CN1247492C - Cobalt catalyst composition for ethylene oligomerization and use thereof - Google Patents

Cobalt catalyst composition for ethylene oligomerization and use thereof Download PDF

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CN1247492C
CN1247492C CNB01131138XA CN01131138A CN1247492C CN 1247492 C CN1247492 C CN 1247492C CN B01131138X A CNB01131138X A CN B01131138XA CN 01131138 A CN01131138 A CN 01131138A CN 1247492 C CN1247492 C CN 1247492C
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cobalt
di
catalyst composition
butylphenyl
methylphenyl
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CN1403424A (en
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阎卫东
刘彬彬
胡友良
徐文清
王航
马建江
姜涛
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中国石油天然气股份有限公司
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

本发明涉及一种乙烯齐聚的钴系催化剂组合物及其应用,所述的催化剂组合物由主催化剂钴系(II)亚胺基配位化合物和助催化剂为甲基铝氧烷、烷基铝和GaCl The present invention relates to a cobalt-based catalyst compositions and the use of an ethylene oligomerization, the catalyst composition of cobalt-based procatalyst (II) complex and imino cocatalyst is methyl aluminoxane, alkyl aluminum and GaCl

Description

一种乙烯齐聚的钴系催化剂组合物及其应用 An ethylene oligomerization catalyst is cobalt-based compositions and uses thereof

技术领域 FIELD

本发明涉及烯烃低聚催化剂,具体说来就是一种乙烯齐聚的钴系催化剂组合物及其应用。 The present invention relates to an olefin oligomerization catalyst, specifically an ethylene oligomerization is cobalt-based catalyst composition and its application.

背景技术 Background technique

线性α-烯烃作为石化工业重要的共聚单体、表面活性剂和润滑油及其添加剂的重要的合成原料和中间体,历来是石油化工市场上的紧俏商品,其中绝大部分的α-烯烃均是由乙烯齐聚制备得到的。 Linear α- olefin as comonomer important petrochemical industry, a surfactant and a lubricating oil additive and important synthetic intermediates and raw materials, has always been in short supply on the commodity petrochemical market, most of which were the α- olefin prepared by the oligomerization of ethylene is obtained. 乙烯齐聚法所用的催化剂主要有镍系、铬系、锆系、铝系和钴系等,近年来由于钴系催化剂以其对α-烯烃的高选择性、高催化活性而日渐受到重视。 Catalyst for ethylene oligomerization process used mainly nickel-based, chromium-based, zirconium, aluminum, and cobalt, etc., in recent years, since the cobalt catalyst in its high selectivity for α- olefins, with high catalytic activity increasing attention. 已报道的钴系催化剂(J.Am.Chem.Soc.,1998,120:7143;Chem.Commun.1998,849;WO 99/02472)的结构为: Cobalt catalyst (J.Am.Chem.Soc, 1998,120.: 7143; Chem.Commun.1998,849; WO 99/02472) reported the structure of: 其中,R1、R2、R3、R4均分别为氢原子、碳数1~30的烃基、取代烃基或惰性基团,X为阴离子;助催化剂为烷基铝。 Wherein, R1, R2, R3, R4 are each a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a substituted hydrocarbyl or an inert group, X is an anion; aluminum alkyl cocatalyst. 这类钴系催化剂组合物催化乙烯齐聚所得α-烯烃的碳数分布在C10~C32之间,其中C6~C20α-烯烃的含量>50%。 Such cobalt-based ethylene oligomerization catalyst compositions resulting α- olefin carbon number distribution between C10 ~ C32, wherein the content of olefins C6 ~ C20α-> 50%.

近年来,随着聚烯烃工业和表面活性剂工业的飞速发展,作为聚烯烃共聚单体的C6~C8和作为洗涤剂主要原料的C10~C18部分的线性α-烯烃的需求量均日益增大,因此努力提高该部分线性α-烯烃在总产品中的含量具有非常重要的经济价值和现实意义。 In recent years, with the rapid development of polyolefin industry and the industry of surfactant, linear C10 ~ C18 detergent portion as a main raw material α- demand as polyolefin comonomer C6 ~ C8 olefins both increasing and It has a very important economic value and practical significance, and therefore part of efforts to improve the content of the linear α- olefins in the total product.

本发明的目的就在于提供一种可以提高碳数分布为C6~C18的α-烯烃在产品中的相对含量的催化剂组合物及其制备方法和使用该催化剂组合物催化乙烯齐聚制备线性α-烯烃的方法,以满足目前化工行业的迫切需求。 Object of the present invention to provide a carbon number distribution of relative content of α- C6 ~ C18 olefins in the product of the catalyst composition and its preparation method can be improved using the catalyst composition prepared Linear Ethylene Oligomerization α- olefins, to meet the urgent needs of the chemical industry.

采用本发明的催化剂组合物所获得的线性α-烯烃的碳数分布在C6~C28之间,其中C6~C20大于80%。 Linear α- olefin carbon number of the present invention catalyst composition obtained is distributed between C6 ~ C28, C6 ~ C20 wherein more than 80%.

发明内容 SUMMARY

本发明涉及一种乙烯齐聚的钴系催化剂组合物及其应用,其特征是主催化剂为以钴系(II)亚胺基配位化合物,助催化剂为甲基铝氧烷、三异丁基铝和GaCl3的混合物。 The present invention relates to a cobalt-based catalyst compositions and the use of an ethylene oligomerization, characterized in that the catalyst is a cobalt-based master (II) imino complex, cocatalyst methylalumoxane, triisobutyl of a mixture of aluminum and GaCl3. 该催化剂组合物用于催化乙烯齐聚,使得到的线性α-烯烃的碳数分布在C6~C28之间,其中C6~C20大于80%。 Carbon atoms of the catalyst composition is used to catalyze the oligomerization of ethylene, the linear α- olefin obtained is distributed between C6 ~ C28, C6 ~ C20 wherein more than 80%.

在本发明的催化剂组合物中,所述的主催化剂为钴系(II)亚胺基配位化合物,其中亚胺基配位化合物是由2,6-二乙酰基吡啶或2,5-二乙酰基吡咯与2-甲基-4-烷氧基苯胺或2-甲基-4-苯氧基苯胺反应得到。 In the catalyst compositions of the present invention, the primary catalyst is cobalt (II) complex compound imino, imino wherein the coordination compound is 2,6 or 2,5-diacetylpyridine acetyl pyrrole or 4-phenoxy-2-methyl aniline is reacted with 2-methyl-4-alkoxy aniline obtained.

所述的2-甲基-4-烷氧基苯胺中,烷氧基为C1~C4的烷基与氧结合而成。 The 2-methyl-4-alkoxy anilines, alkoxy group of C1 ~ C4 alkyl group bonded to oxygen. 如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、叔丁氧基。 Such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy.

所述的2-甲基-4-苯氧基苯胺中的苯氧基为C6~C12的苯基及取代芳基。 The 2-methyl-4-phenoxy-phenoxy aniline is a substituted phenyl group and a C6 ~ C12 aryl group. 如苯氧基、2-甲基苯氧基、4-甲基苯氧基、2,4-二甲基苯氧基、2,6-二甲基苯氧基、2,4,6-三甲基苯氧基,2-甲氧基苯氧基、4-甲氧基苯氧基、2,4-二甲氧基苯氧基、2,6-二甲氧基苯氧基、2,4,6-三甲基苯氧基,2-乙基苯氧基、4-乙基苯氧基、2,4-乙甲基苯氧基、2,4,6-三乙基苯氧基,2-氯苯氧基、4-氯苯氧基、2,4-二氯苯氧基、2,4,6-三氯苯氧基,2-溴苯氧基、4-溴苯氧基、2,4-二溴苯氧基、2,4,6-三溴苯氧基,2-溴-4-甲基苯氧基、2-溴-6-甲基苯氧基、2,6-二溴-4-甲基苯氧基、4-溴-2,6-二甲基苯氧基,2-氯-4-甲基苯氧基、2-氯-6-甲基苯氧基、2,6-二氯-4-甲基苯氧基、4-氯-2,6-二甲基苯氧基。 Aryloxy such as phenoxy, 2-methylphenoxy, 4-methylphenoxy, 2,4-dimethylphenoxy, 2,6-dimethylphenoxy, 2,4,6-tris methylphenoxy, 2-methoxyphenoxy, 4-methoxyphenoxy, 2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2, 4,6-trimethylphenoxy, 2-phenoxy, 4-ethylphenoxy, 2,4-ethyl-methylphenoxy, 2,4,6-triethylbenzene group , 2-chlorophenoxy, 4-chlorophenoxy, 2,4-dichlorophenoxy, 2,4,6-trichlorophenoxy, 2-bromophenoxy, 4-bromophenoxy , 2,4-dibromophenyl group, 2,4,6-tribromophenoxy, 2-bromo-4-methylphenoxy, 2-bromo-6-methylphenoxy, 2,6 - dibromo-4-methylphenoxy, 4-bromo-2,6-dimethylphenoxy, 2-chloro-4-methylphenoxy, 2-chloro-6-methylphenoxy , 2,6-dichloro-4-methylphenoxy, 4-chloro-2,6-dimethylphenoxy.

所述的助催化剂为一种混合物,其特征为由甲基铝氧烷、三异丁基铝和GaCl3三部分组成。 Said cocatalyst is a mixture, characterized by methylalumoxane, triisobutylaluminum and GaCl3 three parts. 其中甲基铝氧烷与三异丁基铝的物质的量比100∶1~1∶1混合,尤其是90∶1~10∶1。 Wherein the molar ratio of methylaluminoxane and triisobutylaluminum 100:1 ~ 1:1 of mixing, especially 90 parts per 1 ~ 10:1. GaCl3与甲基铝氧烷和三异丁基铝的物质的量比为1∶100∶10~1∶10000∶100。 GaCl3 and the molar ratio of methylaluminoxane and triisobutylaluminum is 1:100:10 ~ 1:10000:100.

所述的钴系催化剂组合物的应用,其特征在于用于催化乙烯齐聚制备线性α-烯烃的方法为:在无水无氧条件下,乙烯压力0.1~10MPa、反应温度0~100℃时,顺序加入有机溶剂、助催化剂和主催化剂溶液,反应5~60分钟后,冷却至-10~0℃,加入甲醇终止反应,最后经精馏分离得到线性α-烯烃。 Application of the cobalt-based catalyst composition, characterized in that the catalytic oligomerization of ethylene for the preparation of linear α- olefin is: under anhydrous oxygen-free conditions, the ethylene pressure 0.1 ~ 10MPa, reaction temperature 0 ~ 100 ℃ after sequential addition of the organic solvent, main catalyst and co-catalyst solution was reacted for 5 to 60 minutes, cooled to -10 ~ 0 ℃, methanol was added to terminate the reaction, and finally isolated by distillation to obtain a linear α- olefin. 所得的线性α-烯烃选择性>96%,碳数分布在C6~C28之间,其中C6~C20大于80%。 The resulting linear α- olefin selectivity of> 96%, carbon number distribution between C6 ~ C28, C6 ~ C20 wherein more than 80%.

所述的钴系催化剂组合物的应用,其特征在于所述的有机溶剂为石油醚、甲苯、二甲苯,所述的主催化剂溶液的溶剂为1,2-二氯乙烷、二氯甲烷、三氯甲烷和邻二氯苯,所述的助催化剂与主催化剂的物质的量比(以Al/Co计)为2000∶1~200∶1,尤其以1500∶1~500∶1为佳。 The application of a cobalt-based catalyst composition, wherein said organic solvent is petroleum ether, toluene, xylene, solvent solution of said main catalyst is 1,2-dichloroethane, dichloromethane, chloroform and o-dichlorobenzene, and the molar ratio of the cocatalyst to the procatalyst (in Al / co basis) of 2000:1 200:1 ~, ~ 500:1 1500:1 especially preferred.

具体实施方式 Detailed ways

实施例1:200毫克2,6-二乙酰基吡啶和6毫升2-甲基-4-甲氧基苯胺加入到250毫升双口瓶,加入50毫升二氯甲烷,滴加0.2毫升甲酸,回流30小时。 Example 1: 200 mg of 2,6-diacetylpyridine and 6 ml of 2-methyl-4-methoxyaniline was added to 250 ml two-port flask, 50 ml of methylene chloride was added dropwise 0.2 ml of formic acid, at reflux 30 hours. -30℃冷冻12小时。 -30 ℃ freezer for 12 hours. 过滤并用冷冻甲醇洗涤3次。 Filtered and washed 3 times with chilled methanol. 所得产物为2,6-二[1-(2-甲基-4-甲氧基苯亚胺)乙基]吡啶。 The resulting product is 2,6-bis [1- (2-methyl-4-methoxy-imide) ethyl] pyridine. 产物真空干燥后,在氩气中保存。 After drying the product under vacuum, stored under argon.

实施例2: Example 2:

200毫克2,6-二乙酰基吡啶和3毫升2-甲基-4-叔丁氧基苯胺加入到250毫升双口瓶,加入50毫升二氯甲烷,滴加0.1毫升甲酸,回流30小时。 200 mg of 2,6-diacetylpyridine and 3 ml of 2-methyl-4-t-butoxy-aniline was added to 250 ml two-port flask, 50 ml of methylene chloride was added dropwise 0.1 ml of formic acid was refluxed for 30 hours. -30℃冷冻12小时。 -30 ℃ freezer for 12 hours. 过滤并用冷冻甲醇洗涤3次。 Filtered and washed 3 times with chilled methanol. 所得产物为2,6-二[1-(2-甲基-4-叔丁氧基苯亚胺)乙基]吡啶。 The resulting product is 2,6-bis [1- (2-methyl-4-t-butoxy-phenylimine) ethyl] pyridine. 产物真空干燥后,在氩气中保存。 After drying the product under vacuum, stored under argon.

实施例3:200毫克2,6-二乙酰基吡啶和8毫升2-甲基-4-异丙氧基苯胺加入到250毫升双口瓶,加入50毫升二氯甲烷,滴加0.1毫升甲酸,回流30小时。 Example 3: 200 mg of 2,6-diacetylpyridine and 8 ml of 2-methyl-4-isopropoxy-aniline was added to 250 ml two-port flask, 50 ml of methylene chloride was added dropwise 0.1 ml of formic acid, reflux for 30 hours. -30℃冷冻12小时。 -30 ℃ freezer for 12 hours. 过滤并用冷冻甲醇洗涤3次。 Filtered and washed 3 times with chilled methanol. 所得产物为2,6-二[1-(2-甲基-4-异丙氧基苯亚胺)乙基]吡啶。 The resulting product is 2,6-bis [1- (2-methyl-4-isopropoxy-phenyl imide) ethyl] pyridine. 产物真空干燥后,在氩气中保存。 After drying the product under vacuum, stored under argon.

实施例4:200毫克2,6-二乙酰基吡啶和10毫升2-甲基-4-苯氧基苯胺加入到250毫升双口瓶,加入50毫升二氯甲烷,滴加0.3毫升甲酸,回流48小时。 Example 4: 200 mg of 2,6-diacetylpyridine and 10 ml of 2-methyl-4-phenoxyaniline was added to 250 ml two-port flask, 50 ml of methylene chloride was added dropwise 0.3 ml of formic acid, at reflux 48 hours. -30℃冷冻12小时。 -30 ℃ freezer for 12 hours. 过滤并用冷冻甲醇洗涤3次。 Filtered and washed 3 times with chilled methanol. 所得产物为2,6-二[1-(2-甲基-4-苯氧基苯亚胺)乙基]吡啶。 The resulting product is 2,6-bis [1- (2-methyl-4-phenoxy benzene imide) ethyl] pyridine. 产物真空干燥后,在氩气中保存。 After drying the product under vacuum, stored under argon.

实施例5:200毫克2,6-二乙酰基吡啶和3毫升2-甲基-4-(2,6-二甲基苯基)苯胺加入到250毫升双口瓶,加入50毫升1,2-二氯乙烷,滴加0.1毫升甲酸,回流30小时。 Example 5: 200 mg of 2,6-diacetylpyridine and 3 ml of 2-methyl-4- (2,6-dimethylphenyl) aniline were added to 250 ml two-port flask, 50 ml of 1,2 - dichloroethane was added dropwise 0.1 ml of formic acid was refluxed for 30 hours. -30℃冷冻12小时。 -30 ℃ freezer for 12 hours. 过滤并用冷冻甲醇洗涤3次。 Filtered and washed 3 times with chilled methanol. 所得产物为2,6-二[1-(2-甲基-4-(2,6-二甲基苯基)苯亚胺)乙基]吡啶。 The resulting product is 2,6-bis [1- (2-methyl-4- (2,6-dimethylphenyl) imine phenyl) ethyl] pyridine. 产物真空干燥后,在氩气中保存。 After drying the product under vacuum, stored under argon.

实施例6:在100毫升双口反应瓶中抽真空—充氩气反复三次后,在氩气保护下分别加入120毫克实施例1~3的产物和80毫克FeCl2·4H2O,加入30毫升无水四氢呋喃,室温搅拌10小时,得到蓝色固体。 Example 6: In a 100 ml vacuum flask Dual Port reaction - product was repeatedly flushed with argon three times, under argon were added 120 mg of protection of Examples 1 to 3 and 80 mg of FeCl2 · 4H2O, 30 ml of anhydrous tetrahydrofuran, stirred at room temperature for 10 hours to give a blue solid. 过滤并用冷冻无水乙醚洗涤3次。 Filtered and washed with diethyl ether and washed three times with freeze-dry. 真空干燥,氩气下保存。 Dried in vacuo, stored under argon.

实施例7:在100毫升双口反应瓶中抽真空—充氩气反复三次后,在氩气保护下分别加入150毫克实施例4~5的产物和80毫克FeCl2·4H2O,加入30毫升无水四氢呋喃,室温搅拌8小时,得到蓝色固体。 Example 7: In a 100 ml vacuum flask Dual Port reaction - product was repeatedly flushed with argon three times, under argon were added 150 mg of protected Examples 4 to 5 and 80 mg of FeCl2 · 4H2O, 30 ml of anhydrous tetrahydrofuran, stirred at room temperature for 8 hours to give a blue solid. 过滤并用冷冻无水乙醚洗涤3次。 Filtered and washed with diethyl ether and washed three times with freeze-dry. 真空干燥,氩气下保存。 Dried in vacuo, stored under argon.

实施例8:在250毫升双口反应瓶中抽真空—乙烯反复三次后,充入乙烯至0.1MPa,加入100毫升的甲苯。 Example 8: evacuation port in a 250 ml reaction flask bis - ethylene after repeated three times, charged with ethylene to 0.1MPa, 100 ml of toluene. 注入5.0毫升按甲基铝氧烷:三异丁基铝:GaCl3物质的量比为1000∶10∶1的助催化剂甲苯混合溶液,该混合溶液按铝计为10%。 By injecting 5.0 ml of methyl alumoxane: triisobutylaluminum: GaCl3 substance ratio cocatalyst 1000:10:1 toluene mixed solution, the mixed solution by 10% in terms of aluminum. 注入2.5毫升实施例6的1×10-6mol/L催化剂1,2-二氯乙烷溶液。 Injecting 2.5 ml 1 × 10-6mol 6 / L of 1,2-dichloroethane in Example catalyst. 迅速增加乙烯压力至1.5MPa,90℃反应20分钟。 Rapid ethylene pressure was increased to 1.5MPa, reaction was 90 ℃ 20 minutes. 冷却至0℃,加入丙酮终止反应。 Was cooled to 0 ℃, acetone was added to terminate the reaction. 精馏分离产物。 Distillation of the product. 色谱分析,线性α-烯烃为96%,碳数分布在C6~C24之间,其中C6~C20为81%。 Chromatographic analysis, linear α- olefin is 96%, carbon number distribution between C6 ~ C24, C6 ~ C20 wherein 81%.

实施例9:在250毫升双口反应瓶中抽真空—乙烯反复三次后,充入乙烯至0.1MPa,加入100毫升的石油醚。 Example 9: a vacuum port in a 250 ml reaction flask bis - ethylene after repeated three times, charged with ethylene to 0.1MPa, 100 ml of petroleum ether. 注入3.0毫升按甲基铝氧烷:三异丁基铝:GaCl3物质的量比为100∶10∶1的助催化剂甲苯混合溶液,该混合溶液按铝计为10%。 By injecting 3.0 ml of methyl alumoxane: triisobutylaluminum: GaCl3 substance ratio cocatalyst 100:10:1 toluene mixed solution, the mixed solution by 10% in terms of aluminum. 注入2.5毫升实施例6的1×10-6mol/L催化剂1,2-二氯乙烷溶液。 Injecting 2.5 ml 1 × 10-6mol 6 / L of 1,2-dichloroethane in Example catalyst. 迅速增加乙烯压力至5.0MPa,50℃反应10分钟。 Rapid ethylene pressure was increased to 5.0MPa, reaction was 50 ℃ 10 minutes. 冷却至0℃,加入丙酮终止反应。 Was cooled to 0 ℃, acetone was added to terminate the reaction. 精馏分离产物。 Distillation of the product. 色谱分析,线性α-烯烃为96%,碳数分布在C6~C24之间,其中C6~C20为81%。 Chromatographic analysis, linear α- olefin is 96%, carbon number distribution between C6 ~ C24, C6 ~ C20 wherein 81%.

实施例10:在250毫升双口反应瓶中抽真空—乙烯反复三次后,充入乙烯至0.1MPa,加入100毫升的1,2-二氯乙烷。 Example 10: evacuated in a 250 ml reaction flask dual port - after ethylene repeated three times, charged with ethylene to 0.1MPa, 100 ml of 1,2-dichloroethane. 注入4.0毫升按甲基铝氧烷:三异丁基铝:GaCl3物质的量比为100∶10∶1的助催化剂甲苯混合溶液,该混合溶液按铝计为10%。 By injecting 4.0 ml of methyl alumoxane: triisobutylaluminum: GaCl3 substance ratio cocatalyst 100:10:1 toluene mixed solution, the mixed solution by 10% in terms of aluminum. 注入2.5毫升实施例6的1×10-6mol/L催化剂1,2-二氯乙烷溶液。 Injecting 2.5 ml 1 × 10-6mol 6 / L of 1,2-dichloroethane in Example catalyst. 迅速增加乙烯压力至5.0MPa,20℃反应20分钟。 Rapid ethylene pressure was increased to 5.0MPa, reaction was 20 ℃ 20 minutes. 冷却至0℃,加入丙酮终止反应。 Was cooled to 0 ℃, acetone was added to terminate the reaction. 精馏分离产物。 Distillation of the product. 色谱分析,线性α-烯烃为96%,碳数分布在C6~C24之间,其中C6~C20为84%。 Chromatographic analysis, linear α- olefin is 96%, carbon number distribution between C6 ~ C24, C6 ~ C20 wherein 84%.

Claims (9)

1.一种乙烯齐聚的钴系催化剂组合物,由主催化剂和助催化剂组成,其特征在于所述的主催化剂为结构式如下所示的钴系(II)亚胺基配位化合物: A cobalt-based ethylene oligomerization catalyst composition, procatalyst and a cocatalyst, wherein said main catalyst is represented by the formula cobalt (II) complex compound imino follows: 其中,R为C1~C4烷基、苯基、被C1~C4烷基一、二或三取代的苯基或被卤素一、二或三取代的苯基或被卤素和C1~C4烷基一、二或三取代的苯基;所述的助催化剂是由甲基铝氧烷、三异丁基铝和GaCl3所组成的混合物。 Wherein, R is C1 ~ C4 alkyl, phenyl, C1 ~ C4 alkyl mono-, di- or tri-substituted phenyl or phenyl substituted with halo, di- or tri-substituted by halogen and a C1 ~ C4 alkyl group , di- or tri-substituted phenyl; said cocatalyst is methylalumoxane, triisobutylaluminum and a mixture consisting of GaCl3.
2.根据权利要求1所述的钴系催化剂组合物,其特征是:主催化剂的亚胺基配位化合物由2,6-二乙酰基吡啶或2,5-二乙酰基吡咯与2-甲基-4-0R-苯胺反应获得,其中R如权利要求1所定义。 The cobalt-based catalyst composition according to claim 1, characterized in that: an alkylene group with a compound of the procatalyst or 2,6-diacetylpyridine and 2,5-diacetyl-2-pyrrole -4-0R- group obtained by reacting aniline in which R is as defined in claim 1 claims.
3.根据权利要求1所述的钴系催化剂组合物,其特征为:GaCl3与甲基铝氧烷和三异丁基铝的物质的量比为1∶100∶10~1∶10000∶100。 The cobalt-based catalyst composition of claim 1, wherein the claim: GaCl3 and the molar ratio of methylaluminoxane and triisobutylaluminum is 1:100:10 ~ 1:10000:100.
4.根据权利要求1所述的钴系催化剂组合物,其特征在于C1~C4烷基为甲基、乙基、丙基、异丙基、正丁基、异丁基或叔丁基。 The cobalt-based catalyst composition according to claim 1, wherein the C1 ~ C4 alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
5.根据权利要求1所述的钴系催化剂组合物,其特征在于被C1~C4烷基一、二或三取代的苯基为2-甲基苯基、4-甲基苯基、2,4-二甲基苯基、2,6-二甲基苯基、2,4,6-三甲基苯基,2-乙基苯基、4-乙基苯基、2,4-二乙基苯基、2,4,6-三乙基苯基,2-丙基苯基、4-丙基苯基、2,4-二丙基苯基、2,6-二丙基苯基、2,4,6-三丙基苯基,2-异丙基苯基、4-异丙基苯基、2,4-二异丙基苯基、2,6-二异丙基苯基、2,4,6-三异丙基苯基,2-丁基苯基、4-丁基苯基、2,4-二丁基苯基、2,6-二丁基苯基、2,4,6-三丁基苯基,2-异丁基苯基、4-异丁基苯基、2,4-二异丁基苯基、2,6-二异丁基苯基、2,4,6-三异丁基苯基,2-叔丁基苯基、4-叔丁基苯基、2,4-二叔丁基苯基、2,6-二叔丁基苯基、2,4,6-三叔丁基苯基。 The cobalt-based catalyst composition according to claim 1, wherein the C1 ~ C4 alkyl mono-, di- or tri-substituted phenyl is 2-methylphenyl, 4-methylphenyl, 2, 4-methylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2,4-diethyl phenyl, 2,4,6-ethylphenyl, 2-propylphenyl, 4-propylphenyl, 2,4-propylene, 2,6-propylphenyl, 2,4,6-propylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2,4-diisopropylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropyl-phenyl, 2-butylphenyl, 4-butylphenyl, 2,4-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4 , 6-trimethyl-butylphenyl, 2-isobutylphenyl, 4-isobutylphenyl, 2,4-di-isobutylphenyl, 2,6-di-isobutylphenyl, 2,4 , 6-trimethyl-isobutylphenyl, 2-tert-butylphenyl, 4-tert-butylphenyl, 2,4-di-t-butylphenyl, 2,6-di-tert-butylphenyl, 2, 4,6-tri-t-butylphenyl.
6.根据权利要求1所述的钴系催化剂组合物,其特征在于被卤素一、二或三取代的苯基为2-氯苯基、4-氯苯基、2,4-二氯苯基、2,4,6-三氯苯基,2-溴苯基、4-溴苯基、2,4-二溴苯基、2,4,6-三溴苯基。 6. A cobalt-based catalyst composition according to claim 1, characterized in that the halogen is mono-, di- or tri-substituted phenyl is 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl , 2,4,6-trichlorophenyl, 2-bromophenyl, 4-bromophenyl, 2,4-dibromophenyl, 2,4,6-tribromophenyl.
7.根据权利要求1所述的钴系催化剂组合物,其特征在于被卤素和C1~C4烷基一、二或三取代的苯基为2-溴-4-甲基苯基、2-溴-6-甲基苯基、2,6-二溴-4-甲基苯基、4-溴-2,6-二甲基苯基,2-氯-4-甲基苯基、2-氯-6-甲基苯基、2,6-二氯-4-甲基苯基、4-氯-2,6-二甲基苯基。 The cobalt-based catalyst composition according to claim 1, wherein one, two or three of halogen-substituted C1 ~ C4 alkyl and phenyl 2-bromo-4-methylphenyl, 2-bromo 6-methylphenyl, 2,6-dibromo-4-methylphenyl, 4-bromo-2,6-dimethylphenyl, 2-chloro-4-methylphenyl, 2-chloro 6-methylphenyl, 2,6-dichloro-4-methylphenyl, 4-chloro-2,6-dimethylphenyl.
8.权利要求1所述的钴系催化剂组合物在催化乙烯齐聚制备线性α-烯烃中的应用,其特征在于:在无水无氧条件下,乙烯压力0.1~10MPa、反应温度0~100℃时,顺序加入有机溶剂、助催化剂和主催化剂溶液,反应5~60分钟后,冷却至-10~0℃,加入甲醇终止反应,最后经精馏分离得到线性α-烯烃,由此所得的线性α-烯烃选择性>96%,碳数分布在C6~C28之间,其中C6~C20大于80%。 Cobalt-based catalyst composition according to claim 1 in the preparation of linear olefins α- application catalytic oligomerization of ethylene, wherein: under anhydrous oxygen-free conditions, the ethylene pressure 0.1 ~ 10MPa, reaction temperature 100 ~ 0 when ℃, the order of adding an organic solvent, main catalyst and cocatalyst solution, the reaction after 5 to 60 minutes, cooled to -10 ~ 0 ℃, methanol was added to terminate the reaction, and finally isolated by distillation to obtain a linear α- olefin thus obtained linear α- olefin selectivity> 96%, carbon number distribution between C6 ~ C28, C6 ~ C20 wherein more than 80%.
9.根据权利要求8所述的钴系催化剂组合物的应用,其特征在于所述的有机溶剂为石油醚、甲苯、二甲苯,所述的主催化剂溶液的溶剂为1,2-二氯乙烷、二氯甲烷、三氯甲烷或邻二氯苯,所述的助催化剂与主催化剂的物质的量比以Al/Co计为2000∶1~200∶1。 9. The use of claim 8 cobalt-based catalyst composition according to claim, wherein said organic solvent is petroleum ether, toluene, xylene, solvent solution of the procatalyst is 1,2-dichloroethane dioxane, dichloromethane, chloroform or o-dichlorobenzene, the substance of the cocatalyst to procatalyst ratio Al / co in terms 2000:1 ~ 200:1.
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