CN1028369C - 使用阳离子聚合催化剂的聚合方法 - Google Patents
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Abstract
一种加聚方法,其中的加成聚合催化剂符合下面的通式:
CpMXn+A-
其中Cp是环戊二烯基或取代环戊二烯基,M是钛或锆;X是氢化物或选自卤代基、烷基、芳香基、甲硅烷基、甲锗烷基、芳氧基、烷氧基、酰胺、甲硅烷氧基的基团或混合基团,A-是非配位的、相容的质子酸盐的阴离子,n与M的价数有关,为1或2。
Description
本发明涉及一些用作催化剂的组合物,一种制备这些催化剂的方法以及一种将这些催化剂用于聚合可加成聚合单体的方法。
在EP-A-0277004中披露了由一个双环戊二烯基金属络合物与含有一个非配位相容阴离子的质子酸盐反应所形成的某些双环戊二烯基金属化合物。该文献披露了这一事实,即这样的络合物可以有效地用作烯烃聚合反应的催化剂。
尽管在上述先有技术文献中所披露的催化剂是有效的,但仍需要生产更有效和更有用的加成聚合催化剂。特别是本研究工作已使我们得到了这样一些含某些化合物的某种改进的金属络合物,这些化合物具有高的聚合活性和可以满意地供各种各样单体及其混合物的聚合之用。
本发明提供了一种含有对应于结构式
CpMX+ nA-
的化合物的单环戊二烯基或取代的单环戊二烯基金属络合物。其中:
Cp是一个通过一取代基以任意地共价键的方式键合到M上的单一的η5-环戊二烯基或η5-取代环戊二烯基团;
M是以η5键合方式连接到环戊二烯基或取代环戊二烯基上的周期表中镧系或3-10族金属;
X每一个是氢化物或者是选自卤代基、烷基、芳基、硅烷基、甲锗烷基、芳氧基、烷氧基、酰胺基、硅烷氧基和它们的结合体(如卤代烷基、卤代芳基、卤代硅烷基、烷芳基、芳烷基、硅烷基、芳氧芳基、烷氧烷基、酰胺烷基、酰胺芳基、等等)的基团,具有最多到20个非氢原子,以及具有最多到20个非氢原子的路易斯碱配位体,或者是任意一个X与Cp一起形成一带有M的金属取代环。
n是1或2,取决于M的化合价;
A-是一质子酸盐的非配位相容阴离子。
这样一些化合物可有效地用于配位型聚合反应过程,以制备用于模塑、薄膜、片材挤压成型泡沫和其它一些用途的聚合物。这些化合物也可以被用于氢化反应、催化裂化和其它工业过程。
本发明的这些化合物可以通过合并(a)和(b)来制备:
(a)至少一种第一组分,该组分是含有至少一个取代基的元素周期表中镧系或3-10族金属的单环戊二烯基衍生物,这一取代基将与一第二组分(在下文中述及)的阳离子结合,第一组分能形成一个通常具有的配位数比其化合价小的阳离子。
(b)和至少一个第二组分,该第二组分是一质子酸盐和一个在惰性、非质子传递溶剂中的非配位相容阴离子,而且,如果需要可回收到所产生的产物。
更具体些说,质子酸盐的非配位相容阴离子可以由一个单一的配位化合物所组成,这一配位化合物又是由一个带电荷金属或准金属核所组成,该阴离子体积庞大又是非亲核性的。在这里所用的“准金属”这一表述,包括呈现半金属特性的象硼、磷之类的非金属。
在这里所提到的元素周期表都是指CRC印刷公司1989年发表并持有版板的元素周期表。此外,关于族的位次编排,所提到的族都与用IUPAC系统的元素周期表中所表示的族相同。
这里所用的“非配位相容阴离子”这一表述是指这样的阴离子,它或者不与含有阳离子的单环戊二烯基或取代的单环戊二烯基配位,或者,仅与上述阳离子很弱的配位,从而留有足够的不稳定性使之能被一个中性的路易斯碱所取代。非配位相容阴离子特指这样一种相容阴离子,即当它在本发明的催化体系中起一个电荷配平阴离子的作用时,它并不将阴离子的取代基或碎片转移到上述阳离子上,从而形成一个中性的四配位金属茂和一个中性金属副产物。“相容阴离子”是那些最初所形成的络合物分解时并不降解至中性而且对于所希望的随后的聚合反应或络合物的其它用途不产生干扰作用的阴离子。
用于本发明的单环戊二烯基和取代的单环戊二烯基团可用下面的通式表示:
其中:
每一个R′都是氢或者是选自卤素、烷基、芳基、卤代烷基、烷氧基、芳氧基、硅烷基中的一部分,和具有最多达20个非氢原子的它们的结合体,或者是两个或更多R′基团在一起形成一个稠环体系;
R″是R′或者一个具有结构式为-Z-Y-的以共价键形式键合到M上的基团,其中:
Z是一个二价基团,包括氧、硼或元素周期表中14族中的一个元素;
Y是共价键的形式与金属键合的键连基团,金属包括氮、磷、氧或硫,或者是Z和Y随意连在一起形成一个稠环体系。
在本发明的一个实例中R′和R″分别是甲基。
在一个更理想的实例中R″是
其中:
每一个E都是碳、硅或锗;
P是一个1至4的整数;
Y′是氮或磷,和
每一个R′″是烷基、芳基、硅烷基或者是具有最多达10个碳或硅原子的这些基团的结合体(例如烷芳基、芳烷基、硅烷基等)。
本发明更理想的组合物对应于下式:
其中:
M是锆或钛;
Cp是以η5键合方式连结到M上的环戊二烯基或取代环戊二烯基团;
Z是SiR* 2,CR* 2,SiR* 2,SiR* 2,CR* 2,CR* 2,CR*=CR*CR* 2,SiR* 2,或是GeR* 2;
Y是含有氮或磷的基团,对应于通式为:
-N(R″″)-或-P(R″″)-
其中:
每个R*都是氢或选自烷基、芳基、硅烷基、卤代烷基、卤代芳基的一部分,或具有最多达20个非氢原子的这些基团的结合体;
R″″是C1-10烷基或C6-10芳基,或两个及更多R*基团或一个或更多R*基团和R″″一起形成一个具最多达30个非氢原子的稠合环体系;
每一个X都是具有最多达20个碳原子的卤代基、烷基、芳基、烷氧基或芳氧基。
n是1或2;
A-是一个质子酸盐的非配位相容阴离子。
可用于制备本发明化合物的单环戊二烯基金属组分(第一组分)的实例是钛、锆、铪、铬、镧等的衍生物。这些实例仅用于说明,但不限于此。较理想的组分是钛或锆的化合物。适宜的单环戊二烯基金属化合物的实例是:象三甲基环戊二烯基锆,三乙基环戊二烯基锆,三丙基环戊二烯基锆、三甲基环戊二烯基钛,三苯基环戊二烯基钛,双对甲苯基环戊二烯基钛,2,4-戊二烯基环戊二烯基铬,双(双三甲硅烷基甲基)五甲基环戊二烯基镱,双(双三甲硅甲基)五甲基环戊二烯基钪,双(双三甲基硅甲基)五甲基环戊二烯基镧等这样的烃基取代单环戊二烯基金属化合物;象三异丙氧基环戊二烯基钛,三苯氧基环戊二烯基锆等这样的烃氧基取代化合物;象三氯环戊二烯基锆,三氯茚基钛,三氯戊甲基环戊二烯基铪和二氯环戊二烯基镱等这样的卤代化合物;和象异丙氧基二甲基环戊二烯基钛,甲基二氯代五甲基环戊二烯基锆,氯代异丙氧基环戊二烯基镧,二氯代(叔丁基酰胺基)(四甲基-η5-环戊二烯基)-1,2-联二甲基锆,二氯代(叔丁基酰胺基)(四甲基-η5-环戊二烯基)-1,2-乙烷二联钛,二氯代(甲酰氨基)(四甲基-η5-环戊二烯基)-1,2-联二甲基锆,二氯代(甲酰氨基)(四甲基-η5-环戊二烯基)-1,2-乙联二甲基钛,二氯代(乙酰胺基)(四甲基-η5-环戊二烯基)亚甲基钛,(叔丁基酰胺基)二苄基(叔丁基-η5-环戊二烯基硅烷二苄基锆,(苄基酰胺基)二甲基(四甲基-η5-环戊二烯基)硅烷二氯化钛,(苯磷基)二甲基(四甲基-η5-环戊二烯基)硅烷二苄基锆等这样的由混合取代基所组成的化合物。
上面列举的后几个化合物是在金属原子和环戊二烯基环之间含有共价键的化合物的例子。较理想的取代基是那些能够δ-键合于金属原子上的取代基。通过将相应的金属氯化物与象环戊二烯基联二烷基、环戊二烯基硅烷酰胺或磷化环戊二烯基这样的取代环戊二烯基的二锂盐化合即可以很容易地制得这样的组分。反应用惯常的合成程序在四氢呋喃、C5-10烷烃、甲苯等这样的惰性液体中进行。
本发明的化合物的制备中可用作第二组分的化合物是由一个阳离子和一个非配位相容阴离子组成的,而所述阳离子是一个能提供质子的质子酸。较理想的阴离子是那些含有由一个带电荷金属或准金属核所组成的单个配位络合物的阴离子。上述带电荷金属或准金属核阴离子相当大(体积大),能够使由两种组分结合时形成的活性催化体(3-10族或镧系阳离子)稳定,上述阴离子足够不稳定以至于可被烯、双烯和炔属不饱和物质或其它象醚、腈之类的中性路易斯碱所取代。适宜的金属包括(但不限于)铝,金、铂之类。适宜的准金属包括(但不限于)硼、磷、硅之类。当然,含有由包含一个单一金属原子或准金属原子的配位络合物所组成的阴离子的化合物是大家所熟知的,特别是在阴离子部分含有单个硼原子的化合物,其中有一些是市场上可卖到的。根据这一点,含有由包含单个的硼原子的配位络合物所组成的阴离子的盐是更为可取的。
宜用于制备本发明催化剂的第二组分可以用下列通式来表示:
(L-H)+[A]-
其中:
L是一中性路易斯碱:
(L-H)+是一个质子酸,和
A是一相容非配位阴离子。
A-最好是相当于结构式
[M′m+Qn]
其中:
m是一个1至7的整数;
n是一个2至8的整数;
M′是一个金属或选自元素周期表中5-15族的准金属;和
每个Q是氢化物或选自二烷基酰胺基、卤代物、烷氧化物、芳氧化物和烃基的基团,或具有最多达20个碳原子的取代烃基,但限于在该基团中Q是卤代物的情况不多于一个。
在本发明的催化剂的制备中特别有用的由硼组成的第二组分可以用下列通式表示:
[L-H]+[BQ4]-
其中:
L是一中性路易斯碱;
[L-H]+是一质子酸;
B是价态为3的硼;和
Q如前所定义。
在本发明改进的催化剂的制备中可以用作第二组分的硼化物的例子是象四苯基硼酸三乙铵,四苯基硼酸三丙铵,四苯基硼酸三正丁铵,四对甲苯基硼酸三甲铵,四(五氯苯基)硼酸三丁铵,四(2,4-二甲基苯基)硼酸三丙铵,四(3,5-二甲基苯基)硼酸三丁铵,四(3,5-二-三氟甲基苯基)硼酸三乙铵这样的三烷基取代铵盐。这些例子只是用来说明的,但不限于此。同样适宜的象四苯基硼酸N,N-二甲基苯铵,四苯基硼酸N,N-二乙基苯铵,四苯基硼酸N,N-2,4,6-五甲基苯铵这样的N,N-烷基苯铵盐;象四(五氟苯基)硼酸二异丙铵,四苯基硼酸双环己基铵这样的二烷基铵盐;和象四苯基硼酸三苯磷,四(五氟苯基)硼酸三(甲基苯基)鏻,四苯基硼酸三(甲基苯基)这样的三芳基鏻盐。
必须注意,以上的列举并非打算使之详尽无遗,其它的硼化合物也将是有用的,对于那些熟悉本工艺的人员来说,从上述通式和实例将会很容易地了解那些含有其它金属或准金属的有用的组分。
通常,尽管大多数上面所确定的第一组分可以和大多数上面所确定的第二组分化合生成一个活性烯烃聚合催化剂,然而重要的是使聚合反应操作继续下去,因此,最初由第一组分形成的金属阳离子或者它们的分解产物应该是一个相当稳定的催化剂。同样重要的是,当使用铵盐时第二化合物的阴离子应对水解稳定。此外,这一点也是重要的,即相对于第一组分,第二组分的酸度应足以促进所需要的质子转移。相反,金属络合物的碱度也必须足以促进所需的质子转移。某些金属茂化合物除了最强的质子酸外都不与第二组分发生反应,因而不适合于作为第一组分而与所有的第二组分形成本发明的催化剂。最理想的单环戊二烯基金属化合物是那些能被水溶液水解的化合物。
就第一组分(含金属)与第二组分化合物形成本发明的催化剂来说,应该注意的是,这两个被化合以制备活性催化剂的组分应加以选择,以避免具有阴离子碎片,尤其是芳基,或是卤素或者氢原子转移动到金属阳离子上,从而形成无催化活性的物质。这一点应通过位阻来解决,这种位阻产生于环戊二烯基碳原子上的取代基以及阴离子的芳香碳原子上的取代基。它遵循这样一点,由全氢烃基取代的环戊二烯基所组成的第一组分比起那些由未取代的环戊二烯基所组成的第一组分能更有效地与更大范围的第二组分一起使用。然而,随着环戊二烯基上取代基的数量和体积的减小,由含有抗降解性较好的阴离子(例如在苯环邻位上有取代基的那些阴离子)的第二化合物可以得到更有较的催化剂。使阴离子更不易降解的另一手段是对阴离子实行氟取代,尤其是全氟取代。氟取代稳定化了的阴离子可以在较宽的范围内与第一组分共用。
一般来说,该催化剂可以通过在约-100℃至300℃范围的温度内在一种适宜的溶剂中将两种组分化合来制备。该催化剂可以用来聚合具有2个至约18个碳原子的α-烯烃及(或)炔属不饱和单体,及(或)具有4个至约18个碳原子的单一的或混合的二烯。该催化剂还可以用来聚合α-烯烃、二烯和/或炔属不饱和单体与其它不饱和单体的混合物。在一个优选的实例中,采用这些催化剂来制备乙烯基芳香族单体混合物与非乙烯基芳香族单体的烯烃的共聚物,尤其是苯乙烯与乙烯或丙烯的共聚物。一般地说,聚合反应可以在先有工艺中熟知的条件下来完成。当数,如果催化剂体系的组分直接加入到聚合过程中并在所述的聚合过程中使用一种包括缩聚单体在内的适宜的溶剂或稀释剂,那末这种就地形成的催化剂体系一定更令人欣赏。然而,最好是在一个独立的步骤中用一合适溶剂配制好催化剂,然后将其加到聚合步骤中。该催化剂不能含有引火物质,其组分对潮湿和氧气都很敏感,应在惰性气氛中(如在氮、氩或氦的气氛中)操作和转移。
如前所述,本发明改进的催化剂最好在一种适宜的惰性的非质子传递性溶剂或稀释剂中制备。合适的溶剂或稀释剂包括在先有工艺中熟知的在烯烃、二烯烃和炔属不饱和单体聚合反应中使用的任何一种溶剂。适宜的溶剂包括但并不限于以下溶剂:直链和支链的烷烃,如异丁烷、丁烷、戊烷、
己烷、庚烷、辛烷等等;环烃和脂环烷烃,如环己烷、环庚烷、甲基环己烷、甲基环庚烷等等;以及芳香族化合物或烷基取代的芳香族化合物,如苯、甲苯、二甲苯等等。适宜的溶剂还包括可以作为单体或共聚单体反应的液体烯烃,包括乙烯、丙烯、丁二烯、环戊烯、1-己烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1,4-己烯、1-辛烯、1-癸烯、苯乙烯等等。
虽然本发明人并不希望被任何特定的理论所束缚,但可以相信,当用来制备本发明改进的催化剂的两组分在适宜的溶剂或稀释剂中进行化合时,第二组分的全部或部分阳离子(酸质子)与第一组分上的取代基(X)中的一个相化合。结果释放出一种中性化合物XH,该中性化合物或保留在溶液中或作为气体放出。在这点上,应该注意的是,如果第一组分中的X是氢化物,则可能有氢气放出。类似地,如果X是甲基,则会有甲烷气体放出。如果X是烷氧基,则产生醇等等。
尽管仍不希望被任何特定的理论所约束,还相信当第一组分取代基中的一个释放后,原本含在用于催化剂制备的第二组分中非配位阴离子与第一组分形成的金属阳离子或其分解产物的电荷相平衡。金属阳离子和非配位阴离子保持如此的结合状态直到催化剂与一种或多种烯烃、二烯烃和/或炔属不饱和单体相接触为止,上述单体是以单独的形式、或以与一种或更多种其它单体或一中性路易斯酸形成混合物的形式与催化剂接触的。如前所述,在第二化合物中所含的阴离子必须足够的不稳定从而能够被单体迅速置换来促进聚合反应。
当优选的含硼化合物作为第二组分时,形成本发明的催化剂所发生的化学反应参考一般反应式可以表示如下:
CpMXn+1+[L-H]+[BQ4]-→[CpMXn]+[BQ4]+X-H+L
式中Cp、M、X、n和Q如前定义。
一般地说,前述反应式中的产物(尤其是金属阳离子)的稳定性和形成速度的变化取决于溶剂的选择、所选用的[L-H]+的酸性(尤其是阴离子L)、完成反应的温度以及所选择的金属单环戊二烯衍生物。初形成的离子对通常是活性聚合催化剂,并能使单独的或与其它单体混合烯烃、二烯烃或炔属不饱和单体聚合。然而,在某些情况下,起初的金属离子会分解得到一种活性聚合催化剂。
如前所述,大部分前面确定的第一化合物会与第二化合物化合产生一种活性的催化剂,尤指一种活性聚合催化剂。但是这种具有有效活性的催化剂物质总是不够稳定以使它能够分离及连续鉴定。并且许多初形成的金属阳离子相对较稳定,很显然它们常常分解成一个或更多个其它催化活性的物质。
一般地说,可选用本发明的催化剂用以生产不含某些微量金属的聚合产物,这些金属常存在于用含有诸如铝或镁基化合物等辅助催化剂的Ziegler-Natta型催化剂催化产生的聚合物中。用本发明的催化剂所产生的聚合产物应比通常的Ziegler-Natta型催化剂产生的聚合产物具有更广的应用范围,Ziegler-Natta型催化剂含有烷基化金属,如烷基铝或铝氧烷。催化剂可以作为均相催化剂使用或附着在适宜的载体(如氧化铝或硅胶)的表面上使用。
在本发明最优选的实例中,Cp是五甲基环戊二烯,M是钛或锆,n是2,X是C1-4烷基或烷氧基,A是四(五氟基苯基)硼酸。
在进一步的优选的实例中,该催化剂用来聚合一种或更多种C2-C8α-烯烃,特别是乙烯或丙烯,最好是乙烯,所用的反应条件为,温度在0℃至200℃的范围内,最好25℃至100℃,压力在常压至1000pslg(7MPa)范围内,最好15至500Psig(0.1-3.5MPa)。在本发明最优选的实例中,该催化剂可用来单独使乙烯聚合或使乙烯与C3-C8α-烯烃(包括苯乙烯)共聚而得到共聚物。在这两个优选和最优选的实例中,单体在聚合条件下维持一段很短的时间,在约1至约60分钟范围内,催化剂的用量,按浓度计,在每摩尔单体约10-7至10-1摩尔的范围内。
本发明已经得到了充分的描述,可以相信通过参考如下举例本发明将更为明了。然而,应该意识到,列举这些实例的目的仅在于说明本发明,而不应认为来限制本发明。
实施例1
五甲环戊二烯基二甲基异丙氧基钛和四(五氟苯基)硼酸三乙基铵
在一个干燥的箱中,室温下将33mg五甲环戊二烯基二甲基异丙氧基钛(CpTi(O-i-Pr)Me2)(0.12mmol)与1ml苯混合,所得溶液用吸管转
入250ml三颈烧瓶中。烧瓶上加一个塞子、一个真空接管和一个固体加料漏斗。在加料漏斗中加入80mg(0.10mmol)四(五氟苯基)硼酸三乙基铵(〔HNEt3〕+〔B(C6F5)4〕-)。塞上加料漏斗口并将该装置和真空管线相连。在真空下除去烧瓶中的苯,再在真空下于-78℃加入烧瓶中75ml新蒸馏的苯。溶液温热到室温后通以1大气压(0.1MPa)的乙烯。在室温下加入固体(〔HNEt3〕+〔B(C6F5)4〕-),可以观察到溶液变为黄色。20分钟后溶液呈黑色并观察到有聚乙烯沉淀。一小时后,聚合物用甲醇沉淀出,收集后用甲醇洗涤,真空干燥过液,得到0.49g聚合物。
实施例2
五甲环戊二烯基三甲基钛和四(五氟苯基)硼酸三乙基铵
采用五甲环戊二烯基三甲基钛和四(五氟苯基)硼酸三乙基铵,基本重复例1的反应条件。反应在甲苯中室温下进行约10小时。可以观察到甲烷气和氨副产物。在45℃左右加热一小时后真空除去甲苯,留下一种黑色固体。该固体用石油醚洗三次并在真空下干燥。回收到的产物被鉴定为所期望的五甲环戊二烯基二甲基钛四(五氟苯基)硼酸盐,它可以在已知的Zigler-Natta聚合条件下使烯烃发生聚合反应。
实施例3
(叔丁酰胺基)二甲基(四甲基-η5-环戊二烯基)硅烷二甲基钛和四(五氟苯基)硼酸三乙铵
在一个25ml的烧瓶中装入275mg(叔丁酰胺基)(二甲基)(η5-四甲环戊二烯基)硅烷二氯化钛(0.75mmol),并将烧瓶与一个小玻璃瓶(frit)相连,玻璃瓶减压将15ml乙醚真空转入烧瓶中。在-78℃,用注射器从侧阀加入1.1mlMeLi(1.4M在己烷中,1.54mmol,2.05当量),未发现颜色变化。5分钟后,移出浴槽,使溶液温热至室温。1小时后,溶液呈暗绿色并且不透明。除去乙醚并用10ml己烷代替。在25℃搅拌溶液10分钟然后过滤。将固体减少到约2ml,将溶液冷却至-78℃,将上述小玻璃瓶冷冻回转,可收集到一种暗橄榄色固体。真空干燥30分钟后,得到固体(叔丁酰胺基)二甲基-η5-环戊二烯基)硅烷二甲基钛(138mg,56%)。
聚合
在一个100ml三颈烧瓶中装入32mg(98μmol)(叔-丁酰胺基)二甲基(四甲基-η5-环戊二烯基)硅烷二甲基钛。在烧瓶上装有一个塞子、一个真空接管和一个固体加料漏斗。加料漏斗中加入77mg〔HNEt3〕+〔B(C6F5)4〕-并塞住。烧瓶减压,蒸入50ml苯于固体上。将溶液温热至25℃并通入1大气压(0.1MPa)的乙烯。然后加入固体〔HNEt3〕+〔B(C6F5)4〕-得到一黄色溶液。一小时后,该粘稠的黄色溶液仍然吸收乙烯。所得胶状混合物用甲醇急冷得到一种白色沉淀。过滤后用甲醇洗涤两次,真空干燥得0.56g聚乙烯。
Claims (6)
1、一种使选自含2-18碳原子的α-烯烃的单体或单体混合物聚合的方法,该方法包括在0-200℃温度和大气压至1000大气压的压力下使所述单体或单体混合物与符合下式的加聚催化剂相接触:
式中:
Cp是环戊二烯基、五甲基环戊二烯基或茚基;
Co p是环戊二烯基或四甲基环戊二烯基;
M是钛或锆;
Z是Si(CH3)2;
Y是-N(R′″)-或-P(R′″)-,式中R′″是C1-10烷基或C6-10芳基;
X是卤素、苄基或最多含20个碳原子的烷基、芳基、烷氧基或芳氧基;和
A-是通式为BQ- 4的非配位的、相容的阴离子,
式中B是硼,Q是氢化物或选自二烷基酰胺基、卤化物、烷氧化物、芳氧化物、烃基或最高达20个碳的卤取代烃基,但限定Q中卤素不超过一个,
所述催化剂与单体的当量比为10-7∶1至10-1∶1。
2、根据权利要求1所述的方法,其中A-是四(五氟苯基)硼酸盐。
3、根据权利要求1所述的方法,其中M是钛。
4、根据权利要求1所述的方法,其中的催化剂是五甲基环戊二烯基二甲基异丙氧基钛四(五氟苯基)硼酸盐、五甲基环戊二烯基三甲基钛四(五氟苯基)硼酸盐、(叔丁酰胺盐)二甲基(四甲基-η5-环戊二烯基)硅烷二甲基钛四(五氟苯基)硼酸盐或(叔丁基酰胺基)二甲基(四甲基-η5-环戊二烯基)硅烷二甲基锆四(五氟苯基)硼酸盐)。
5、根据权利要求1所述的方法,其中催化剂还含有载体。
6、根据权利要求1所述的方法,其中单体是乙烯、丙烯、丁二烯、环戊烯、1-己烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1,4-己二烯、1-辛烯、1-癸烯、苯乙烯或它们的混合物。
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