CN100389129C - 用于活化金属茂前催化剂的助催化剂和该助催化剂的生产方法 - Google Patents
用于活化金属茂前催化剂的助催化剂和该助催化剂的生产方法 Download PDFInfo
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- CN100389129C CN100389129C CNB031277535A CN03127753A CN100389129C CN 100389129 C CN100389129 C CN 100389129C CN B031277535 A CNB031277535 A CN B031277535A CN 03127753 A CN03127753 A CN 03127753A CN 100389129 C CN100389129 C CN 100389129C
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Abstract
通过使用特殊类型的金属茂催化剂的聚合方法得到有独特性能组合的聚烯烃弹性体，即高分子量(Mw)、高门尼粘度(125℃下的ML1+4)、低多分散指数(Mw/Mn)、低玻璃化转变温度(Tg)和低滞后现象(tanδ)。该聚烯烃弹性体适用于制造各种产品，包括橡胶制品如胶管、皮带和模塑制品，含有一或多种其它烃聚合物的聚合物共混物，和所述弹性体在其中作为粘度调节剂的润滑油。还公开了用于活化金属茂前催化剂的产生阳离子的助催化剂，优选在烯烃单体存在下活化。
Description
本申请是申请日为1997年4月1日、发明名称为“生产聚烯烃弹性体的聚合方法、用于活化金属茂前催化剂的产生阳离子的助催化剂、有独特性能组合的聚烯烃弹性体及由其制造的产品”的中国专利申请97193715.X的分案申请。
发明背景
1.发明领域
本发明涉及用于生产聚烯烃弹性体的液相聚合方法，例如，一种由乙烯，另一种α-烯烃如丙烯和可选地二烯烃衍生，本发明还涉及用于活化可用于该聚合方法中的金属茂前催化剂的产生阳离子的助催化剂，涉及有理想的高分子量(Mw)、高门尼粘度(125℃下的ML1+4)、低多分散指数(Mw/Mn)、低玻璃化转变温度(Tg)和低滞后现象(tanδ)的所得聚烯烃弹性体，及由其制造的各种产品，包括橡胶制品如胶管、皮带和模制品，含有一或多种其它烃聚合物的聚合物共混物，和润滑油，其中所述弹性体起粘度调节剂的作用。
2.现有技术
目前生产的最常用的聚烯烃弹性体是乙烯和丙烯的共聚物(EP)，及乙烯、丙烯和一种二烯烃的三元共聚物(EPDM)。常规的EP弹性体可用固化剂如有机过氧化物固化，而使用硫作为固化剂需加入二烯烃。EPDM弹性体通常用钒-有机铝催化剂即齐格勒-纳塔催化剂生产。
与更熟知的EP和EPDM聚合物一道，代替丙烯加入其它α-烯烃如1-丁烯、1-戊烯、1-己烯、苯乙烯及其混合物的共聚物和三元共聚物也是公知的。EPDMs是更大类乙烯-α-烯烃二烯弹性体(EODEs)的代表。在EODEs中，EPDMs因为有很多性能使它们适用于需要良好的耐气候性、耐酸性和高低温性能的应用而尤为突出。EPDMs的引人注意的应用包括它们在诸如胶管、垫片、电动传送带、传送带、保险杠、汽车挤压模塑制品、挡雨条、用于塑料和橡胶如聚丙烯、聚苯乙烯和丁基橡胶的共混组分、织物涂料、润滑油的粘度调节剂、轮胎侧壁等产品中的应用以及在屋顶材料和其它膜应用、鞋底、鞋跟和许多其它橡胶制品中的应用。EPDMs的另一值得注意的应用是由于它们有极好的介电性而在电线电缆的绝缘材料中的应用。
有合理的快固化速率和高固化态的EPDM是理想的，要求有相对高的二烯烃含量，例如3％或更高。EPDM弹性体的固化速率和固化制品的最终性能与所加二烯烃的类型相关。例如，在可比的二烯烃重量百分率的基础上，用5-亚乙基(ethylidiene)-2-降冰片烯(ENB)作为二烯烃生产的EPDM将有比含二环戊二烯(DCPD)或1，4-己二烯(HD)的EPDM更快的用硫固化的固化速率。
关于固化EPDM的性能，已知用己二烯作为第三单体生产的EPDMs表现出良好的耐热性。对于大多数工业弹性体应用，EPDM的重均分子量(Mw)应为至少约300 000，或者用门尼粘度表示时在125℃下的ML1+4应为至少约20。在许多应用中，还要求EPDM的分子量分布(MWD)特征在于重均分子量与数均分子量之比(Mw/Mn)即多分散指数不大于约7，优选不大于约5。
EPDM弹性体的性能如其拉伸强度、加工性和粘着性可能与其结晶度有关。由于在多数工业应用中使用分子量高于塑料的弹性体，所以结晶度太高可能使EPDM难以在常温下加工。尽管希望有良好的物理性能，尤其在胶管、管、电线和电缆等应用中，过高的结晶度可能使EPDM表现出很高的硬度和刚性，而形成表面粘着性差的“塑性”而非“橡胶”表面。
一般地，工业上应用的塑料，为乙烯、丙烯、和较高α-烯烃的均聚物和共聚物，不需有象工业应用的乙烯-α-烯烃弹性体如EPDM那样高的分子量。就每种所用催化剂而言，生产有弹性体范围内Mw组成的共聚物时，提供高Mw塑性共聚物的催化剂可生产不适用于弹性体应用的低Mw聚合物。类似地，可出现不希望的MWD变化或组成分布可能改变。因此，用于生产塑料的催化剂性能没有用于生产弹性体的催化剂性能的征兆。
在大多数现行的EPDM生产中，传统用于生产高分子量EPDM弹性体的催化剂是可溶性钒催化剂如VCl4、VOCl3、VO(Ac)3、或VO(OR)3(其中R为烷基)与有机铝化合物。这些钒催化剂的活性相对较低，例如产生5-20kg聚合物/g钒。
在目前的工业级EPDM中，结晶度随聚合物的乙烯含量和其生产中所用催化剂体系而改变。对于给定的聚合物组成，催化剂体系控制能够结晶的长乙烯序列中存在的乙烯单元的分数。在任何给定的催化剂和反应器结构下，乙烯含量较高的聚合物将有较长的乙烯序列而更易结晶。
在目前基于钒催化剂生产EPDM中，产品EPDM聚合物在乙烯含量低于约55wt％的情况下是完全无定形的(非晶形的)。相反，在乙烯含量为约55wt％或更高的情况下，EPDM将有明显的结晶。结晶度与EPDM的二烯烃含量的相关度低于与乙烯百分率的相关度。
为使催化剂体系适用于EPDM弹性体的工业生产，希望聚合物的结晶度大致与目前可用于大多数应用的工业级EPDM的结晶度相当。
金属茂催化剂典型地由夹在环结构之间形成空间位阻位的过渡金属原子组成。用金属茂催化剂得到的塑料趋于有增加的抗冲击强度和韧性、良好的熔融特性和改善的膜透明度。
实践中，金属茂催化剂可有效地代替聚合物生产中传统催化剂的程度取决于催化剂体系的成本和效率。金属茂催化剂成本明显高于传统的齐格勒-纳塔催化剂，但金属茂体系的生产率也更高。在某些情况下，金属茂催化剂相对于齐格勒-纳塔催化剂增加的生产率在每磅催化剂多生产一至两个数量级的聚合物的范围内。
由于近来将铝氧烷活化的金属茂催化剂引入聚乙烯、聚丙烯、及乙烯和α-烯烃的共聚物如线型低密度聚乙烯(LLDPE)的生产中，已做了一些努力将这些催化剂用于EPDM弹性体的生产中。对于此应用，希望该催化剂在合理的聚合时间内生产高产量的EPDM，从而加入足量的二烯烃单体，提供任意分布的单体，能在宽范围内良好地控制Mw，产生相对窄的MWD。
Kaminsky et al.，聚合物科学杂志(J.Poly.Sc.)，Vol.23，2151-2164(1985)公开了用金属茂-甲基铝氧烷(MAO)催化剂体系生产低分子量EPDM弹性体，即Mws不大于约150 000。这种催化剂需要很长的反应时间且产率很低，因而对于工业EPDM的生产不现实。类似地，JP62-121 771描述了一种以低产率生产高乙烯含量的乙烯-1-丁烯-二烯烃弹性体的金属茂催化的聚合方法。
以使用由铝氧烷如MAO活化的金属茂催化剂为特征的其它生产EPDMs的聚合方法描述在例如US4 871 705、5 001 205、5 229 478和5 442 020，EP347 129和WO 95/16716中。如后面更充分地论述的，在高分子量弹性体的生产中缺少更广泛工业应用的金属茂催化剂至少部分是由于需要使用非常大量的铝氧烷助催化剂以使金属茂活化至可接受的水平。
EP-A-593 083描述了一种用于生产EPDM的气相聚合法，采用桥连的金属茂催化剂(1)：
二氯·二苯亚甲基(环戊二烯基)(芴基)合锆
然而气相聚合有一些技术难题，其中包括反应堵塞，在此类生产EPDM弹性体方法被工业普遍接受之前需克服这些技术难题。
EP-A-612 769和EP 653 445均公开了在生产线型低[分子量]丙烯-二烯烃弹性体(LLPDE)的液相聚合法中使用金属茂催化剂(1)，与本发明目的的高分子量弹性体相反。
US5 401 817描述了一种聚合方法，采用桥连的金属茂催化剂(2)：
二氯·二苯基甲硅烷基(环戊二烯基)(芴基)合锆
但在该专利中未提及生产弹性体。
Green et al.，化学会志道尔顿会刊(J.Chem.Soc.DaltonTrans.)，657-665(1994)描述了丙烯和苯乙烯的聚合，采用桥连的金属茂催化剂(3)：
氯·二苯亚甲基(环戊二烯基)(茚基)合锆
该公开中未提及生产弹性体。
Kaminsky et al.，应用化学(国际英文版)(Angew.Chem.Int.Ed. Engl.)，34，2273-2275(1995)描述了桥连的金属茂催化剂(4)，与MAO一起，用于乙烯与庞大的环烯烃的共聚：
二氯·二苯基甲硅烷基(环戊二烯基)(茚基)合锆
本发明的另一方面在于发现不是所有的桥连金属茂催化剂均提供高分子量的弹性体。例如，已发现桥连的金属茂催化剂(5)
二氯·二甲基亚甲基(环戊二烯基)(芴基)合锆
其仅在连接两个环戊二烯基-衍生的配体的桥基的性能方面与上述金属茂(1)-(4)不同，它提供低分子量(＜50 000)的乙烯-丙烯共聚物。与此结果相反，如本文所发现的，活化的金属茂催化剂(1)提供高分子量(＞300 000)的弹性体。
分别有双(茚基)和双(芴基)结构的桥连的金属茂催化剂(6)和(7)能提供高分子量的非晶形乙烯-丙烯共聚物：
二氯·外消旋-二甲基甲硅烷基双(2-甲基茚基)合锆
二氯·亚乙基桥连的双(芴基)合锆
金属茂(6)和(7)描述在US5 145 819(茚基)和5 436 305(芴基)中用于生产均聚物。这两篇专利中未提及采用所公开的金属茂生产EPDM型弹性体。
如前面所述，已发现金属茂催化剂获得广泛工业应用的障碍之一在于使用铝氧烷作为助催化剂。铝氧烷很贵，要活化相关的金属茂催化剂需要大量铝氧烷。
发明概述
本发明的目的之一是提供一种用于生产聚烯烃弹性体的液相聚合方法，即在溶液或淤浆条件下间歇或连续进行的聚合方法，采用活化的桥连金属茂作为催化剂组合物，其中所述桥连基有至少两个庞大基团。
本发明的另一目的是提供这样一种烯烃聚合方法，以提供高分子量的EP和EODEs如EPDMs。
本发明的再一目的是提供一种催化活性的组合物，包括由特殊类型的产生阳离子的助催化剂活化的金属茂前催化剂。
本发明的其它目的包括提供有高分子量、高门尼粘度、低多分散指数、低玻璃化转变温度和低滞后现象组合的聚烯烃弹性体，及由其制造的各种产品。
与本发明的这些和其它目的一致，提供了一种乙烯、至少一种其它α-烯烃和可选的至少一种二烯烃单体液相聚合产生弹性体的方法，该方法包括使所述单体在液相聚合条件下与催化有效量的催化剂组合物接触，所述催化剂组合物包括通过混合(a)金属茂前催化剂(优选含有有至少两个庞大基团的桥连基的)和(b)助催化剂(优选如后面所述产生阳离子的助催化剂)所得的产物。
本发明方法所得到的聚烯烃弹性体本身是新的，有组合的比加入等量相同烯烃的已知聚烯烃弹性体更高的分子量(Mw)、更高的门尼粘度(125℃下的ML1+4)、更低的多分散指数(Mw/Mn)、更低的玻璃化转变温度(Tg)和更低的滞后现象(tanδ)。这些弹性体使由其制造的产品具有比由已知弹性体制造的相同产品更优越的性能。
本文所用术语“金属茂”和“金属茂前催化剂”应理解为意指有过渡金属M、至少一个由非环戊二烯基衍生的配体X和零或一个含杂原子的配体Y的化合物，所述配体与M配位，数量与其化合价对应。这种化合物、适用于其活化以提供可用于烯烃聚合提供聚烯烃均聚物和共聚物的金属茂催化剂的助催化剂、和/或采用一或多种该金属茂催化剂的聚合方法描述在以下文献中：US 4 752 597；4 892 851；4 931417；4 931 517；4 933 403；5 001 205；5 017 714；5 026 798；5 034 549；5 036 034；5 055 438；5 064 802；5 086 134；5 087677；5 126 301；5 126 303；5 132 262；5 132 380；5 132 380；5 145 819；5 153 157；5 155 080；5 225 501；5 227 478；5 229478；5 241 025；5 243 002；5 278 119；5 278 265；5 281 679；5 296 434；5 304 614；5 308 817；5 324 800；5 328 969；5 329031；5 330 948；5 331 057；5 349 032；5 372 980；5 374 753；5 385 877；5 391 629；5 391 789；5 399 636；5 401 817；5 406013；5 416 177；5 416 178；5 416 228；5 427 991；5 439 994；5 441 920；5 442 020；5 449 651；5 453 410；5 455 365；5 455366；5 459 117；5 466 649；5 470 811；5 470 927；5 477 895；5 491 205；和5 491 207，这些文献的内容均引入本文供参考。
附图简述
图1为在本发明范围之内(实施例21)和之外(对比例30)的由产生阳离子的助催化剂活化的金属茂前催化剂的稳定性的图示比较，催化剂的稳定性以规定时间之外所消耗单体的量表示。
优选实施方案的描述
本文的聚合方法采用用适合的助催化剂活化金属茂前催化剂得到的催化剂组合物。
金属茂前催化剂优选为以下通式之一或之二的一种金属茂化合物或其混合物：
(Cp1R1 m)R3 n(Cp2R2 p)MXq (I)
(Cp1R1 m)R3 nYrMXs (II)
其中配体(Cp1R1 m)的Cp1和配体(Cp2R2 p)的Cp2为相同或不同的环戊二烯基环，R1和R2独立地为卤素或最多约20个碳原子的烃基、卤代烃基(halocarbyl)、烃基-取代的有机准金属或卤代烃基-取代的有机准金属基团，m为0至5，p为0至5和与此相连的环戊二烯基环的相邻碳原子上的两个R1和/或R2取代基可连接在一起形成含4至约20个碳原子的环，R3为桥连基团，n为0或1，Y为含杂原子的配体(其中所述杂原子与M配位)，M为有3至6价的过渡金属，每个X为非环戊二烯基配体且独立地为卤素或最多约20个碳原子的烃基、氧烃基、卤代烃基、烃基-取代的有机准金属、氧烃基-取代的有机准金属或卤代烃基-取代的有机准金属基团，q等于M的化合价减2，r有n的值，和s当r为0时等于M的化合价减1而当r为1时等于M的化合价减2。
这些和其它适用的金属茂前催化剂的制备方法为本领域所公知，不构成本发明的一部分。
金属茂前催化剂(I)可用铝氧烷活化，或优选用本文后面所述的产生阳离子的助催化剂活化。如果金属茂前催化剂完全为式(II)之一，则用上述产生阳离子的助催化剂活化。但当金属茂前催化剂为式(I)之一和助催化剂完全是铝氧烷时，配体(Cp1R1 m)必须与配体(Cp2R2 p)不同，桥连基团R3必须含有至少两个庞大的基团，且n的值必须为1。这些桥连金属茂中，优选桥连基团R3有以下结构：
其中庞大基团R4和R5独立地为或包含含有最多约20、优选6至约12个碳原子和0至3个杂原子如氧、硫、叔氮、硼或磷的环烃基，具体地为环烷基、杂环烷基、环烯基、杂环烯基、芳基、杂芳基、烷芳基、烷基杂芳基、芳烷基、杂芳烷基等，M为钛、锆或铪，q为2和每个X为卤素。
此优选的桥连金属茂中，还更优选其中配体(Cp1R1 m)为未取代的环戊二烯基、配体(Cp2R2 p)为茚基或芴基、M为锆、R4和R5各为苯基、和X配体均为氯的那些。这些更优选的金属茂对应于上述已知金属茂化合物(1)-(4)。
可用于本发明聚合方法中的其它更优选的桥连金属茂(I)包括：
二氯·二苯亚甲基(茚基)(芴基)合锆，
二氯·二苯亚甲基(环戊二烯基)(4，5，6，7-四氢茚基)合锆，
二氯·二苯亚甲基(环戊二烯基)(2-甲基茚基)合锆，
二氯·二苯亚甲基(2，4-二甲基环戊二烯基)(3’，5’-二甲基环戊二烯基)合锆，
二氯·二苯亚甲基(2-甲基-4-叔丁基环戊二烯基)(3’-叔丁基-5’-甲基环戊二烯基)合锆，
二氯·二-二甲苯基亚甲基(2，3，5-三甲基环戊二烯基)(2’，4’，5’-三甲基环戊二烯基)合锆，
二氯·二-二甲苯基亚甲基(2，4-二甲基环戊二烯基)(3’，5’-二甲基环戊二烯基)合锆，
二氯·二-二甲苯基亚甲基(2-甲基-4-叔丁基环戊二烯基)(3’-叔丁基-5-甲基环戊二烯基)合锆，
二氯·二-二甲苯基亚甲基(环戊二烯基)(芴基)合锆，
二氯·二邻甲苯基亚甲基(环戊二烯基)(3，4-二甲基环戊二烯基)合锆，
二氯·二邻甲苯基亚甲基(环戊二烯基)(3，4-二甲基环戊二烯基)合锆，
二氯·二邻甲苯基亚甲基(环戊二烯基)(3，4-二甲基环戊二烯基)合锆，
二氯·二邻甲苯基亚甲基(环戊二烯基)(茚基)合锆，
二氯·二苄基亚甲基(环戊二烯基)(四甲基环戊二烯基)合锆，
二氯·二苄基亚甲基(环戊二烯基)(茚基)合锆，
二氯·二苄基亚甲基(环戊二烯基)(芴基)合锆，
二氯·二环己基亚甲基(环戊二烯基)(茚基)合锆，
二氯·二环己基(环戊二烯基)(芴基)合锆，
二氯·二环己基亚甲基(2-甲基环戊二烯基)(芴基)合锆，
二氯·二苯基甲硅烷基(2，4-二甲基环戊二烯基)(3’， 5’-二甲基环戊二烯基)合锆，
二氯·二苯基甲硅烷基(2，4-二甲基环戊二烯基)(3’， 5’-二甲基环戊二烯基)合锆，
二氯二苯基甲硅烷基(2，3，5-三甲基环戊二烯基)(2，4，5-三甲基环戊二烯基)合锆，
二氯·四苯基二甲硅烷基(环戊二烯基)(茚基)合锆，
二氯·四苯基二甲硅烷基(3-甲环戊二烯基)(茚基)合锆，
二氯·四苯基二甲硅烷基(环戊二烯基)(芴基)合锆，
二氯·二邻甲苯基甲硅烷基(环戊二烯基)(三甲基环戊二烯基)合锆，
二氯·二邻甲苯基甲硅烷基(环戊二烯基)(四甲基环戊二烯基)合锆，
二氯·二邻甲苯基甲硅烷基(环戊二烯基)(3，4-二乙基环戊二烯基)合锆，
二氯·二邻甲苯基甲硅烷基(环戊二烯基)(三乙基环戊二烯基)合锆，
二氯·二苄基甲硅烷基(环戊二烯基)(芴基)合锆，
二氯·二苄基甲硅烷基(环戊二烯基)(2，7-二叔丁基芴基)合锆，和
二氯·二环己基甲硅烷基(环戊二烯基)(芴基)合锆。
在优选的式(II)金属茂前催化剂中，n和r均为1，M的化合价为4，X为卤素和s为2。可被本发明产生阳离子的助催化剂活化的这种优选金属茂前催化剂(II)的例子如下：
二氯·二甲基甲硅烷基(四甲基环戊二烯基)(环己酰氨基)合锆，
二氯·二甲基甲硅烷基(3，4-二甲基环戊二烯基)(环己酰氨基)合铪，
二氯·二甲基甲硅烷基(四甲基环戊二烯基)(丁酰氨基)合钛，
二氯·二甲基甲硅烷基(3，4-二叔丁基环戊二烯基)(环十二烷酰氨基)合钛，
二氯·二甲基甲硅烷基(2，5-二甲基环戊二烯基)(环十二烷酰氨基)合钛，
二氯·二正丙基甲硅烷基(2，5-二甲基环戊二烯基)(对正丁基苯酰氨基)合钛，
二卤·二并丙基甲硅烷基(2-茚基)(环己酰氨基)合锆，
二卤·二苯基甲硅烷基(四正丙基环戊二烯基)(异丙酰氨基)合锆，和
二卤·二甲基亚甲基(2-甲基-5-叔丁基环戊二烯基)(二甲酰氨基)合锆。
如前所述，与式(I)的优选桥连金属茂前催化剂一起使用的助催化剂或活化剂可以是任何已知的活化金属茂前催化剂的铝氧烷。铝氧烷助催化剂包括烷基铝氧烷如MAO的更详细描述参见例如US5 227478。一般地，桥连金属茂前催化剂在反应器中的存在量以其过渡金属含量表示可为约0.0001至约0.02、优选约0.0002至约0.015、更优选约0.0002至约0.01mmol/l。与这些过渡金属量相对应，铝氧烷助催化剂的用量可为约0.01至约100、优选约0.02至约75、更优选约0.025至约50mmol/l。当然，应知道桥连金属茂前催化剂和铝氧烷助催化剂的最佳含量在某种程度上取决于所选的具体前催化剂和助催化剂以及其它聚合工艺变量。
使用铝氧烷助催化剂时，它包括三烷基铝如三甲基铝、三乙基铝、三正丙基铝、三异丙基铝、三正丁基铝和三异丁基铝等可能是有利的，以降低适当地活化金属茂前催化剂所需铝氧烷的量。一般地，可选择使用的三烷基铝与金属茂前催化剂的摩尔比为约1至约1000，优选约2至约500。
但优选用下述组成的产生阳离子的助催化剂活化金属茂前催化剂(I)和(II)。该优选的助催化剂可用于部分或全部取代铝氧烷，不仅用于上述优选的桥连金属茂，而且用于本发明涉及的桥连或不桥连的任何金属茂前催化剂。更具体地，本文中产生阳离子的助催化剂包括：作为第一组分，能够独立地用氢原子或最多约20个碳原子的烃基(carbohydryl)或最多约20个碳原子的氧烃基(oxycarbohydryl)交换所述金属茂前催化剂中的至少一个X配体最多至其总数的含金属和/或准金属的化合物；作为第二组分，具有至少一个含有至少一个吸电子取代基的芳基的含中性金属和/或准金属的化合物；和作为第三组分，具有至少一个含有至少一个吸电子取代基的芳基的含金属和/或准金属阴离子的化合物。
金属茂前催化剂的活化可通过使金属茂与产生阳离子的助催化剂的上述组分同时或者以任何次序以任何时间间隔混合而实现。由于下面所述原因，优选就地活化该前催化剂，即在单体存在下的聚合反应器内。但以其它方式活化该前催化剂也在本发明的范围内，例如，使金属茂前催化剂与助催化剂的第一组分反应，然后使反应产物同时或相继在烯烃单体内或在不存在烯烃单体的情况下与助催化剂的第二和第三组分混合。一般地，助催化剂的第一组分与金属茂前催化剂之摩尔比可为1至约500，优选约2至约500，助催化剂的第二和第三组分与金属茂前催化剂之摩尔比可独立地为约0.5至约10，优选约0.8至约5。
用于提供本文产生阳离子的助催化剂的含金属或准金属的第一组分可利于为以下通式的铝化合物：AlR4R5R6，其中R4、R5、和R6独立地为最多约20个碳原子的烃基(如烷基)或氧烃基(如烷氧基)或氢，条件是R4、R5、和R6中不多于两个可以为氢。适合的铝化合物包括三甲基铝、三乙基铝、三正丙基铝、三异丙基铝、三正丁基铝、三正丙基铝、三异丁基铝、三正己基铝、三正辛基铝、氢化二甲基铝、氢化二乙基铝、氢化二异丙基铝、氢化二正丙基铝、氢化二异丁基铝、氢化二正丁基铝、乙氧基化二甲基铝、乙氧基化二正丙基铝、乙氧基化二异丁基铝、乙氧基化二正丁基铝等。上述铝化合物中，优选三烷基铝，其中更优选三乙基铝和三异丁基铝。可用作助催化剂的第一组分的其它代表性化合物是碱金属有机金属化合物、碱土金属有机金属化合物和有机金属卤化合物(例如格利雅试剂)，金属和有机准金属如硼、锌、镓、锗、砷、碲、汞、铅等的烃基配合物。
适用于提供优选助催化剂的第二组分包括硼烷如三(五氟苯基)硼烷、三(甲氧基苯基)硼烷、三(三氟甲基苯基)硼烷、三(3， 5-二[三氟甲基]苯基)硼烷、三(四氟二甲苯基)硼烷、三(四氟邻甲苯基)硼烷等。上述硼烷中，优选三(五氟苯基)硼烷和三(3，5-二[三氟甲基]苯基)硼烷。其它适用的第二组分包括上述化合物的铝同系物。
可用于优选助催化剂的具体第三组分包括硼酸盐如四(五氟苯基)硼酸锂、四(三氟甲基苯基)硼酸锂、四(3，5-二[三氟甲基]苯基)硼酸锂、四(五氟苯基)硼酸钠、四(五氟苯基)硼酸钾、四(五氟苯基)硼酸镁、四(五氟苯基)硼酸钛、四(五氟苯基)硼酸锡等。上述硼酸盐中，优选碱金属硼酸盐如四(五氟苯基)硼酸锂和四(3，5-二[三氟甲基]苯基)硼酸锂。其它适用的第三组分包括上述化合物的铝酸盐同系物。
可预先制备活化的金属茂催化剂组合物，然后加入聚合反应器中。但使用上述优选的产生阳离子的助催化剂时，非常优选用助催化剂组分就地活化金属茂前催化剂，即在单体存在下活化。这样就地活化有很多优点。
其中每个X配体均为卤素的金属茂前催化剂是很稳定的化合物，没有特殊的处理或储存需要。但其中一或多个X配体为氢原子或烃基的金属茂暴露于氧气、潮气、光和/或热中时很容易降解。预先制备时，必须小心地以排除所有这些条件的方式储存这些金属茂。尤其是氢化金属茂，极不稳定。为此，优选在存在单体的聚合反应器内用优选的助催化剂活化金属茂前催化剂。以此方式活化该前催化剂避免或极大地减小了形成催化钝性的降解产物的可能性。
就地活化金属茂前催化剂还有其它显著的优点。即，就地活化为调节助催化剂中铝组分的量提供了灵活性，以校正聚合反应器内的工艺条件，例如通过极性杂质的反应性清除。使用预形成的金属茂氢化物、烃基化物或氧烃基化物需要单独加入这种清除剂，因而聚合方法复杂。此外，本文中已观察到在烯烃单体存在下活化导致初始聚合活性明显高于预先活化后加入聚合反应器的相同催化剂。
适用于制备本文中弹性体的α-烯烃含有3至约20个碳原子，包括丙烯、1-丁烯、3-甲基丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-辛烯、1-癸烯、1-十二碳烯、和乙烯基芳族单体如苯乙烯、α-甲基苯乙烯等，优选的α-烯烃是丙烯。
可选的二烯烃单体可以是共轭或非共轭的。共轭的单体包括丁二烯、异戊二烯、2，3-二甲基丁二烯和环戊二烯。
适合的非共轭二烯烃的例子包括直链无环二烯烃如1，4-己二烯、1，5-己二烯、1，6-庚二烯、和1，7-辛二烯；支链无环二烯烃如4-甲基-1，5-己二烯、5-甲基-1，4-己二烯、3，7-二甲基-1，6-辛二烯、3，7-二甲基-1，7-辛二烯、及二氢月桂烯和二氢罗勒烯的混合异构体；未取代和取代的环状二烯烃如1，4-环己二烯、1，5-环辛二烯和1，5-环十二碳二烯；和多环二烯烃如四氢茚、甲基四氢茚、二环戊二烯；二环-(2，2，1)-庚-2，6-二烯；链烯基、亚烷基、环烯基和亚环烷基降冰片烯如5-亚甲基-2-降冰片烯、5-亚乙基-2-降冰片烯、5-丙烯基-2-降冰片烯、5-亚异丙基-2-降冰片烯、5-丁烯基-2-降冰片烯、5-(4-环戊烯基)-2-降冰片烯、5-亚环己基-2-降冰片烯、5-乙烯基-2-降冰片烯和降冰片二烯。典型地用于制备EODEs的二烯烃中，优选1，4-己二烯、5-亚乙基-2-降冰片烯、5-亚乙烯基-2-降冰片烯、5-亚甲基-2-降冰片烯和二环戊二烯，其中更优选5-亚乙基-2-降冰片烯、1，4-己二烯和二环戊二烯。
使用导致产品弹性体中支化即使有也很少的二烯烃如1，4-己二烯、亚乙基-2-降冰片烯、二环戊二烯、1-甲基环戊二烯和茚等时，可有利于产品弹性体的性能以在单体混合物内包括提供分支的二烯烃。支化二烯烃(如它们可这样称呼)包括支化或未支化的无环二烯烃如1，5-己二烯、1，7-辛二烯或4-甲基-1，5-己二烯；取代或未取代的环状二烯烃如环戊二烯、3-甲基-1，4-环戊二烯、乙烯基环己烯或降冰片二烯；链烯基取代的降冰片烯如5-亚甲基-2-降冰片烯、5-乙烯基-2-降冰片烯、5-丙烯基-2-降冰片烯或5-丁烯基-2-降冰片烯；共轭的无环二烯烃如丁二烯、异戊二烯或2，3-二甲基丁二烯；和二链烯基芳族二烯烃如二乙烯基苯。
优选的弹性乙烯-α-烯烃共聚物和EODEs可含有最多约90、优选约30至约85、更优选约35至约80wt％的乙烯，其余为α-烯烃和可选的二烯烃单体。二烯烃单体(使用时)可以约0.1至约30、优选约1至约25、更优选约1至约20wt％的水平加入EODE中。
使用本发明催化剂的上述单体的聚合在液相中连续或间歇地进行，即以溶液或淤浆法。这些方法一般在这样的条件下进行：温度在约-20℃至约300℃的范围内，优选约0℃至约200℃，压力为约5至约2000psig。可使用的稀释溶剂包括直链和支链烃如丁烷、戊烷、己烷、庚烷、辛烷等，环族和脂环族烃如环戊烷、环己烷、环庚烷、甲基环戊烷、甲基环己烷、甲基环庚烷等，和烷基取代的芳香化合物如甲苯、二甲苯等。
典型的间歇溶液聚合法可通过先将烃溶剂如环己烷加入搅拌的罐式反应器中进行。然后将由乙烯、α-烯烃如丙烯、和二烯烃(如果使用)组成的单体进料喷入液相中。然后将助催化剂的烃溶液接着是金属茂前催化剂的烃溶液按需要量加入反应器的液相中。聚合速率由催化剂的浓度控制。反应器温度利用冷却盘管等控制，用恒定的气态单体流保持反应器的初始总压。通过保持气流通过反应器的速率比聚合速率快，反应器内的条件将接近稳态条件。弹性体产品的乙烯含量由所用金属茂催化剂和反应器中乙烯与δ-烯烃的比率决定，反应器中乙烯与δ-烯烃的比率通过操纵这些单体向反应器中的相对进料速率控制。聚合后，催化剂失活，然后弹性体凝结，弹性体可通过任何适合的方法回收，再按需要处理。
在淤浆聚合法中，在已加入乙烯、α-烯烃、任何可选的二烯烃和催化剂组合物的组分的烃稀释剂中形成固体颗粒聚合物的悬浮液。淤浆聚合象溶液聚合一样进行。
可由本文聚合方法获得的优选聚烯烃弹性体具有独特的高分子量(Mw)、高门尼粘度(ML1+4)、低多分散指数(Mw/Mn)、低玻璃化转变温度(Tg)和低滞后现象(tanδ)的性能组合，使之不同于已知的聚烯烃弹性体。本发明新的聚烯烃弹性体在固化前Mw为约200000至约2 000 000，优选约275 000至约1 750 000，更优选约300 000至约1 500 000；125℃下的ML1+4为约10至约200，优选约15至约175，更优选约20至约150；Mw/Mn为约1.25至约10，优选约1.5至约8.5，更优选约2.0至约7.5；Tg(℃)低于约-25，优选低于约-30，更优选低于-35；和tanδ为约0.3至约7，优选约0.35至约6，更优选约0.4至约5。
这些优越性能可在各种产品中利用。因此，可制备聚合物共混物，含有本发明的弹性体和一或多种已知弹性体如EPDMs与之相容的其它烃聚合物，例如聚(α-烯烃)均聚物和共聚物、聚苯乙烯、乙烯/环烯烃共聚物、丁基橡胶、聚异戊二烯、聚丁二烯等。本文所述弹性体可掺入任何种橡胶制品中，如胶管、管子、动力传送带包括V-形皮带、传送带、定时皮带和工业平板皮带、气垫、屋顶膜材料、挡雨条、套管、振动支座、桥梁轴承垫、鞋底、鞋跟、电线或电缆的外套等。本发明弹性体还适用作润滑油的粘度调节剂。
为便于聚合物共混物的制造，在与其它烃聚合物混合之前可以充油聚合物形式提供本文的弹性体。该弹性体可按公知方法充油，从聚合反应器回收聚合物后，向其中加入油。所述油可选自环烷油或石蜡油，其用量典型地为每100重量份弹性体约5至约150重量份油。或者，可将部分或全部油在共混操作期间加入弹性体和其它烃聚合物中。
本发明弹性体可以公知方式用任何常用的配料成分配制，例如含有一或多种硫化剂、加速剂、活化剂、缓聚剂等的硫化或固化包装。其它常用的配方成分包括防臭氧剂、抗氧化剂、塑化油和软化剂、填料、增强颜料和炭黑。
实施例
以下实施例包括说明本发明的(实施例1-27)和说明已知聚合方法、催化剂和弹性体的(对比例1-48)。这些实施例中所用前催化剂、MAO助催化剂、产生阳离子的助催化剂组分、溶剂和单体如下：
1.二氯·双(环戊二烯基)合锆[Cp2ZrCl2]
2.二氯·二苯基亚甲基(环戊二烯基)(芴基)合锆[Ph2C(Cp-9-Flu)ZrCl2 ]
3.二氯·二苯基甲硅烷基(环戊二烯基) (芴基)合锆[Ph2Si(Cp-9-Flu)ZrCl2 ]
4.二氯·二苯基亚甲基(环戊二烯基)(茚基)合锆[Ph2C(Cp-9’-Ind)ZrCl2]
5.二氯·二苯基甲硅烷基(环戊二烯基)(茚基)合锆[Ph2Si(Cp-9’-Ind)ZrCl2]
6.二氯·二甲基亚甲基(环戊二烯基)(芴基)合锆[Me2C(Cp-9-Flu)ZrCl2]
7.二氯·外消旋-二甲基甲硅烷基双(2-甲基茚基)合锆[rac-Me2Si(2-Me-Ind)2ZrCl2]
8.二氯·二甲基甲硅烷基双(环戊二烯基)合锆[Me2Si(Cp)2ZrCl2]
9.二氯·二甲基甲硅烷基双(芴基)合锆[Me2Si(Flu)2ZrCl2]
10.二氯·外消旋-亚乙基双(茚基)合锆[rac-Et(Ind)2ZrCl2]
11.二氯·外消旋-二甲基甲硅烷基双(茚基)合锆[rac-Me2Si(Ind)2ZrCl2 ]
12.二氯·外消旋-亚乙基双(茚基)合铪[rac-Et(Ind)2HfCl2]
13.二氯·外消旋-二甲基甲硅烷基双(茚基)合铪[rac-Me2Si(Ind)2]
14.二氯·二甲基甲硅烷基(四甲基环戊二烯基)(叔丁酰氨基)合钛[Me2Si(Cp＊)(NBut)TiCl2]
15.三(五氟苯基)硼烷[B(C6F5)3]
16.四(五氟苯基)硼酸三苯甲酯[Ph3CB(C6F5)4]
17.四(五氟苯基)硼酸二甲苯胺[HNMe2PhB(C6F5)4]
18.四(五氟苯基)硼酸锂[LiB(C6F5)4]
19.甲基铝氧烷[MAO]
20.三异丁基铝[Al(Bui)3]，25wt％Al的己烷溶液，0.86M Al
己烷溶剂经3
分子筛纯化。甲苯溶剂从熔融钠中蒸馏并用干燥的脱氧氩气脱气。乙烯和丙烯均为高纯度等级的单体，经过分子筛和脱氧化催化剂提纯。二烯烃单体5-亚乙基-2-降冰片烯[ENB]、二环戊二烯[DCPD]、5-乙烯基-2-降冰片烯[VNB]和1，7-辛二烯[OD]经活化氧化铝去抑制并保存在4
分子筛上。
以下方法用于测定弹性体的性能。
重均分子量(M
w
)、数均分子量(M
n
)和(M
w
/M
n
)
弹性体的分子量Mw和Mn在130℃的邻二氯苯中在装有WatersRA401折射指数检测器和Waters Styragel HT柱(10E5
、10E4
、10E3
和10E6
)的Waters GPC 150C凝胶渗透色谱仪上测量。分子量由来自American Polymer Standards Corp.的聚苯乙烯标准校正的洗脱时间计算(窄分子量分布，Mn为9300至2.1×106)。
门尼粘度(125℃下的ML
1+4
)
弹性体的门尼粘度(125℃下的ML1+4)按ASTM标准D1646在Monsanto门尼粘度计(Mooney Viscometer)model MV 2000上测量。
玻璃化转变温度(T
g
)
弹性体的玻璃化转变温度(Tg)是通过对20-25mg在150℃模塑15分钟然后在室温退火24小时的聚合物用示差扫描量热法测量。Tg是以Perkin Elmer DSC7示差扫描量热计上记录的试样的加热曲线(以20℃/分钟的加热速率从-100℃至180℃)上玻璃化转变的中点报告的。
滞后现象(tanδ)
弹性体的滞后现象(tanδ；ASTM标准D945)用Monsanto橡胶加工分析仪(Rubber Process Analyzer)model RPA 2000测量，以0.25rad/s的频率和1°弧度(14％)的应变在150℃所作十次测量结果的平均值报告。
乙烯：丙烯之比和二烯烃含量
弹性体的乙烯∶丙烯之比和二烯烃含量按ASTM标准D3900通过薄聚合物膜在Perkin-Elmer红外分光光度计Paragon 1000 PC上测量。
总的溶液聚合法A(使用MAO助催化剂)
将金属茂前催化剂放入低管形瓶中称皮重，在氩气下在剧烈混合下与适当等分的MAO溶液混合。所得催化剂溶液在使用前老化30分钟。在一聚合试验中，使0.056克(100微摩尔)二氯·二苯基亚甲基(环戊二烯基)(芴基)合锆[Ph2C(Cp-9-Flu)ZrCl2 ]与40.0ml MAO溶液反应。产生Zr＝2.0mM和Al/Zr之比为1250的催化剂溶液。
然后，将1500ml己烷、1.2ml Al(Bui)3(相当于1.0mmol Al)、适当等分的二烯烃、及乙烯和丙烯各50psi(质量流量在转子流量计上测量)装入一2升玻璃反应器中，使之热平衡。
然后将催化剂溶液注入该反应器中。按需供给乙烯和丙烯以使反应器压力保持在50psi。用100ml酸化甲醇(1vol％浓度的HCl)终止聚合，使所得聚合物凝固，然后研磨-干燥。
总的溶液聚合法B(使用产生阳离子的助催化剂)
将1500ml己烷、1.2ml Al(Bui)3(1.0mmol Al)、适当等分的二烯烃、及乙烯和丙烯各50psi(质量流量在转子流量计上测量)装入一2升玻璃反应器中，使之热平衡。将1.0ml Ph2C(Cp-9-Flu)ZrCl2(0.056g，100微摩尔在10ml甲苯中)的10mM溶液注入该反应器中，使之与Al(Bui)3反应2分钟。
将助催化剂的其余组分，例如1.0ml B(C6F5)3(0.102g，100微摩尔)和LiB(C6F5)4(0.152g，100微摩尔)在10ml甲苯中的10mM溶液，注入该反应器中。按需供给乙烯和丙烯以使反应器压力保持在50psi。用100ml酸化甲醇(1vol％浓度的HCl)终止聚合，使所得聚合物凝固，然后研磨-干燥。
通过IR光谱法分析聚合物产品确定E∶P之比和二烯烃含量。此外，对于多数试样，测量分子量Mw、热转变(DSC)、tanδ、和125℃下的门尼粘度。
每个实施例的具体聚合条件和所得聚合物的物性示于后面的表1-6中。
对比例1-19
用上述溶液聚合法A，用几种MAO活化的其桥连基缺少庞大基团的桥连金属茂催化剂制备EP和EPDM型弹性体。各聚合条件和所得聚合物的性能示于下表1中。
如这些数据所示，对比例1-3和7-9说明使用锆基金属茂催化剂产生低门尼粘度的聚合物，对比例4-6和10-12说明使用铪基金属茂催化剂表现出不能接受的低活性。对比例1-13中使用的所有催化剂均对丙烯表现出相对差的活性。对比例13-18仅产生共聚物，而非三元共聚物；未掺入二烯烃，观察到二烯烃的阻聚作用。对比例19表现出低催化剂活性，所得弹性体有低门尼粘度。
实施例1-3
用上述溶液聚合法A，用MAO活化的其桥连基有两个庞大基团的桥连金属茂催化剂制备弹性体。各聚合条件和所得弹性体的性能示于表2中。
表2：实施例1-3
A.聚合 条件
＊加入用于降低MAO/Zr之比。
在这些实施例中，产量均很高且均得到良好的E∶P比。在实施例2和3中，二烯烃成功地掺入聚合物中而得到EPDM弹性体。所有弹性体均表现出良好的性能。实施例1-3还证明良好的结果需要MAO与金属茂之比高。
实施例4-9
这些实施例中所用聚合方法与实施例1-3中相似，目的是要表明用其它二烯烃单体作为支化剂对所得EPDM型弹性体的某些性能的有益影响，特别是它们的门尼粘度、Mw、Mw/Mn、和tanδ值。各聚合条件和所得聚合物的性能示于表3中。
实施例4至7所用MAO/金属茂之比高达实施例8和9的两倍，得到高得多的产量和高得多的活性，后者进一步证明要获得最佳结果需要使用非常高的MAO/金属茂之比。实施例5至9表明掺入支化二烯烃导致各弹性体的门尼粘度、Mw、Mw/Mn、和tanδ值(测量时)均相对于不含支化二烯烃的实施例4的弹性体改善。
对比例20-23；实施例10-19
用上述溶液聚合法B，用其桥连基有两个庞大基团的且用在本发明范围之内(实施例10-19)和之外(对比例20-23)的产生阳离子的助催化剂活化的金属茂催化剂制备EPDM弹性体。各聚合条件和所得聚合物的性能示于表4中。
如这些数据所示，对比例20-23中所用催化剂寿命短，在初始暴发的高活性后则没有或几乎没有活性(对比例23的催化剂根本未表现出活性)。相反，说明本发明产生阳离子的助催化剂的作用的实施例10-19在整个聚合期间均表现出良好的活性，结果表明它比对比例的产生阳离子的助催化剂稳定性高得多。考虑到本发明产生阳离子的助催化剂的含硼化合物如对比例20和23中单独使用时得到不能接受的结果，此结果更令人吃惊。
对比例24-43；实施例20-24
用基本上与对比例20-23和实施例10-19相同的方法，用已被在本发明范围之内(实施例20-24)和之外(对比例24-43)的产生阳离子的助催化剂活化的各种金属茂催化剂进行聚合。各聚合条件和所得聚合物的性能示于表5中。
虽然Al(Bui)3+Ph3C助催化剂产生有很高初始活性的活化金属茂催化剂(对比例26、30、34、38和42)，但该活性与用本发明产生阳离子的助催化剂活化金属茂前催化剂得到的稳定得多的催化剂(实施例20-24)相比寿命短。此结果差异示于附图1中，以用Al(Bui)3+Ph3C活化的前催化剂(对比例30)和用Al(Bui)3+LiB+B活化的前催化剂(实施例21)之间对时间的单体消耗的对比表示。用Al(Bui)3+Ph3C助催化剂得到的催化剂在几分钟内失去所有活性，而用本发明Al(Bui)3+LiB+B助催化剂得到的催化剂在所示的整个10分钟聚合时间和大大超出该时间时仍继续提供良好的活性。
对于用Al(Bui)3+Ph3C助催化剂得到的金属茂所观察到的不稳定性在对比例27、31、35和39的用Al(Bui)3+HNMe3Ph助催化剂活化的金属茂中显然也大体相同，后者表现出导致聚合物胶凝的另一缺点。
对比例44-48；实施例25-27
对比例44-48使用溶液聚合法A，说明已知类型的MAO活化的催化剂的应用。实施例25-27使用溶液聚合法B，说明用本发明产生阳离子的助催化剂活化这些对比例中所用的相同前催化剂得到的催化剂的应用。聚合条件、它们的结果和产品聚合物的性能示于表6中。
用MAO活化前催化剂时(对比例44-48)，要获得可接受的催化活性需要超常高的MAO/前催化剂之比。特别是在较高温度(70℃)下，丙烯的反应性不适宜且产品聚合物的Tg不能接受地高。与这些结果相反，使用本发明产生阳离子的助催化剂活化前催化剂(实施例25-27)提供更高的产量和更高的活性，且产生有较好Mw、ML1+4和Tg的聚合物。
在本发明另一种实施方案中，试图通过在聚合期间使用已知的链转移剂如氢气，可有目的地明显降低本文所述弹性体的分子量，产生低分子量、甚至液态的聚合物，它们在特殊应用中可能是理想的。
表7
注：a聚合条件：1500ml己烷，40℃，50psig下的乙烯：丙烯质量流量比为1∶1，三异丁基铝＝0.67mM，[Ph2Cp-9-Flu)ZrCl2]＝[LiB(C6F5)4]＝[B(C6F5)3]＝6.67microM。
聚合时间＝10分钟。其它条件见20、21页的总的溶液聚合方法的内容。
b无丙烯
c由FTIR估算
Claims (13)
1.一种用于在存在或不存在铝氧烷助催化剂条件下活化金属茂前催化剂的产生阳离子的助催化剂，所述助催化剂包括：第一组分，能够独立地用氢原子或最多20个碳原子的烃基或最多20个碳原子的氧烃基交换与金属茂的过渡金属配位的一个或多个非环戊二烯基配体最多至其总数的含金属和/或准金属的化合物；第二组分，具有至少一个含有至少一个吸电子取代基的芳基的含中性金属和/或准金属的化合物；和第三组分，具有至少一个含有至少一个吸电子取代基的芳基的含金属和/或准金属阴离子的化合物。
2.权利要求1的产生阳离子的助催化剂，其中所述第一组分为铝化合物，所述第二组分为硼烷化合物，和所述第三组分为金属硼酸盐化合物。
3.权利要求2的助催化剂，其中所述铝化合物为三烷基铝或氢化二烷基铝，所述硼烷化合物为三(卤代芳基)硼烷，和所述金属硼酸盐化合物为碱金属-、碱土金属-、过渡金属-或准金属四(卤代芳基)硼酸盐。
4.权利要求3的助催化剂，其中所述铝化合物为三烷基铝，所述硼烷化合物为三(卤代苯基)硼烷，和所述金属硼酸盐化合物为碱金属四(卤代苯基)硼酸盐。
5.一种在存在或不存在铝氧烷助催化剂条件下用产生阳离子的助催化剂活化金属茂前催化剂的方法，所述金属茂前催化剂为至少一种通式(I)和/或(II)的化合物：
(Cp1R1 m)R3 n(Cp2R2 p)MXq (I)
(Cp1R1 m)R3 nYrMXs (II)
其中配体(Cp1R1 m)的Cp1和配体(Cp2R2 p)的Cp2为相同或不同的环戊二烯基环，R1和R2独立地为卤素或最多20个碳原子的烃基、卤代烃基、烃基-取代的有机准金属或卤代烃基-取代的有机准金属基团，m为0至5，p为0至5和与此相连的环戊二烯基环的相邻碳原子上的两个R1和/或R2取代基可连接在一起形成含4至20个碳原子的环，
R3为桥连基团，n为0或1，Y为含杂原子的基团，其中所述杂原子与M配位，M为有3至6价的过渡金属，每个X为非环戊二烯基配体且独立地为卤素或最多20个碳原子的烃基、氧烃基、卤代烃基、烃基-取代的有机准金属、氧烃基-取代的有机准金属或卤代烃基-取代的有机准金属基团，q等于M的化合价减2，r取n的值，和s当r为0时等于M的化合价减1而当r为1时等于M的化合价减2，所述产生阳离子的助催化剂包括：第一组分，能够独立地用氢原子或最多20个碳原子的烃基或最多20个碳原子的氧烃基交换所述金属茂前催化剂中的至少一个X配体最多至其总数的含金属和/或准金属的化合物；第二组分，具有至少一个含有至少一个吸电子取代基的芳基的含中性金属和/或准金属的化合物；和第三组分，具有至少一个含有至少一个吸电子取代基的芳基的含金属和/或准金属阴离子的化合物，所述方法包括使所述金属茂前催化剂与所述产生阳离子的助催化剂的组分在烯烃存在下以任何组合形式或以任何次序混合。
6.权利要求5的方法，其中金属茂前催化剂(I)中，桥连基团R3有以下结构：
或
其中庞大基团R4和R5独立地为或包含含有最多20个碳原子和0至3个杂原子的环烃基。
7.权利要求6的方法，其中所述环烃基为环烷基、杂环烷基、环烯基、杂环烯基、芳基、杂芳基、烷芳基、烷基杂芳基、芳烷基、或杂芳烷基。
8.权利要求5的方法，其中配体(Cp1R1 m)为未取代的环戊二烯基，配体(Cp2R2 p)为茚基或芴基，M1为锆，R4和R5配体均为苯基，和X均为氯。
9.权利要求5的方法，其中金属茂前催化剂(II)中，n和r均为1，M的化合价为4，配体X为卤素，和s为2。
10.权利要求5的方法，其中所述产生阳离子的助催化剂中，所述第一组分为铝化合物，所述第二组分为硼烷化合物，和所述第三组分为金属硼酸盐化合物。
11.权利要求10的方法，其中所述铝化合物为三烷基铝或氢化二烷基铝，所述硼烷化合物为三(卤代芳基)硼烷，和所述金属硼酸盐化合物为碱金属-、碱土金属-、过渡金属-或准金属四(卤代芳基)硼酸盐。
12.权利要求11的方法，其中所述铝化合物为三烷基铝，所述硼烷化合物为三(卤代苯基)硼烷，和所述金属硼酸盐化合物为碱金属四(卤代苯基)硼酸盐。
13.在用铝氧烷助催化剂活化金属茂前催化剂以提供金属茂催化剂的方法中，其中改进包括用产生阳离子的助催化剂取代部分或全部所述铝氧烷助催化剂，所述产生阳离子的助催化剂包括：第一组分，能够独立地用氢原子或最多20个碳原子的烃基或最多20个碳原子的氧烃基交换与所述金属茂的过渡金属配位的一或多个非环戊二烯基配体最多至这种配体存在的总数的含金属和/或准金属的化合物；第二组分，具有至少一个含有至少一个吸电子取代基的芳基的含中性金属和/或准金属的化合物；和第三组分，具有至少一个含有至少一个吸电子取代基的芳基的含金属和/或准金属阴离子的化合物。
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- 1997-04-01 DK DK97917770T patent/DK0892816T3/da active
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- 1997-04-01 CN CNA2007101802372A patent/CN101186658A/zh active Pending
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- 1997-04-01 JP JP53627897A patent/JP3274686B2/ja not_active Expired - Fee Related
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- 1997-04-01 KR KR10-2004-7014875A patent/KR100505840B1/ko not_active IP Right Cessation
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151470A (zh) * | 2009-07-01 | 2014-11-19 | Lg化学株式会社 | 一种乙烯-丙烯-二烯弹性聚合物 |
| US9315605B2 (en) | 2009-07-01 | 2016-04-19 | Lg Chem, Ltd. | Method for producing an elastomer using a transition metal catalyst |
| CN106366226A (zh) * | 2015-07-23 | 2017-02-01 | 中国石油化工股份有限公司 | 一种过渡金属催化剂组合物及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| PT892816E (pt) | 2003-04-30 |
| US6060572A (en) | 2000-05-09 |
| JP3274686B2 (ja) | 2002-04-15 |
| EP0892816A1 (en) | 1999-01-27 |
| US6147025A (en) | 2000-11-14 |
| US6136744A (en) | 2000-10-24 |
| WO1997038019A1 (en) | 1997-10-16 |
| JP2000507635A (ja) | 2000-06-20 |
| CN1215408A (zh) | 1999-04-28 |
| RU2205837C2 (ru) | 2003-06-10 |
| KR100505840B1 (ko) | 2005-08-03 |
| DK0892816T3 (da) | 2003-03-31 |
| DE69717614T2 (de) | 2003-07-24 |
| CN100436484C (zh) | 2008-11-26 |
| ES2190529T3 (es) | 2003-08-01 |
| HK1019609A1 (en) | 2000-02-18 |
| CN1544484A (zh) | 2004-11-10 |
| BR9708645A (pt) | 2002-06-04 |
| KR20040091150A (ko) | 2004-10-27 |
| DE69717614D1 (de) | 2003-01-16 |
| ATE229039T1 (de) | 2002-12-15 |
| US6225426B1 (en) | 2001-05-01 |
| CN101186658A (zh) | 2008-05-28 |
| JP2002249521A (ja) | 2002-09-06 |
| JP2001302731A (ja) | 2001-10-31 |
| EP0892816B1 (en) | 2002-12-04 |
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