施例係供進一步舉例說明本發明,但非視為限 制性。除非有相反陳述,否則全部份數及百分比係以重量 為基準表示。「隔夜」一詞於使用時表示約16_18小時時間 ,「室溫」於使用時表示2〇_25t:溫度。 王部沙及有機金屬 ----- π <珥鳅皆係使用標準胥蘭克 ⑽lenk)設備及技術於惰性氮氣氣氛下、或於手套箱内進 行。後文中「THF」表示四氣咬喃,心㈣表示乙基# 半氯化銘,(CH3)3sia表示三甲基氯石夕烧,「麵」表示 36 200302235 玖、發明說明 1,2-二甲氧基乙烷,「Me」表示「甲基」,「Et」表示「乙 基」,「Bu」表示「丁基」,「Ph」表示「苯基」,「MMAO」 或「MMAO-3a」表示「改性甲基鋁氧烷」以及「PMAO-IP」表示「帶有改良性能之聚合物曱基鋁氧烷」,二者皆 5 係購自艾克左諾貝爾公司。「IBAO」表示「異丁基鋁氧烷 」以及「MAO」表示「甲基鋁氧烷」,二者皆係購自艾爾 巴瑪(Albemarle)公司。所述壓力為絕對壓力。聚合反應係 於排除水分及氧氣之下於氮氣氣氛下進行。產物係利用 SEC(尺寸排除層析術)、元素分析、NMR[布魯克(Bmker) 10 分析公司之亞凡司(Avance)400裝置(4=400 MHz ; 13C = 100 MHz)]以及IR(布魯克光學公司之IFS 66 FT-IR光譜儀) 。IR樣本係使用硫化碳做為膨脹劑且使用兩倍或四倍溶劑 製備。DSC(差異掃描卡計)係使用TA儀器公司之DSC 2920 測量。 15 Μη及Mw為分子量,係藉SEC通用校準測定。Mw/Mn 為分子量分布,於此處稱做多分散性。 丁二烯或異戊間二烯聚合物之1,4-順-、1,4-反_及1,2-聚二烯間之比例係由IR及13C-NMR-光譜術測定。聚合物之 玻璃轉換溫度(TG)係藉DSC測定。 20 實施例1 1.始錯合物 1.1辛酸姑1 辛酸鈷(Co 10 HEX-CEM)係呈鈷錯合物(10%鈷)於礦 油精D 60之溶液而得自OMG公司。 37 200302235 玫、發明說明 2·聚合 2·〗聚合程序之說明 2·Μ聚合程序之說明-方法1 聚合係於雙重壁2升鋼製反應器進行,反應器於加入 5有機溶劑、金屬錯合物、活化劑、單體、電子受體或電子 施體成分、烷基鹵化鋁成分或其它成分(如芳香族改性劑) 之前,使用氮氣掃除。若無其它陳述,則聚合反應器回火 至25°C。然後下列成分以下述順序添加至聚合反應器:有 機溶劑、部分活化劑1、部分共軛二烯單體、視需要使用 1〇之第二烯烴以及部分烷基函化鋁成分。讓混合攪拌3〇分鐘。 於另一個200宅升之雙重壁鋼製反應器内(回火至聚合 反應器之相同溫度),以下述順序加入下列各成分··有機 /谷劑、部分活化劑1、部分烷基_化鋁成分、視需要使用 之芳香族化合物以及部分共軛二烯單體。讓混合物攪拌下 歹J %間。然後加入鈷化合物,所得混合物又攪拌經歷下列 時間。 聚合反應係藉添加200毫升鋼製反應器内容物至2升聚 合容器而開始。除非有其它陳述否則聚合係於25。〇進行。 聚合時間依實驗各異。 )Q s, -马了結束聚合過程,聚合溶液移入第三雙重壁鋼製反 ^㈣’反毫升甲醇含有艾歐諾做為聚合物安定 劑〇升甲醇含2克艾歐諾)。此混合物攪拌15分鐘。然後回 收之^合物使用水蒸氣汽提j小日寺而去除溶劑及其它揮發 物且於45 C之供箱内脫水24小時。 38 200302235 玖、發明說明 2· 1.2聚合程序之說明-方法2 聚合反應係於雙重壁2升鋼製反應器進行,反應器内 於ο、加有機/谷劑、金屬錯合物、活化劑、單體、電子受體 或電子施體成分、烷基函化鋁成分或其它化合物前,使用 5氮氣掃除。除非另行陳述,否則聚合反應器回火至25°C。 下列成分係以下述順序添加··有機溶劑、活化劑、共扼二 烯單體、視需要使用之第二烯烴、烷基_化鋁成分以及視 品要使用之方香無化合物。讓混合物擾拌一段下列時間, 然後加入始化合物而開始聚合。 10 除非另行陳述,否則聚合係於25X:進行。聚合時間依 實驗而各異。 為了結束聚合過程,聚合溶液移入第三雙重壁鋼製反 應器内’反應器含50毫升甲醇含有艾歐諾做為聚合物安定 劑(1升甲醇含2克艾歐諾)。此混合物攪拌丨5分鐘。然後回 15 收之聚合物使用水療氣汽提1小時而去除溶劑及其它揮發 物,且於45°C之烘箱内脫水24小時。 3.聚合實施例 3.1 1,3· 丁二烯之聚合 3.1.1使用1,2,4-三甲氧基苯之1,3-丁二烯之聚合 2〇 A)使用金屬錯合物1、MMA0-3a、乙基倍半氣化紹及 1,2,4-三曱氧基苯進行1,3-丁二烯之聚合(回合^ 實驗係根據前述概略聚合程序(2·1·1)進行。聚合係於 含373克環己烷及125克甲苯之聚合溶劑進行。如此338克 環己烷,22.2克曱笨,49.8克(〇·92莫耳)U_丁二稀單體, 39 200302235 玖、發明說明 MMAO-3a(1.6克庚烷溶液含4.1毫莫耳MMAO),0.248克 (1.47亳莫耳)1,2,4-三曱氧笨及0.5克(0·2毫莫耳)乙基倍半氯 化I呂添加至聚合反應器。35克環己烷,64.8克曱苯,3.5克 (0.06莫耳)l,3-丁二烯單體,6.2克庚烷溶液含毫莫耳 5 ΜΜΑΟ及2.0克(0.8亳莫耳)乙基倍半氣化鋁攪拌丨小時,隨 後於另一反應容器混合156亳克(0.264毫莫耳)金屬錯合物1 及攪拌10分鐘。 隨後所得混合物移入聚合反應器内開始聚合反應。 經1小時又4分鐘後,如前述結束聚合反應(參考211) 10 。此時,單體轉化成聚丁二烯之轉化率為99.9%。汽提處 理結果回收53.2克聚丁二烯。 根據C-NMR之測定,聚合物含有go』%順_ι,4-; 6.0%反-1,4-,4.0% 1,2-聚丁二烯。 聚合物分子量達368,000克/莫耳,多分散性達594 15 (Μη=62,000 ; Μζ= 1,228,000)。慕尼值達27」。 Β)使用金屬錯合物i,MMA〇_3a,乙基倍半氣化鋁及 1,2,4-二甲氧基苯之ι,3-丁二烯之聚合(回合2) 實驗係根據前述概略聚合程序(211)進行。聚合係於 含505.9環己烷之聚合溶劑進行。如此4〇2·7克環己烷, 20 5(M克(0·9莫耳)1,3-丁二烯單體,MMAO-3a(1.7克庚烷溶 液含4.3毫莫耳MMAO),0.248克(1·47亳莫耳)ι,2,4·三甲氧 基苯及0.5克(0.2亳莫耳)乙基倍半氯化鋁添加至聚合反應 器内。103.2克環己烷,3·5克(〇〇6莫耳)](,3· 丁二烯單體, 6.3克庚烷溶液含16·3毫莫耳ΜΜΑ〇及2〇克(〇·8亳莫耳)乙 40 200302235 玖、發明說明 基倍半氯化鋁攪拌丨小時又3分,隨後於分開反應容器混合 156¾克(0.264毫莫耳)金屬錯合物i及攪拌1〇分鐘。 隨後所得混合物移入聚合反應器而開始聚合反應。 、、ί 1小k 14分後’如前述結束聚合反應(參考2.1.1)。 5此時,單體轉化成聚丁二烯之轉化率為67.2%,汽提結果 回收36.0克聚丁二烯。 根據nC-NMR之測定,聚合物含有82〇%順],‘; 10.0%反-1,4-,8.0% 1,2·聚丁二烯。 聚合物分子量達63,000克/莫耳,多分散性達21 10 (Μη=30,000 ; Μζ= 113,〇〇〇)。 C)使用金屬錯合物i,MMA0_3a,乙基倍半氯化鋁及 1,2,4-三甲氧基苯進行丨,3_ 丁二烯之聚合(回合1〇) 實驗係根據前述概略聚合程序進行(2·^)。聚合反應 係於含3 814克環己烧及1 〇〇〇克甲苯之聚合溶劑進行。如此 15 3814克環己烷,1000克甲苯,537·4克(99莫耳)u· 丁二烯 單體’ MMAO-3a(8.0克庚烷溶液含20.5毫莫耳MMAO), 1.24克(7.35毫莫耳)1,2,4-三甲氧基苯及2.5克(17.2毫莫耳) 乙基倍半氣化鋁添加至聚合反應器。i 80克甲苯,4 〇克 (0.07莫耳)1,3-丁二烯單體,31·〇克含79 5毫莫*MMA〇庚 20烧溶液及1〇·〇克(87.8亳莫耳)乙基倍半氯化鋁攪拌1小時, 隨後於分開反應容器混合780毫克(1.320毫莫耳)金屬錯合 物1及攪拌5分鐘。 隨後所得混合物移入聚合反應器而開始聚合反應。 經1小時又2分後,如前述結束聚合反應(參考2.1.1)。 41 200302235 玖、發明說明 此時’單體轉化成聚丁二烯之 回收恨9克聚丁二婦。 b率切.5%,汽提結果 3·】·2 1,3-丁二烯根據聚合方法2聚合 使用金屬錯合物〗, ,MA〇-3a,乙基倍半氯化鋁及 1,2,4-二甲氧基苯進行 — 返仃!,3-丁-烯之聚合(回合3) 實驗係根據前述概略聚人 %。私序(2丄2)進行。聚合係於 3 5002克甲苯之聚合溶劑進行。如此簡克甲苯,542克 ίο 15 ⑽莫耳單體,Μ财3a(78 7克庚焼溶液含 綱·!毫莫耳讀,,2.48克(147毫莫耳)124_三甲氧基 笨及24.56克(9.94¾莫耳)乙基倍半氯化紹添加至聚合反應 器。混合物攪拌1小時。隨後出毫克(2.26毫莫耳)钻錯合 物1添加至聚合反應器而開始聚合反應。 1小時後,單體轉化成聚丁二烯之轉化率為73·8% (400.1克)。2小時又1〇分後,如前述結束反應(參考n o 。汽提結果回收356.6克聚丁二烯。 根據nC-NMR之測定,聚合物含有91〇%順_154_ ; 6.0%反-1,4-,3.0% 1,2-聚丁二烯。聚合物分子量達 302,000 克 / 莫耳,多分散性達 2·77(Μη=109,000 ; Mz = 649,000) ° 慕尼值達35.0。 3.1.3 1,4-丁二烯與笨乙烯之共聚合 3.1.3.1 1,4-丁二烯及笨乙烯使用金屬錯合物1,MMAO-3a ,及1,2,4-三曱氧基苯及乙基倍半氯化鋁之共聚合 反應(回合4) 42 20 200302235 玖、發明說明 實驗係根據前述概略聚合程序進行(211)。聚合係於 含510.9克環己烷之聚合溶劑進行。如此4〇3·7克環己烷, 27.0克(0.5莫耳)1,3-丁二烯單體,庚烷溶 液含3〇.0亳莫耳ΜΜΑ0),26.0克(0.25莫耳)苯乙稀單體, 5 0.248克(1.47毫莫耳):1二4_三甲氧基苯及156克(6.3毫莫耳) 乙基倍半氯化鋁添加至聚合反應器。1〇7·2克環己烷,4〇 克(0.07莫耳)1,3_丁二烯單體及〇57克(23毫莫耳)乙基倍半 乳化鋁攪拌1小時,隨後與470毫克(0.798毫莫耳)鈷錯合物 1於分開反應容器混合及攪拌15分鐘。 1〇 隨後反應混合物移入聚合反應器而開始共聚合反應。 經1小時又15分後,如前述結束共聚合反應(參考 2·1·1)。此時單體轉化成聚合物之轉化率為34.0%。汽提處 理結果回收19.4克聚合物。 聚合物含有1.5%苯乙烯(50%苯乙烯含量偵測得為聚苯 15乙烯段)。根據】3c-nmr測定,共聚物之聚丁二烯部分含有 88·5%順],‘ ;6.5%反-1,4-,3.5% 1,2-聚丁二稀。 聚合物分子量達76,000克/莫耳,多分散性達13〇 (Mn=6?〇〇〇 ; Mz= 357,000) 〇 3.1.4比較例 2〇 A)1,3· 丁二烯使用錯合物1&MMA0-3a之聚合(回合5 ;比 較例) 實驗係根據前述概略聚合程序(2.1.1)進行。聚合反靡、 係於500克環己烷溶劑進行。如此4〇9克環己烷,5〇〇克 (0·92莫耳)U_ 丁二烯單體及MMA〇_3a(9〇克庚烷溶液含 43 200302235 玖、發明說明 23.1毫莫耳MMAO)添加至聚合反應器。91克環己烷,4.〇 克(0.07莫耳)1,3 -丁二稀單體及2.7克克庚烧溶液含6.9亳莫 耳MMAO,於分開反應容器内混合470毫克(0·80毫莫耳)金 屬錯合物1及攪拌10分鐘。 5 隨後所得混合物移入聚合反應器開始聚合反應。 經1小時後,如前述結束共聚合反應(參考2.1.1)。此 時單體轉化成聚丁二烯之轉化率為41 · 8 %。汽提處理結果 回收21·2克聚丁二烯。 根據13C-NMR之測定,聚合物含有97.0%順-l,4-; 10 1.5%反-1,4-,1.5% 1,2-聚丁二烯。 聚合物分子量達123,000克/莫耳,多分散性達6.25 (Μη=20,〇〇〇 ; Μζ= 21〇,〇〇〇)。 Β)使用金屬錯合物},MMA0-3a以及乙基倍半氯化鋁進行 聚合(回合6,比較例) 15 實驗係根據前述概略聚合程序(2.1.1)。聚合係於含 381克環己烷及118克甲苯之聚合溶劑進行。如此33丨克環 己烧’ 87克甲苯,50·2克(0·93莫耳)u_丁二烯單體, MMAO-3a(1.6克含4·1毫莫耳MMAO庚烷溶液)及〇.5克(〇.2 毫莫耳)乙基倍半氯化鋁添加至聚合反應器。50克環己烷 20 ’ 31克甲苯,3·5克(〇·〇6莫耳)1,3-丁二烯單體,6.2克含 16.1亳莫*ΜΜΑ〇庚烷溶液及2 〇克(〇 8毫莫耳)乙基倍半氯 化鋁攪拌65分鐘,隨後於分開反應容器混合156毫克(0.264 笔莫耳)金屬錯合物1,及攪拌10分鐘。 隨後所得混合物移入聚合反應器開始聚合反應。 44 200302235 玖、發明說明 經1小時又5分鐘後,如前述結束共聚合反應(參考 2.1.1) 。此時單體轉化成聚丁二烯之轉化率為87.3%。汽提 處理結果回收46.9克聚丁二烯。 根據UC-NMR之測定,聚合物含有93.5%順-1,4-; 5 3.5%反-1,4-,3.0% 1,2-聚丁二稀。 聚合物分子量達378,000克/莫耳,多分散性達4.85 (Mn=78,000 ; Mz= 1,114,000)。慕尼值達32.7。 C)使用金屬錯合物1,MMAO-3a以及乙基倍半氯化鋁進行 聚合(回合7,比較例) 10 實驗係根據前述概略聚合程序(2·1·1)進行。聚合係於 含571 ·9克環己烧之聚合溶劑進行。如此462.1克環己烧, 51.2 克(0.95 莫耳)1,3-丁二稀單體,]y[MAO-3a(46.8 克含 120 毫莫耳MMAO庚烷溶液)及3·12克(12.6亳莫耳)乙基倍半氯 化鋁添加至聚合反應器内。使用乙烯氣體將聚合反應器内 15部壓力調整至7巴。109.8克環己烷,3.0克(〇.〇6莫耳口,弘丁 二烯單體及2.0克(0.8毫莫耳)乙基倍半氣化鋁攪拌丨小時, 隨後於分開反應容器混合470毫克(0.798毫莫耳)金屬錯合 物1,及攪拌10分鐘。 隨後所得混合物移入聚合反應器開始聚合反應。隨後 20聚合反應器壓力使用乙婦氣體調整至9.3巴。 經1小時又30分鐘後,如前述結束共聚合反應(參考 2.1.1) 。此時單體轉化成聚丁二烯之轉化率為95 〇%。汽提 處理結果回收5 1.5克聚丁二烯。 根據13c-nmr之測定,聚合物含有91·5^ι|Μ_Μ_ ; 45 200302235 玖、發明說明 5.5%反-1,4-,3.0% 1,2-聚丁二烯。 聚合物分子量達18,000克/莫耳,多分散性達2.25 (Mn=8,000 ; Mz= 31,000)。 D) 使用金屬錯合物1,MMAO-3a以及三甲基(氯)矽烷進行 5 聚合(回合8,比較例) 實驗係根據前述概略聚合程序(2.1.1)進行。如此298.9 克甲苯,51.1克(〇·94莫耳)1,3-丁二烯單體添加至聚合反應 器。74.0克甲苯,4.3克(0.07莫耳)1,3- 丁二烯單體, MMAO-3a(13.9克含35.3毫莫耳MMAO庚烷溶液)及2.08克 10 (〇·〇19亳莫耳)三甲基(氯)矽烷攪拌10分鐘,隨後於分開反 應容器混合119毫克(0.201毫莫耳)金屬錯合物丨及攪拌4分 鐘。 隨後所得混合物移入聚合反應器開始聚合反應。 經2小時又1 8分鐘後,如前述結束共聚合反應(參考 15 2,1 ·丨)。此時單體轉化成聚丁二烯之轉化率為23.5%。汽提 處理結果回收13 · 0克聚丁二稀。 根據13C-NMR之測定,聚合物含有順一; 4.0%反-1,4-,3.0% 1,2-聚丁二烯。 聚合物分子量達86,000克/莫耳,多分散性達441 20 (Mn=19,500 ; Mz= 645,000)。 E) 使用鈷錯合物!,MMA0_3a及第三丁基氯之聚合(回合9 ;比較例) 實驗係根據前述概略聚合程序(2丄2)進行。聚合係於 含504克環己烷之聚合溶劑進行。如此5〇4克甲苯,54·6克 46 200302235 玖、發明說明 (1.01 莫耳)1,3-丁二烯單體,MMAO-3a(11.9 克含 30.3 毫莫 耳MMAO庚烷溶液)及2.2克(24毫莫耳)第三丁基氯添加至 聚合反應器。混合物攪拌13分鐘。隨後115毫克(0.20亳莫 耳)金屬錯合物1添加至聚合反應器而開始聚合反應。 5 經2小時又19分鐘後,如前述結束共聚合反應(參考 2.1.1)。此時單體轉化成聚丁二烯之轉化率為29·5%。汽提 處理結果回收16.1克聚丁二烯。 根據nC-NMR之測定,聚合物含有25.0%順-1,4-; 66.0%反,9.0% 1,2-聚丁二烯。 10 3·2聚合活性-比較 回合 活性 [千克{聚合物}/毫莫耳{始}[小時] 回合 活性 [千克{聚合物}/毫莫耳{銘}[小時] 1 0.64** 6 0.35** 2 0.51** (0.82*) 7 0.18** 3 0.42** 8 0.11** 4 0.08** 9 0.14** 5 0.12** 10 1.18** (1.72*) C·.··比較例;* 6分鐘後測量;** 15分鐘後測量; ***...· 20分鐘後測量 3 · 3分子量-比較 回合 Mw Μη Μζ 回合 Mw Μη Μζ 1 368,000 62,000 1,228,000 6 378,000 78,000 1,114,000 2 63,000 30,000 113,000 7 18,000 8,000 31,000 3 302,000 109,000 649,000 8 86,000 19,500 645,000 4 76,000 6,000 357,000 9 未測定 未測定 未測定 5 123,000 20,000 210,000 47 200302235 玖、發明說明 3.4分子量分布(MWG)及慕尼黏度-比較 —---- 回合 Mw/Mn 慕尼 Tg,°C 回合 Mw/Mn 慕尼 Tg,°c 5.94 27.1 未測定 6 4.85 32.7 未測定 2 2.1 未測定 未測定 7 2.25 未測定 未測定 3 — 2.77 35.0 未測定^ 8 4.41 未測定 未測定 4 —----— 13.0 未測定 未測定 9 未測定 未測定 未測定 5 ---——. 6.25 未測定 未測定 3 · 5微結構-比較 回合 順-1,4-PB 反-1,4-PB 1,2- 聚合物 回合 順-1,4-PB 反-1,4-PB 1,2- 聚合物 1 90.0 6.0 4.0 6 93.5 3.5 3.0 2 82.0 10.0 8.0 7 91.5 5.5 3.0 3 91.0 6.0 3.0 8 93.0 4.0 3.0 4 88.5 6.5 3.5 9 25.0 66.0 9.0 5 97.0 1.5 1.5 PB=聚丁二烯 Tg =破璃轉換溫度 本發明之優點為聚合反應催化活性顯著增高。實施例 證實本發明之以鈷為主的催化劑所得活性比以羧酸鈷為主 之催化劑高2至3倍。根據本發明定義之含催化劑改性劑之 1〇催化劑系統之聚合活性(參考回合1及回合2)與缺本發明之 催化劑改性劑之催化劑系統(參考前述比較例特別回合5_9 ’ 3.2段)做比較。例如辛酸鈷,改性鋁氧烷(MMA〇_3a), 乙基倍半氣化鋁及1,2,4-三甲氧基苯之組合聚合丨,3·丁二烯 於壤己烧溶劑,聚合活性高達0.64千克[聚丁二烯]/亳莫耳[ 15鈷]小時(參考回合1),或聚合活性高達0.18千克[聚丁二烯 48 200302235 玖、發明說明 ]/宅莫耳[鈷]小時(參考回合19)。不含丨,2,4_三甲氧基笨做 為催化劑改性劑,聚合活性達018千克[聚丁二烯]/毫莫耳[ 姑]小時(參考比較例回合7)。辛酸鈷組合改性紹氧烧做為 催化劑,結果獲得聚合活性為〇12千克[聚丁二烯]/亳莫耳[ 5鈷]小時(參考比較例回合5)。當環己烷/甲苯混合物用作為 聚合溶劑時可觀察得相同趨勢(比較回合2及6)。 其它可能之催化劑混合物例如辛酸鈷、改性鋁氧烷 (MMAO-3a)與三甲基氣矽烷之組合(回合8),或第三丁基 氯(回合9)做為含氯陰離子化合物,獲得較低聚合活性 1〇 (0·11或〇·Η、0.12千克[聚丁二烤]/毫莫耳[姑]小時)。 本發明之另一優點為本發明催化劑無需分開老化步驟 (參考回合3),若需採用視需要使用之老化步驟,則其優點 為無需長時間老化。因此,可恰於所需順序添加催化劑成 分之聚合反應器開始聚合反應。聚合係始於例如添加催化 15劑前驅物做為最末成分(參考回合10、u&12)。若視需要 之老化步驟結合於催化劑製備/聚合程序,則老化時間短 ,例如10分鐘(參考回合丨及幻但非限制性,可於溫和條件( 如25t:但非限制性)進行,催化活性高。催化劑老化與聚 合之溫度範圍分別係選自_50〇c S+25〇c>c且較佳]〇它至 20 +120 C,及更佳0°C及80°c。例如聚合回合i(聚合溫度25 C,老化溫度25t)之催化活性達〇·64千克聚丁二烯/亳莫 Z鈷/小時。本發明之另—優點為催化劑老化時無需極端 溫度。其優點為可誘生聚合反應而無需等候或延遲時間, 或當添加最末催化劑成分至聚合反應器時無需實質等候時 49 200302235 玖、發明說明 間或延遲。 、本&月之X U為共聚合共輛二稀與烴,較佳 為芳香族⑽烴。例如(參考回合4),以丁二稀與苯乙稀 共聚合獲得T二婦-苯乙缔共聚物(笨乙稀含量i 5%)。 5 本發明之金屬催化劑之又-優點(金屬錯合物與第!型 及第2型活化劑化合物以及與催化劑改性劑之特定組幻為 f造量身訂製之聚合物。特別,活化劑、金屬錯合物以及 芳香族催化劑改性劑(比較第丨型活化劑係以化學計算量或 較低量使用)之選擇以及催化劑製備方式、及聚合反應用 10溶劑(非芳香族或芳香族)以及使用之溶劑(芳香族及非芳香 族)比例、二烯濃度及聚合溫度等選擇可允許只使用特定 鈷錯合物而調整聚合物微結構(順_、反_及乙烯基含量比) 以及調整所得聚二烯分子量。 本發明之一稀聚合反應之另一優點為催化劑製備方式 15 (例如催化劑成分添加順序以及催化劑老化)可有利地影響 聚合物性質如分子量。 根據本發明之催化劑可使用適當技術(例如噴霧技術 但非限制性)用於溶液聚合法也可用於氣相聚合法。 【圖式簡單說明】 20 益 【圖式之主要元件代表符號表】 益 50Still more preferred catalyst modifiers contain three hydroxyl groups. When an organic metal compound is selected as the catalyst modifier. The molar ratio of the catalyst modifier to the metal center of the cobalt complex is usually 1:10 to 1,000: 1, more preferably 1:10 to 500: 1 and most preferably 1 ·· 1 to 250: 1 range. Unexpectedly, the effective use of the catalyst modifier combination of the cobalt 20 complex, the type 1 activator compound, and the type 2 activator compound according to the present invention allows the production of diene polymers with relatively high catalytic efficiency. In addition, when a small amount of catalyst 32 200302235 发明, description of the invention when the modifier is used in the polymerization reaction, the use of a relatively small amount of expensive alumoxane activator compound 'can achieve comparable catalyst efficiency. In addition, polymers with lower aluminum residues and thus higher clarity can be obtained. 5 10 In addition to the metal complex and the activator compound according to the present invention, the catalyst composition also contains a small amount of other organometallic compounds, which can be used as a so-called scavenger. A scavenger is added to react the impurities in the reaction mixture. It can be added at any time, but it is usually based on the metal complex and activator compound, and the scavenger is added to the reaction mixture. Timing compounds are often used as scavengers. Scavengers are, for example, trioctylamine, triethylsaw, and triisobutylaluminum. Those skilled in the art understand that metal complexes, type i activators, type 2 activator compounds, and catalyst modifiers can exist in the catalyst composition in a single form :: as a mixture of several ingredients. For example, if you need 2 polymer molecular materials (such as molecular weight distribution), you need to use 20 mixed prostitutes. ^ According to the present invention, the metal complex can be used for the homopolymerization of rare monomers and special ... special encapsulation-type diene For the second wife, a total of two wives are preferred. Invention 2 = the monomer is an aromatic or non-aromatic hydrocarbon. According to this :: genus: substances are particularly suitable for-or a variety of co-polymerization ", isoprene-J :: into: group 'contains: 1,3-butadiene, 1,3H, butadiene), 2 , 3-Dimethyl-1,3 · butane-1 丄 heptane-2, 2, heart hexadiene, π hexamethylene dichloride, hexadiene, di =: dilute, ~ pentane, cyclopentane, 4 fields, % Octadiene, orthobornadiene, ethylene ~, or cyclopentadiene 33 200302235 玖, invention description 嫦. Preferred aromatic alpha olefins are styrene, p-methylstyrene, divinylbenzene such as 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, and divinyltoluene such as 2 1,3-divinyltoluene, 2,4-divinyltoluene, 2,5-divinyltoluene, 2,6-divinylmethylbenzyl, 3,4-divinyltoluene 5, 3,5- Divinyl toluene monomer. More preferably, styrene is used as the aromatic alpha olefin. Preferred non-aromatic alpha olefins are ethylene and alkylenes having an alkyl chain having 1 to 35 carbon atoms (e.g., propylene, butene, 1-hexene, 1-octene, 1-decene). Monomers intended for such products and methods are known to those skilled in the art. Using the metal complex according to the present invention, an amorphous or rubbery or rubber polymer can be prepared depending on the monomers used. -The polymerization of the ene precursor can be carried out in a known manner in the gas phase and in the liquid phase. In the case described later, it is suitable to dissolve the silk and liquid-liquid polymerization. The amount of metal used is usually a concentration of metal in the dispersant of 0.8 to 3.0 Mo 15 20 ears / liter, and fortunately X Jia 1GMG, ears / liter. The polymerization method can be carried out in a gas phase polymerization (for example, in a fluidized bed reactor), as a suspension / liquid phase polymerization, as a solid phase powder polymerization, or as a bulk polymerization method, in which an excessive amount of dilute smoke monomer is used as a reaction medium. The dispersant is suitable for the polymerization reaction. The dispersant may be selected from the group consisting of the following groups, but is not limited to cyclic burners such as cyclohexanone; saturated, straight-chain or branched aliphatic hydrocarbons such as butan, Puyuan, hexane, Residual, scorched, pentamethylheptane or mineral oil fractions such as light or conventional petroleum, naphtha, tar, or soot fluids or similar liquids are also suitable for this ... Suitable for this purpose. Some fragrances $ ㈣❹, purely considered by Lu'an, Wei removes solvent during manufacture. In the μ method of technology «= 34 200302235 玖, description of invention 5 10 Use transcripts of aliphatic hydrocarbons or mixtures thereof, such as petrochemical caps, for sale as solvents, or use low-cost aliphatic hydrocarbons in combination with aromatic solvents, or use Aromatic solvents. If aliphatic smoke is used as the solvent, the solvent may optionally contain a small amount of aromatic smoke such as "." If, for example, "Jiming Oxygen (MAO)" is used as the activator compound, toluene may be used as the MAO solvent.俾 Supply MA0 to the polymerization reactor in dissolved form. When using these solvents, dehydration or purification of the solvent is required; this can be achieved by skilled artisans without any problems. In the polymerization method, the metal complex, activator compounds (types 1 and 2), and catalyst modifiers are used in a catalytically effective amount. In other words, any amount of polymer that can be successfully produced is used. This amount is conveniently determined by a skilled artisan through routine experimentation. Gu Yi, a skilled person, understands that the catalyst composition used according to the present invention can also be prepared in situ. If solution polymerization or bulk polymerization is to be used, it is preferably typically in the range of 0 to 24 μm and more preferably to ⑽. The reaction is carried out at a temperature of c, but is not limited. The polymerization method can also be carried out under the conditions of suspension or gas phase polymerization, and the type is carried out at a temperature below 150 ° C, but it is not limited. ^ Polymers obtained by polymerization can be subsequently processed by known methods. The catalyst is usually deactivated at some point during the polymer treatment. Deactivation can also be carried out in Example 4 using 7] C or alcohol. Since the catalyst content in the catalyst system of the present invention is used, the content of the catalyst, especially the element and metal content is extremely low, so the removal of the catalyst residue can be deleted. However, if desired, the content of the catalytic back J residue in the polymer can be reduced in known ways, such as by washing. The dehydration step may be followed by a stripping step [removal of organic from (homo) polymer 35 200302235 玖, description of invention solvent]. Polymerization can be carried out continuously or discontinuously at atmospheric pressure, below atmospheric pressure, or at elevated pressures up to 500 MPa. The preferred polymerization reaction is in the range of 0.01 to 500 MPa, most preferably 0.01 to 10 MPa, and a pressure of 0.1 to 2 Mpa in 5 rows. Higher pressures can be applied. In such a high pressure treatment, the metal complex according to the present invention can also be used with good results. Slurry polymerization and solution polymerization are usually carried out at a lower pressure, preferably below 10 MPa. Polymerization can also be performed in series and / or in parallel in several steps. If desired, the catalyst composition, monomer composition, temperature, hydrogen concentration, pressure, 10 dwell time, etc. may vary from step to step. In this way, products with a broad distribution of properties, such as a broad molecular weight distribution, can also be obtained. By using the metal complex according to the present invention for the polymerization of olefins, polymers having polydispersity (Mw / Mn) = 1.0-50 can be obtained. tEmbodiment 3 15 Example 20 It should be understood that the present invention can be operated without any components not specifically disclosed. The following examples are provided to further illustrate the invention, but are not to be considered as limiting. Unless stated to the contrary, all parts and percentages are expressed on a weight basis. The term "overnight" means about 16-18 hours when used, and "room temperature" means 20-25t when used: temperature. Wang Busha and organometallics ----- π < 珥 鳅 are all carried out using standard 胥 lenk) equipment and technology in an inert nitrogen atmosphere or in a glove box. In the following, "THF" means tetragas, palpitate means ethyl # semichloride, (CH3) 3sia means trimethylchlorite, and "face" means 36 200302235 玖, description of the invention 1, 2-2 Methoxyethane, "Me" means "methyl", "Et" means "ethyl", "Bu" means "butyl", "Ph" means "phenyl", "MMAO" or "MMAO-3a "" Modified methylaluminoxane "and" PMAO-IP "means" polymer fluorenyl aluminoxane with improved properties ", both of which were purchased from Extron Nobel Corporation. "IBAO" means "isobutylalumoxane" and "MAO" means "methylalumoxane", both of which were purchased from Albemarle. The pressure is an absolute pressure. The polymerization is carried out under a nitrogen atmosphere while excluding water and oxygen. The products are SEC (size exclusion chromatography), elemental analysis, NMR [Avance 400 device of Bmker 10 Analytical Company (4 = 400 MHz; 13C = 100 MHz)] and IR (Brook Optics The company's IFS 66 FT-IR spectrometer). IR samples were prepared using carbon sulfide as the bulking agent and using two or four times the solvent. DSC (Differential Scanning Card Meter) was measured using DSC 2920 from TA Instruments. 15 Mη and Mw are molecular weights, which are determined by SEC universal calibration. Mw / Mn is the molecular weight distribution and is referred to herein as polydispersity. The ratio between 1,4-cis-, 1,4-trans-, and 1,2-polydiene of butadiene or isoprene polymer is determined by IR and 13C-NMR-spectroscopy. The glass transition temperature (TG) of the polymer is measured by DSC. 20 Example 1 1. Initial complex 1. Cobalt octanoate (Co 10 HEX-CEM) was obtained from OMG as a solution of cobalt complex (10% cobalt) in mineral spirit D 60. 37 200302235 Description of the invention 2 · Polymerization 2 · 〖Description of the polymerization procedure 2 · M description of the polymerization procedure-Method 1 The polymerization is performed in a double-walled 2 liter steel reactor. The reactor is charged with 5 organic solvents and metal complex Before purging substances, activators, monomers, electron acceptors or electron donor components, alkyl aluminum halide components or other components (such as aromatic modifiers), use nitrogen to sweep away. Unless otherwise stated, the polymerization reactor was tempered to 25 ° C. The following ingredients were then added to the polymerization reactor in the following order: organic solvent, part of the activator 1, part of the conjugated diene monomer, a second olefin using 10 as needed, and part of the aluminum alkylating ingredient. Let mix for 30 minutes. In another 200-litre double-walled steel reactor (tempered to the same temperature of the polymerization reactor), add the following ingredients in the following order: organic / cereal, part of the activator, and part of the alkylation Aluminum components, aromatic compounds used as needed, and partially conjugated diene monomers. Let the mixture stir for% J%. The cobalt compound was then added and the resulting mixture was stirred for the following time. The polymerization was started by adding 200 ml of the steel reactor contents to a 2 liter polymerization vessel. Unless stated otherwise, the polymerization is at 25. 〇 Performed. The polymerization time varies from experiment to experiment. ) Q s,-The polymerization process was ended, and the polymerization solution was transferred to a third double-walled steel reactor. The anti-ml methanol contained Ionol as a polymer stabilizer (0 liter of methanol contained 2 g of Ionol). This mixture was stirred for 15 minutes. The recovered compound was then stripped with water vapor to remove the solvent and other volatiles and dehydrated in a 45 C supply box for 24 hours. 38 200302235 发明, Description of Invention 2 · 1.2 Description of Polymerization Procedure-Method 2 The polymerization reaction is carried out in a double-walled 2 liter steel reactor. In the reactor, organic / cereal, metal complex, activator, Prior to the monomer, electron acceptor or electron donor component, aluminum alkylate component or other compounds, sweep with 5 nitrogen. Unless otherwise stated, the polymerization reactor was tempered to 25 ° C. The following components are added in the following order: organic solvents, activators, conjugated diene monomers, second olefins as needed, alkyl-aluminum components, and fragrance-free compounds to be used in the products. The mixture was allowed to stir for the following time, and then the starting compound was added to start polymerization. 10 Unless stated otherwise, polymerization is performed at 25X: conducted. The polymerization time varies from experiment to experiment. To end the polymerization process, the polymerization solution was transferred to a third double-walled steel reactor. The reactor contained 50 ml of methanol containing Ionol as a polymer stabilizer (1 liter of methanol contains 2 g of Ionol). This mixture was stirred for 5 minutes. Then the polymer recovered at 15 was stripped with hydrotherapy gas for 1 hour to remove solvents and other volatiles, and dehydrated in an oven at 45 ° C for 24 hours. 3. Polymerization Example 3.1 Polymerization of 1,3 · butadiene 3.1.1 Polymerization of 1,3-butadiene using 1,2,4-trimethoxybenzene 2A) Use of metal complex 1, Polymerization of 1,3-butadiene with MMA0-3a, ethyl sesquigas, and 1,2,4-trimethoxyoxybenzene (round ^ The experiment was based on the above-mentioned rough polymerization procedure (2 · 1 · 1) The polymerization was carried out in a polymerization solvent containing 373 g of cyclohexane and 125 g of toluene. Thus, 338 g of cyclohexane, 22.2 g of benzene, 49.8 g (.92 mole) of U-butadiene monomer, 39 200302235 发明 Description of the invention MMAO-3a (1.6 g heptane solution contains 4.1 millimoles MMAO), 0.248 g (1.47 millimoles) 1,2,4-trioxobenzyl and 0.5 g (0.2 millimoles ) Ethyl sesquichloride was added to the polymerization reactor. 35 grams of cyclohexane, 64.8 grams of toluene, 3.5 grams (0.06 mole) of 1,3-butadiene monomer, 6.2 grams of heptane solution containing Mole 5 MMAO and 2.0 g (0.8 mol) of ethyl sesquihydrate aluminum were stirred for 1 hour, and then 156 亳 (0.264 mmol) of metal complex 1 was mixed in another reaction vessel and stirred for 10 minutes. The resulting mixture is then transferred to a polymerization reactor and opened. Polymerization. After 1 hour and 4 minutes, the polymerization reaction is ended as described above (Ref. 211) 10. At this time, the conversion rate of the monomer to polybutadiene is 99.9%. As a result of the stripping treatment, 53.2 grams of polybutadiene were recovered According to the C-NMR measurement, the polymer contains go ′% cis, 4-; 6.0% trans-1, 4-, 4.0% 1,2-polybutadiene. The molecular weight of the polymer is 368,000 g / mo Ear, polydispersity up to 594 15 (Μη = 62,000; Μζ = 1,228,000). Mooney value is 27 ″. B) The metal complex i, MMA〇_3a, ethyl sesquigas aluminum and 1 The polymerization of 2,4-dimethoxybenzene in 1,3-butadiene (round 2) was performed according to the aforementioned general polymerization procedure (211). The polymerization was performed in a polymerization solvent containing 505.9 cyclohexane. Thus, 4.02 g of cyclohexane, 20 5 (M g (0.9 mol) of 1,3-butadiene monomer, MMAO-3a (1.7 g of a heptane solution containing 4.3 millimoles of MMAO), 0.248 g (1.47 mol), 2,4 · trimethoxybenzene and 0.5 g (0.2 mol) of ethyl sesquichloride were added to the polymerization reactor. 103.2 g of cyclohexane, 3 5 g (〇06mol)] (3, butadiene monomer, 6.3 g heptane solution containing 16.3 millimoles MMA0 and 20 g (0.8 mole) B 40 200302235发明, description of the invention: Stirring aluminum sesquichloride for 1 hour and 3 minutes, followed by mixing 156¾ g (0.264 mmol) of metal complex i in a separate reaction vessel and stirring for 10 minutes. The resulting mixture was then transferred to a polymerization reactor and Start the polymerization reaction. After 1 minute and 14 minutes, end the polymerization reaction as described above (refer to 2.1.1). 5 At this time, the conversion rate of the monomer to polybutadiene is 67.2%, and the stripping result is recovered 36.0 G polybutadiene. According to nC-NMR measurement, the polymer contains 82.0% cis], '; 10.0% trans-1, 4-, 8.0% 1,2 polybutadiene. The molecular weight of the polymer is 63,000 grams / Mole, polydispersity up to 21 10 ( η = 30,000; Mζ = 113,00). C) The metal complex i, MMA0_3a, ethyl sesquichloride and 1,2,4-trimethoxybenzene were used for The polymerization (round 10) experiment was performed according to the above-mentioned rough polymerization procedure (2. ^). The polymerization reaction was carried out in a polymerization solvent containing 3 814 g of cyclohexane and 1000 g of toluene. Thus 15 3814 g of cyclohexane 1000 grams of toluene, 537.4 grams (99 moles) of u · butadiene monomer 'MMAO-3a (8.0 grams of heptane solution containing 20.5 millimoles of MMAO), 1.24 grams (7.35 millimoles) of 1, 2 , 4-trimethoxybenzene and 2.5 g (17.2 mmol) of ethyl sesquihydrate were added to the polymerization reactor. 80 g of toluene, 40 g (0.07 mol) of 1,3-butadiene mono Body, 31.0 g containing 79.5 mmol * MMA 0 heptane solution and 10.0 g (87.8 mol) of ethyl sesquichloride were stirred for 1 hour, and then 780 mg ( 1.320 millimolar) metal complex 1 and stirred for 5 minutes. The resulting mixture was then transferred to a polymerization reactor to start the polymerization reaction. After 1 hour and 2 minutes, the polymerization reaction was terminated as described above (refer to 2.1.1). 41 2 00302235 发明, description of the invention at this time '9 monomer polybutadiene recovered from conversion of monomers into polybutadiene. B rate cut. 5%, stripping result 3 ·] · 2 1,3-butadiene according to polymerization Method 2 Polymerization uses metal complexes, MAO-3a, ethyl sesquichloride, and 1,2,4-dimethoxybenzene—polymerization of 3-but-ene (round 3) The experiment system gathers people according to the above outline. Private sequence (2 丄 2). The polymerization was performed in a polymerization solvent of 3,5002 g of toluene. So simple gram of toluene, 542 grams of ο 15 mol monomer, M Choi 3a (78 7 g of heptane solution containing gang ·! Mol read, 2.48 g (147 mol) 124_trimethoxybenzyl and 24.56 g (9.94 ¾ mole) of ethyl sesquichloride was added to the polymerization reactor. The mixture was stirred for 1 hour. Then milligrams (2.26 mmol) of diamond complex 1 was added to the polymerization reactor to start the polymerization reaction. After 1 hour, the conversion of the monomer to polybutadiene was 73.8% (400.1 g). After 2 hours and 10 minutes, the reaction was terminated as previously described (refer to no. Stripping results recovered 356.6 g of polybutadiene According to nC-NMR measurement, the polymer contains 91% cis-154_; 6.0% trans-1, 4-, 3.0% 1,2-polybutadiene. The molecular weight of the polymer is 302,000 g / mole, and more Dispersibility up to 2.77 (Μη = 109,000; Mz = 649,000) ° Mooney value reaches 35.0. 3.1.3 Copolymerization of 1,4-butadiene and stupid ethylene 3.1.3.1 1,4-butadiene and stupid Copolymerization reaction of ethylene using metal complex 1, MMAO-3a and 1,2,4-trimethoxyoxybenzene and ethyl sesquichloride (round 4) 42 20 200302235 before The outlined polymerization procedure is carried out (211). The polymerization is carried out in a polymerization solvent containing 510.9 g of cyclohexane. Thus, 40.7 g of cyclohexane, 27.0 g (0.5 mole) of 1,3-butadiene monomer , Heptane solution contains 30.0 mol MMA0), 26.0 g (0.25 mol) styrene monomer, 5 0.248 g (1.47 mmol): 1 2 4_trimethoxybenzene and 156 g ( 6.3 millimoles) Ethyl sesquichloride was added to the polymerization reactor. 107.2 grams of cyclohexane, 40 grams (0.07 moles) of 1,3-butadiene monomer and 057 grams ( 23 millimoles) ethyl sesqui-emulsified aluminum was stirred for 1 hour, and then mixed with 470 mg (0.798 millimoles) of cobalt complex 1 in a separate reaction vessel and stirred for 15 minutes. 10 The reaction mixture was then transferred into a polymerization reactor and The copolymerization reaction was started. After 1 hour and 15 minutes, the copolymerization reaction was ended as described above (refer to 2.1.1.1). At this time, the conversion rate of the monomer to polymer was 34.0%. 19.4 g was recovered as a result of the stripping treatment. Polymer. The polymer contains 1.5% styrene (50% styrene content is detected as polystyrene 15 ethylene segments). According to the 3c-nmr measurement, the copolymer polybutadiene Contains 88.5% cis], '; 6.5% trans-1, 4-, 3.5% 1,2-polybutadiene. The molecular weight of the polymer is 76,000 g / mole, and the polydispersity is 13 ° (Mn = 6? 〇〇〇; Mz = 357,000) 〇3.1.4 Comparative Example 2A) 1,3 · butadiene polymerization using complex 1 & MMA0-3a (Round 5; Comparative Example) The experiment is based on the above outline The aggregation procedure (2.1.1) is performed. The polymerization was carried out against 500 g of cyclohexane solvent. So 409 g of cyclohexane, 500 g (0.92 mol) of U_butadiene monomer and MMA 0_3a (90 g of heptane solution contains 43 200302235 玖, description of invention 23.1 millimolar MMAO ) Is added to the polymerization reactor. 91 grams of cyclohexane, 4.0 grams (0.07 moles) of 1,3-butadiene monomer and 2.7 grams of heptane solution containing 6.9 mol mole MMAO, mixed in a separate reaction vessel with 470 mg (0 · 80 Millimoles) of metal complex 1 and stirred for 10 minutes. 5 The resulting mixture is then transferred to a polymerization reactor to begin the polymerization reaction. After 1 hour, the copolymerization reaction was terminated as described above (refer to 2.1.1). At this time, the conversion of the monomer to polybutadiene was 41.8%. As a result of the stripping treatment, 21.2 g of polybutadiene was recovered. According to 13C-NMR measurement, the polymer contains 97.0% cis-1,4-; 10 1.5% trans-1,4-, 1.5% 1,2-polybutadiene. The polymer has a molecular weight of 123,000 g / mole and a polydispersity of 6.25 (Mη = 20,000,000; Mζ = 21.0,000,000). Β) Polymerization using metal complex}, MMA0-3a and ethyl sesquichloride (Round 6, Comparative Example) 15 The experiment was performed according to the aforementioned rough polymerization procedure (2.1.1). The polymerization was performed in a polymerization solvent containing 381 g of cyclohexane and 118 g of toluene. So 33 丨 grams of cyclohexane, 87 grams of toluene, 50.2 grams (0.93 moles) of u-butadiene monomer, MMAO-3a (1.6 grams of a solution containing 4.1 millimoles of MMAO heptane) and 0.5 g (0.2 mmol) of ethyl sesquichloride was added to the polymerization reactor. 50 grams of cyclohexane, 20 '31 grams of toluene, 3.5 grams (0.06 moles) of 1,3-butadiene monomer, 6.2 grams of a solution containing 16.1 moles of MMAO heptane and 20 grams ( 〇8mmol) ethyl sesquichloride was stirred for 65 minutes, and then 156 mg (0.264 pen moles) of metal complex 1 was mixed in a separate reaction vessel, and stirred for 10 minutes. The resulting mixture was then transferred to a polymerization reactor to begin the polymerization reaction. 44 200302235 发明, description of the invention After 1 hour and 5 minutes, the copolymerization reaction is ended as described above (refer to 2.1.1). At this time, the conversion rate of monomer to polybutadiene was 87.3%. As a result of the stripping treatment, 46.9 g of polybutadiene was recovered. According to UC-NMR measurement, the polymer contains 93.5% cis-1,4-; 5 3.5% trans-1,4-, 3.0% 1,2-polybutadiene. The polymer has a molecular weight of 378,000 g / mole and a polydispersity of 4.85 (Mn = 78,000; Mz = 1,114,000). Mooney is worth 32.7. C) Polymerization using metal complex 1, MMAO-3a and ethyl sesquichloride (round 7, comparative example) 10 The experiment was performed according to the aforementioned general polymerization procedure (2 · 1 · 1). The polymerization was performed in a polymerization solvent containing 571.9 g of cyclohexane. In this way, 462.1 grams of cyclohexane, 51.2 grams (0.95 moles) of 1,3-butadiene monomer,] y [MAO-3a (46.8 grams of a solution containing 120 millimoles of MMAO heptane) and 3.12 grams (12.6亳 Mol) ethyl sesquichloride was added to the polymerization reactor. The pressure in 15 parts of the polymerization reactor was adjusted to 7 bar using ethylene gas. 109.8 grams of cyclohexane, 3.0 grams (0.06 moles, butadiene monomer and 2.0 grams (0.8 millimoles) of ethyl sesquigas) were stirred for 丨 hours, and then mixed in a separate reaction vessel for 470 hours. Milligrams (0.798 millimoles) of metal complex 1 and stirred for 10 minutes. The resulting mixture was then transferred to a polymerization reactor to begin the polymerization reaction. Subsequently, the pressure of the 20 polymerization reactor was adjusted to 9.3 bar using ethane gas. After 1 hour and 30 minutes Then, the copolymerization reaction was terminated as described above (refer to 2.1.1). At this time, the conversion rate of the monomer to polybutadiene was 95.0%. As a result of the stripping treatment, 5 1.5 g of polybutadiene was recovered. According to 13c-nmr It was determined that the polymer contained 91 · 5 ^ ι | Μ_Μ_; 45 200302235 玖, description of the invention 5.5% trans-1,4-, 3.0% 1,2-polybutadiene. The polymer molecular weight reached 18,000 g / mol, Polydispersity is 2.25 (Mn = 8,000; Mz = 31,000). D) 5 polymerizations using metal complex 1, MMAO-3a and trimethyl (chloro) silane (round 8, comparative example). The aggregation procedure (2.1.1) is performed. Thus 298.9 g of toluene and 51.1 g (0.94 mol) of 1,3-butadiene monomer were added to the polymerization reactor. 74.0 grams of toluene, 4.3 grams (0.07 moles) of 1,3-butadiene monomer, MMAO-3a (13.9 grams of a solution containing 35.3 millimoles of MMAO heptane) and 2.08 grams of 10 (0.19 moles) Trimethyl (chloro) silane was stirred for 10 minutes, and then 119 mg (0.201 mmol) of the metal complex was mixed in a separate reaction vessel and stirred for 4 minutes. The resulting mixture was then transferred to a polymerization reactor to begin the polymerization reaction. After 2 hours and 18 minutes, the copolymerization reaction was terminated as described above (Ref. 15 2, 1 · 丨). At this time, the conversion of the monomer to polybutadiene was 23.5%. 13.0 grams of polybutadiene were recovered as a result of the stripping treatment. According to the 13C-NMR measurement, the polymer contains cis; 4.0% trans-1,4-, 3.0% 1,2-polybutadiene. The polymer has a molecular weight of 86,000 g / mole and a polydispersity of 441 20 (Mn = 19,500; Mz = 645,000). E) Use Cobalt Complex! Polymerization of MMA0_3a and third butyl chloride (round 9; comparative example) The experiment was performed according to the aforementioned general polymerization procedure (2 丄 2). The polymerization was performed in a polymerization solvent containing 504 g of cyclohexane. Such 504 grams of toluene, 54.6 grams of 46 200302235 玖, invention description (1.01 mole) 1,3-butadiene monomer, MMAO-3a (11.9 grams of MMAO heptane solution containing 30.3 millimoles) and 2.2 Grams (24 mmol) of third butyl chloride were added to the polymerization reactor. The mixture was stirred for 13 minutes. Then 115 mg (0.20 mol) of metal complex 1 was added to the polymerization reactor to start the polymerization reaction. 5 After 2 hours and 19 minutes, the copolymerization reaction is terminated as described above (refer to 2.1.1). At this time, the conversion of the monomer into polybutadiene was 29.5%. As a result of the stripping treatment, 16.1 g of polybutadiene was recovered. According to nC-NMR measurement, the polymer contains 25.0% cis-1,4-; 66.0% trans, 9.0% 1,2-polybutadiene. 10 3 · 2 Polymerization activity-Comparison of round activity [kg {polymer} / millimol [start] [hour] Round activity [kg {polymer} / millimol {ming} [hour] 1 0.64 ** 6 0.35 ** 2 0.51 ** (0.82 *) 7 0.18 ** 3 0.42 ** 8 0.11 ** 4 0.08 ** 9 0.14 ** 5 0.12 ** 10 1.18 ** (1.72 *) C ···· Comparative Example; * Measured after 6 minutes; ** Measured after 15 minutes; *** ... · Measured after 20 minutes 3 · 3 Molecular Weight-Comparative Round Mw Μη Μζ Round Mw Μη Μζ 1 368,000 62,000 1,228,000 6 378,000 78,000 1,114,000 2 63,000 30,000 113,000 7 18,000 8,000 31,000 3 302,000 109,000 649,000 8 86,000 19,500 645,000 4 76,000 6,000 357,000 9 Not determined Not determined Not determined 5 123,000 20,000 210,000 47 200302235 玖, Description of the invention 3.4 Molecular weight distribution (MWG) and Mooney viscosity-comparison --------- Round Mw / Mn Mooney Tg, ° C Round Mw / Mn Mooney Tg, ° c 5.94 27.1 Not determined 6 4.85 32.7 Not determined 2 2.1 Not determined Not determined 7 2.25 Not determined Not determined 3 — 2.77 35.0 Not determined ^ 8 4.41 Not determined Not determined 4 —----— 13.0 Not determined Not determined 9 Not determined Not determined Not determined 5 -------. 6.25 Not determined Not determined 3 · 5 Microstructure-Comparison Round Cis-1,4-PB Trans-1,4-PB 1,2- Polymer Round Cis-1,4-PB Trans-1,4-PB 1,2-polymer 1 90.0 6.0 4.0 6 93.5 3.5 3.0 2 82.0 10.0 8.0 7 91.5 5.5 3.0 3 91.0 6.0 3.0 8 93.0 4.0 3.0 4 88.5 6.5 3.5 9 25.0 66.0 9.0 5 97.0 1.5 1.5 PB = Polybutadiene Tg = glass breaking transition temperature The advantage of the present invention is that the catalytic activity of the polymerization reaction is significantly increased. Examples It is confirmed that the activity obtained by the cobalt-based catalyst of the present invention is 2 to 3 times higher than that of the catalyst based on cobalt carboxylate. Polymerization activity of the 10 catalyst system containing the catalyst modifier according to the present invention (refer to Round 1 and Round 2) and the catalyst system lacking the catalyst modifier of the present invention (refer to the aforementioned Comparative Example Special Round 5_9 '3.2) compare with. For example, cobalt octoate, modified aluminoxane (MMA0_3a), combined polymerization of ethyl sesquihydrate aluminum and 1,2,4-trimethoxybenzene. 3, butadiene in hexane burned solvent, Polymerization activity up to 0.64 kg [polybutadiene] / 亳 Mor [15 cobalt] hours (refer to Round 1), or polymerization activity up to 0.18 kg [Polybutadiene 48 200302235 玖, description of the invention] / house mol [Co ] Hours (refer to Round 19). Without 丨, 2,4_trimethoxybenzyl as a catalyst modifier, the polymerization activity reached 018 kg [polybutadiene] / mole [n] hours (refer to Comparative Example Round 7). Cobalt octoate combined with modified sintered oxygen was used as a catalyst, and as a result, a polymerization activity of 012 kg [polybutadiene] / amole [5 cobalt] was obtained (refer to Comparative Example Round 5). The same tendency was observed when a cyclohexane / toluene mixture was used as a polymerization solvent (compare rounds 2 and 6). Other possible catalyst mixtures such as cobalt octoate, a combination of modified aluminoxane (MMAO-3a) and trimethyl aerosilane (round 8), or third butyl chloride (round 9) as a chlorine-containing anion compound, obtain Lower polymerization activity 10 (0.11 or 0.10 kg, 0.12 kg [polybutadiene roasted] / millimolar [gu] hours). Another advantage of the present invention is that the catalyst of the present invention does not require a separate aging step (refer to Round 3). If an aging step is used as required, its advantage is that it does not require long-term aging. Therefore, the polymerization reaction can be started in a polymerization reactor in which the catalyst components are added in the desired order. The polymerization system begins, for example, with the addition of a catalyst 15 precursor as the final component (refer to Round 10, u & 12). If the required aging step is combined with the catalyst preparation / polymerization procedure, the aging time is short, for example, 10 minutes (reference round 丨 and magical but non-limiting, can be performed under mild conditions (such as 25t: but non-limiting), catalytic activity High. The temperature ranges of catalyst aging and polymerization are selected from _50〇c S + 25〇c &c; and preferably] 0 to 20 + 120 C, and more preferably 0 ° C and 80 ° c. For example, polymerization round i (polymerization temperature 25 C, aging temperature 25 t) has a catalytic activity of 0.64 kg of polybutadiene / ammonia Z cobalt / hour. Another advantage of the present invention is that no extreme temperature is required when the catalyst is aging. Its advantage is that it can induce No need to wait or delay time for the polymerization reaction, or no substantial waiting time when adding the last catalyst component to the polymerization reactor. 49 200302235 玖, the description of the invention may be delayed or delayed. And hydrocarbons, preferably aromatic fluorenes. For example (refer to Round 4), copolymers of styrene butadiene and styrene are used to obtain T-bis-styrene-styrene copolymers (styrene content i 5%). Another advantage of the metal catalyst of the invention (metal complex and type! And type 2 activator compounds, and polymers tailored to specific groups of catalyst modifiers. In particular, activators, metal complexes, and aromatic catalyst modifiers (compare type 丨 activation The agent is selected in stoichiometric amount or lower amount) and the preparation method of the catalyst, and the 10 solvents (non-aromatic or aromatic) for the polymerization reaction, the proportion of the solvents (aromatic and non-aromatic) used, and the diene concentration Selections such as polymerization temperature and polymerization temperature allow the use of specific cobalt complexes to adjust the polymer microstructure (cis-, trans-, and vinyl content ratios) and adjust the molecular weight of the resulting polydiene. The advantage is that catalyst preparation method 15 (such as the order of catalyst component addition and catalyst aging) can favorably affect polymer properties such as molecular weight. The catalyst according to the present invention can be used in solution polymerization methods using appropriate techniques (such as spraying techniques but not limiting). Can be used for gas phase polymerization. [Schematic description of the diagram] 20 benefits [representative symbols of the main elements of the diagram] benefit 50
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JO3598B1 (en) | 2006-10-10 | 2020-07-05 | Infinity Discovery Inc | Boronic acids and esters as inhibitors of fatty acid amide hydrolase |
CN102046179B (en) | 2008-04-09 | 2015-01-14 | 英菲尼提制药公司 | Inhibitors of fatty acid amide hydrolase |
EP2531511A1 (en) | 2010-02-03 | 2012-12-12 | Infinity Pharmaceuticals, Inc. | Fatty acid amide hydrolase inhibitors |
ITMI20122199A1 (en) * | 2012-12-20 | 2014-06-21 | Versalis Spa | PROCEDURE FOR THE PREPARATION OF (CO) POLYMERS OF DIENES CONJUGATED IN THE PRESENCE OF A CATALYTIC SYSTEM INCLUDING A BIS-IMMINICO DI COBALTO COMPLEX |
ITMI20122201A1 (en) | 2012-12-20 | 2014-06-21 | Versalis Spa | BONE-AZOTHATE COMPLEX OF COBALT, CATALYTIC SYSTEM INCLUDING THE BONE-AZOTHATE COMPLEX AND PROCEDURE FOR THE (CO) POLYMERISATION OF CONJUGATED DIENES |
ITMI20122206A1 (en) * | 2012-12-20 | 2014-06-21 | Versalis Spa | PROCEDURE FOR THE PREPARATION OF (CO) POLYMERS OF DIENES CONJUGATED IN THE PRESENCE OF A CATALYTIC SYSTEM INCLUDING A BIS-IMMINO-PYRIDINE COMPLEX OF COBALT |
EP3981803A4 (en) * | 2020-05-22 | 2023-04-19 | LG Chem, Ltd. | Liquid rubber preparation method and liquid rubber prepared thereby |
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BE759763A (en) * | 1969-12-02 | 1971-05-17 | Ube Industries | PROCESS FOR THE PREPARPTION OF 1,2-POLYBUTADIENE |
GB1372399A (en) * | 1970-12-25 | 1974-10-30 | Ube Industries | Process for producing polybutadiene |
JPS5529510A (en) * | 1978-08-21 | 1980-03-01 | Japan Synthetic Rubber Co Ltd | Preparation of 1,2-polybutadiene |
JPS5964609A (en) * | 1982-10-05 | 1984-04-12 | Ube Ind Ltd | Production of reinforced polybutadiene |
JP3463811B2 (en) * | 1991-04-24 | 2003-11-05 | Jsr株式会社 | Method for producing butadiene-based polymer |
KR100344230B1 (en) * | 1999-10-13 | 2002-07-24 | 금호석유화학 주식회사 | Preparation of hydroxy high 1,4-cis polybutadiene using molecular oxygen |
-
2003
- 2003-01-09 WO PCT/US2003/000673 patent/WO2003064484A1/en not_active Application Discontinuation
- 2003-01-27 TW TW92101733A patent/TW200302235A/en unknown
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