CN1037686C - 一种链烯烃聚合的方法 - Google Patents
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Abstract
本发明涉及用于链烯烃聚合反应的催经剂体系,它将离子型金属茂催化剂与烷基铝一起使用。该金属茂催化剂是由一种中性金属茂化合物与一种致电离化合物生成的离子对。本发明可用于任何制备离子型金属茂催化剂的方法。将烷基铝与离子型金属茂催化剂一起使用,就无需使用甲基铝 烷(MAO)。用本发明的方法制备的催化剂具有高度的活性。本发明减少了引起活性低下、活性消失或不受控制的聚合反应的使催化剂中毒的毒物。
Description
本发明涉及一种改进的催化剂系统;具体地说,它涉及用于链烯烃聚合的、通过加入烷基铝而得到改进的金属茂催化剂系统以及使用这样一种催化剂的方法。
链烯烃,尤其是丙烯,可以聚合形成各种形式的聚烯烃:全同立构的,间同立构的和无规立构的。全同立构的聚丙烯主要包含相同构型的重复单元,在链中只有少数无定的、短的倒位部分。全同立构聚丙烯的结构可表示为
全同立构聚丙烯可以是一种高结晶度的聚合物,它具有晶体的熔点和其它合乎需要的物理性能,这些性能与无定形(非晶态)聚合物显著不同。
无规立构聚合物则在聚合物链中,重复单元的构型的次序是没有规则的。在工业应用中,一般总有若干百分比的无规立构聚合物与全同立构形式一起制备出来。
链烯烃聚合主要使用Ziegler-Natta催化剂。一类Ziegler-Natta催化剂是以甲基铝噁烷(methylaluminoxane)作为助催化剂的IV族金属茂化合物。已经证明,用于链烯烃聚合的Ziegler-Natta催化剂可以通过使IV族金属茂与一种离子化合物结合而形成。
C* p-五甲基环戊二烯基
M-IV族金属
R-烷基
L-配位体
[C]-阳离子
[A]-阴离子所产生的化合物是一种具有催化剂作用的金属茂阳离子。离子化合物的阳离子[C]与金属茂反应产生一对离子对。阴离子[A]并不配位于金属茂阳离子,或者仅松散地配位于它。
下列各方法已用于产生上面的反应:
单电子氧化——这方法在“利用阳离子性的二(环戊二烯基)合锆(IV)的烷基配合物而进行的乙烯聚合”一文中已有说明,参看R.F.Jordan,C.S.Bajgur,R.Willett,B.Scott,J.Am.Chem.Soc.,p.7410-7411,Vol.108(1986)。这些早期实例使用路易斯碱来减小金属阳离子的亲电子性,阴离子是[BPh4]-,其中Ph是C6H5。反应发生在能与阳离子配位的溶剂中。这些材料通常是低活性的。
质子化——这方法的说明见“阳离子性的烷基·二(环戊二烯基)合钛配合物的插入反应及其合成”(M.Bochmann,L.M.Wilson,J.Chcm.Soc.Commun.,p.1610-1611,(1986);“阳离子性的烷基·二(环戊二烯基)合钛配合物”(M.Bochmann,L.Wilson,Organometallics,p.2556-2563,Vol.6,(1987));“阳离子性的烷基·二(环戊二烯基)合钛配合物中腈的插入反应”(M.Bochmann,L.Wilson,Organometallics,p.1147-1154,Vol.7,(1987))。
欧洲专利申清0-277-003号涉及Turnor用质子化方法以制备催化剂的工作。他将一种二(环戊二烯基)金属化合物与一种化合物相结合,这化合物具有阳离子它能供给一个质子,而它的阴离子含有许多硼原子。该发明可以下列反应为例说明:
二甲基化二(环戊二烯基)合铪
+二(7,8-二碳十一硼酸根)合钴(III)酸N,N-二甲基苯胺
N,N-dimethylaniline bis(7,8-dicarbaundecaborato)
cobaltate(III)
→[Cp Hf Me][B]+CH+N,N-二甲基苯胺
其中[B]是7,8-二碳十一硼烷
欧洲专利申请0-277-004号也涉及Turner用质子化方法制备催化剂的工作。他将一种二(环戊二烯基)金属化合物与一种离子化合物相结合,该离子化合物的阳离子将与金属化合物的一个配位体发生不可逆反应,而它的阴离子有许多亲脂性基团环绕在金属或准金属离子周围。该发明可以下列反应为例说明:
四(五氟苯基)合硼酸三(正丁基)铵tri(n-butyl)ammonium
tetra(pentafluorophenyl)boron
+二甲基化二(环戊二烯基)合锆
→[Cp Zr Me][BPh]+CH+三(正丁基)胺质子化反应所产生的一种副产品是路易斯碱(胺),其中一些能与阳离子配位,因而抑制催化剂的活性。起始材料必须小心选择,以避免产生作为催化毒物的特定的胺类化合物。
碳鎓离子化学——这种方法的说明见“多重的金属一碳键”,R.R.Schrock,P.R.Sharp.J.Am.Chem.Soe.,p.2389-2399,Vol.100,No,8(April,2,1978)。碳鎓离子化学法和质子化方法的共同问题,是它们由于存在于链烯烃和溶剂中的碱性杂质而中毒,常使反应失去控制。聚合反应的反应温度高(超过100℃)、持续时间短,结果使链长度缩短而分子量低。
在没有甲基铝噁烷之类的清除剂存在的情况下,金属茂催化剂对于毒物是敏感的。聚合反应需要高浓度的阳离子,并且常常以反应失去控制或全然不产生聚合物而告终。
因此,本发明的目的之一是提供一种增进链烯烃聚合反应中金属茂催化剂活性的方法。
并且,本发明的一个目的是使用烷基铝作为毒物的清除剂,而该毒物降低了金属茂催化剂的活性。
用烷基铝来改进由质子化、碳鎓离子化学或单电子氧化等方法制成的催化剂的金属茂催化剂活性,也是本发明的一个目的。
降低金属茂催化体系的成本是本发明的进一步目的。
在丙烯的聚合反应中免除甲基铝噁烷(MAO)作为助催化剂也是本发明的目的。
本发明另一个目的,是制出一种金属茂催化剂,它能够不用甲基铝噁烷作为助催化剂而实现受控制的烯烃聚合反应。
这些以及其它目的是通过下面的方法完成的:将烷基铝与链烯烃混合,制备一种金属茂催化剂,然后在没有甲基铝噁烷助催化剂的情况下将该催化剂与烷基铝-烯烃混合物相混合。使该金属茂催化剂是由一种中性的金属茂化合物和一种离子化合物形成的离子对。
本发明涉及不使用甲基铝噁烷助催化剂的烯烃聚合方法,以及用于这一方法的催化剂体系。将一种烷基铝与链烯烃混合,然后引入到离子金属茂催化剂处,该催化剂是把中性金属茂化合物与一种致电离剂混合而制得的。金属茂∶致电离化合物∶烷基铝的摩尔比的范围是从0.5∶1∶0.5到5∶1∶350,更好是0.625∶1∶1.5到1.5∶1∶77,而最好是1∶1∶1。
在金属茂催化剂的新的合成方法的实例中,一种致电离的离子化合物(如四(五氟苯基)合硼酸三苯基碳triphenylcarbeniumtetrakis(pentafluorophenyl)borate与通式为Cp2MRp的中性金属茂甲基衍生物混合而产生下列反应:
将分别溶解于同一种溶剂中的两种反应剂在室温下混合。这样,致电离化合物使金属茂电离,生成离子对,其中的金属茂阳离子就作为催化剂。混合后,将该混合物在实施聚合的条件下加入到链烯烃中。该链烯最好是丙烯。这方法包括在美国专利申请419,046号中,特此参照归并于本申请。
在催化剂合成方法的另一个实例中,有两种组分,第一种是中性的金属茂甲基衍生物,例如二(环戊二烯基)金属化合物,它至少包括一个能与质子反应的取代基,第二种是一种离子化合物,它带有的阳离子能够供给一个质子,而阴离子是许多亲脂性基团和一个金属的配位复合物。该阴离子是庞大而易变的,可使两种化合物反应形成的金属阳离子变得稳定。由阳离子所提供的质子与金属茂的一个配位体发生反应。作为该反应的直接产物或分解产物就被回收而得到一种活性催化剂。这就是上面所说的质子化方法。上述方法包含在欧洲专利申请公布0-277-004号中,特此参照归并于本申请。
金属茂的中性衍生物的通式是Cp2MR’p,其中Cp是环戊二烯基或被取代的环戊二烯基团,每一Cp可以相同或不同,M是III、IV、V或VI族金属,R’是烃基原子团,每个R’可以相同或不同,p等于1到3。M较好的是钛、锆或铪,特别是锆为最好。R’最好是碳原子为数20以下的烷基、芳基、链烯基、烷芳基或芳烷基。金属茂的中性衍生物最好是二甲基·亚乙基双(四氢茚基)合锆或二甲基·亚乙基双(茚基)合锆,特别是二甲基·亚乙基双(茚基)合锆。离子化合物最好是四(五氟苯基)合硼酸N,N-二甲基苯胺。(N,N-dimethylanilinium tetrakis(pentafluorophenyl)boronate.)
在催化剂合成方法的另一个实例中,是将一种金属茂的中性衍生物,如通式为Cp2MR2”或Cp2MR”X的环戊二烯基金属化合物(其中Cp是环戊二烯基或被取代的环戊二烯基,M为III、IV、V或VI族金属,X是卤素,R”是烷基)与一种四苯基硼酸金属化合物相结合。金属茂中的一个X-或R-被四苯基硼酸金属化合物中的金属提取出来,结果形成通式为[Cp2MR]+[BPh4]-的离子对,其中BPh4是四苯基硼酸根阴离子。
将一种烷基铝与一种链烯混合并置于反应温度下,烷基铝的通式是AlR3,其中R是碳原子数小于6的烷基,最好是三甲基铝(TMA)或三乙基铝(TEAl),特别是三乙基铝。链烯是任意的,但以丙烯或乙烯为好,最好是丙烯。将这种烷基铝和链烯的混合物与金属茂催化剂接触。催化剂可以通过任何已知的方法制得,包括但不限于上述这些方法。
催化剂系统是通式为[Cp2MRp-1 #]+[A]-的离子性金属茂催化剂,其中[Cp2MRp-1 #]+是金属茂阳离子,Cp是环戊二烯基或被取代的环戊二烯基,每一Cp可以相同或不相同,M是III、IV、V或VI族金属,R#是氢化物,卤素,酰胺或烃基原子团,第一R#可以相同或不同,除非R是氢化物,那就只能有一个R#是氢化物,p等于1到3,而[A]-是一个阴离子。R#最好是烃基原子团,如碳原子数小于20的烷基,芳基,链烯基,烷芳基或芳烷基,特别是碳原子数小于6个的烷基或烷氧基或者是碳原子数小于10个的芳基。M以IV族金属为较好,例如钛、锆和铪,最好是锆或铪。金属茂阳离子以二甲基·亚乙基双(四氢茚基)合锆,二甲基·亚乙基双(茚基)合锆,二甲基·亚乙基双(茚基)合铪和二甲基·异亚丙基(环戊二烯基-1-芴基)合锆为较好,最好是二甲基·二(四氢茚基)合锆。阴离子以四(五氟苯基)合硼酸根为较好。烷基铝已如上述,最好是TMA或TEAl,特别是TEAl。
对于以下的各组金属茂—致电离剂系统,在添加或不加烷基铝的情况下进行了评价:
1.Et(Ind)2ZrMe2/[Ph3C][BPh4 *]
2.Et(Ind)2HfMe2/[Ph3C][BPh4 *]
3.Et(Ind)2ZrMe2/[Me2PhN][BPh4 *]
4.iPr(Cp-1-Flu)ZrMe2/[Ph3C][BPh4 *]
5.Et(H4Ind)2ZrMe2/[Ph3C][BPh4 *]
6.Et(H4Ind)2ZrMe2/[MePhN][BPh]
其中Et(Ind)ZrMe2是二甲基化乙烯二(茚基)合锆;
iPr(Cp-1-Flu)ZrMe是二甲基化异亚丙基(环戊二烯基-1-芴基)合锆;
Et(H4Ind)2ZrMe2是二甲基化乙烯二(四氢茚基)合锆;
[Ph3C][BPh4 *]是四(五氟苯基)合硼酸三苯基碳;
[Me2PhN][BPh4 *]是四(五氟苯基)合硼酸N,N-二甲基苯胺
本发明已作了普通的说明,下面的例子是本发明的具体实施,以显示其实施方法与优点。应该理解,这些例子是为了阐明说明书和下面的权利要求,而不是以任何方式限制它们。第一组:实施例1
将100mg四(五氟苯基)合硼酸三苯基碳溶解于10ml甲苯中。将60mg Et(Ind)2ZrMe2溶解于10ml甲苯中。再将两种溶液在室温下混合5分钟。
反应器温度置定在50℃,向反应器内泵入11丙烯。将催化剂混合物加入到两端装有球阀的40ml不锈钢高压容器内。将400ml丙烯通过该容器泵入反应器。反应器温度维持在50℃,并将反应器内的物质搅动60分钟。聚合反应结束时,将反应器冷却,并把未反应的丙烯从反应器中排出。
在反应产物在真空中约40℃下干燥12小时。然后称量聚合物并分析其熔点。熔点由差示扫描量热法(DSC)求得。结果见表1。实施例2
重复实施例1中的过程,但将反应器内的物质搅动30分钟。结果见表1。实施例3
重复实施例1中的过程,但反应器内物质的置定点温度置定在70℃。结果见表1。实施例4
将0.32毫摩尔三甲基铝(TMA)溶解于5ml甲苯中,加入到处于5磅/平方英寸氮气下的21 Zipperclave反应器中。反应器温度置定在70℃,并将11丙烯泵入反应器。将混合物在1200rpm速度下搅动10分钟。
将100mg四(五氟苯基)合硼酸三苯基碳溶解于10ml甲苯中。将60mg Et(Ind)2ZrMe2溶解于10ml甲苯中。再将两种溶液在室温下混合5分钟。
将催化剂混合物加入到两端装有球阀的40ml不锈钢高压容器内。将400ml丙烯通过该容器泵入反应器。反应器温度保持在70℃,并将反应器内的物质搅动60分钟。聚合反应结束时,将反应器冷却,并把未反应的丙烯从反应器中排出。
把反应产物在真空中约40℃下干燥12小时。然后称量聚合物并分析其熔点。熔点由差示扫描量热法(DSC)求得。结果见表1。实施例5
重复实施例4中的过程,但使用0.33mmol三乙基铝(TEAl),并将反应器内的物质搅动10分钟。结果见表1。实施例6
重复实施例4中的过程,但使用0.33mmol三乙基铝(TEAl),5mg四(五氟苯基)合硼酸三苯基碳和30mg Et(Ind)ZrMe。反应器内的物质搅拌5分钟。结果见表1。实施例7
重复实施例4中的过程,但使用0.33mmol三乙基铝(TEAl),16mg[Ph3C][BPh4 *]和10mg Et(Ind)2ZrMe2。反应器内的物质搅动10分钟。结果见表1。实施例8
重复实施例4中的过程,但使用0.66mmol三乙基铝(TEAl),8mg[Ph3C][BPh4 *]和2.5mg Et(Ind)2ZrMe2。将反应器内物质搅动60分钟。结果见表1。实施例9
重复实施例4中的过程,但使用0.66mmol三乙基铝(TEAl),8mg[Ph3C][BPh4 *]和1.25mg Et(Ind)2ZrMe2。将反应器内物质搅动60分钟。结果见表1。实施例10
重复实施例4中的过程,但使用0.66mmol三乙基铝(TEAl),8mg[Ph3C][BPh4 *]和2.5mg Et(Ind)2ZrMe2。将反应器内物质搅动30分钟。结果见表1。实施例11
重复实施例4中的过程,但使用0.66mmol三乙基铝(TEAl),8mg[Ph3C][BPh4 *]和2.5mg Et(Ind)2ZrMe2。将反应器内物质搅动40分钟。结果见表1。实施例12
重复实施例4中的过程,但使用0.33mmol三乙基铝(TEAl),8mg[Ph3C][BPh4 *]和5mg Et(Ind)2ZrMe2。将反应器内物质搅动30分钟。结果见表1。实施例13
重复实施例4中的过程,但使用5mg的Et(Ind)2ZrMe2,8mg[Ph3C][BPh4 *],0.66mmol三乙基铝,而反应时间为30分钟。结果见表1。实施例14
重复实施例4中的过程,但使用2.5mg Et(Ind)2ZrMe2,8mg[Ph3C][BPh4 *],0.66mmol三乙基铝,而反应时间为60分钟。结果见表1。实施例15
重复实施例4中的过程,但使用2.5mg Et(Ind)2ZrMe2,4mg[Ph3C][BPh4 *],0.66mmol TEAl,而反应时间为30分钟。结果见表1。实施例16
重复实施例4中的过程,但使用2.5mg的Et(Ind)2ZrMe2,4mg[Ph3C][BPh4 *],0.99mmol TEAl,而反应时间为30分钟。结果见表1。实施例17
重复实施例4中的过程,但使用2.5mg的Et(Ind)2ZrMe2,24mg[Ph3C][BPh4 *],0.66mmol TEAl,而反应时间为30分钟。结果见表1。实施例18
重复实施例4中的过程,但使用2.5mg的Et(Ind)2ZrMe2,24mg[Ph3C][BPh4 *],2.00mmol TEAl,而反应时间为30分钟。结果见表1。第二组:实施例19
重复实施例4中的过程,但使用20mg的Et(Ind)2HfMe2,80mg的[Ph3C][BPh4 *],0.42mmol TMA,而反应时间为30分钟。结果见表1。第三组:实施例20
重复实施例1中的过程,但使用2.5mg的Et(Ind)2ZrMe2,7mg的[Me2PhN][BPh4 *],而反应时间为60分钟。结果见表1。实施例21
重复实施例4中的过程,但使用2.5mg的Et(Ind)2ZrMe2,7.0mg[Me2PhN][BPh4 *],0.66mmol的TEAl,而反应时间为5分钟。结果见表1。实施例22
重复实施例4中的过程,但使用0.66mmol的TEAl,7.0mg的[Me2PhN][BPh4 *]和2.5mg Et(Ind)2ZrMe2。将反应器内物质搅动25分钟。结果见表1。实施例23
重复实施例4中的过程,但使用0.66mmol的TEA1,3.5mg的[Me2PhN][BPh4 *]和2.5mg Et(Ind)2ZrMe2。将反应器内物质搅动30分钟。结果见表1。实施例24
重复实施例4中的过程,但使用1.25mg的Et(Ind)2ZrMe2,3.5mg的[Me2PhN][BPh4 *],0.66mmol的TEA1,而反应时间为60分钟。结果见表1。实施例25
重复实施例4中的过程,但使用0.625mg的Et(Ind)2ZrMe2,1.75mg的[Me2PhN][BPh4 *],0.66mmol的TEAl,而反应时间为60分钟。结果见表1。第四组:实施例26
重复实施例1中的过程,但使用40mg的iPr(Cp-l-Flu)ZrMe2,60mg的[Ph3C][BPh4 *],而反应时间为60分钟。结果见表1。实施例27
重复实施例1中的过程,但使用60mg的iPr(Cp-1-Flu)ZrMe2,100mg的[Ph3C][BPh4 *],而反应时间为60分钟。结果见表1。实施例28
重复实施例4中的过程,但使用60mg的iPr(Cp-1-Flu)ZrMe2,100mg的[Ph3C][BPh4 *],0.16mmol的TMA,而反应时间为60分钟。结果见表1。实施例29
重复实施例4中的过程,但使用0.48mmol的TMA,100mg的[Ph3C][BPh4 *],60mg的iPr(Cp-1-Flu)ZrMe2,而反应时间为60分钟。结果见表1。实施例30
重复实施例4中的过程,但使用20mg的iPr(Cp-1-Flu)ZrMe2,60mg的[Ph3C][BPh4 *],0.16mmol的TMA,而反应时间为60分钟。结果见表1。第五组:实施例31
重复实施例1中的过程,但使用15mg的Et(H4Ind)2ZrMe2,30mg的[Ph3C][BPh4 *],而反应时间为60分钟。结果见表1。实施例32
重复实施例1中的过程,但使用20mg的Et(H4Ind)2ZrMe2,40mg的[Ph3C][BPh4 *],而反应时间为60分钟。结果见表1。实施例33
重复实施例1中的过程,但使用20mg的Et(H4Ind)2ZrMe2,40mg的[Ph3C][BPh4 *],而反应时间为5分钟。结果见表1。实施例34
重复实施例4中的过程,但使用2.5mg的Et(H4Ind)2ZrMe2,8mg的[Ph3C][BPh4 *],0.66mmol的TEAl而反应时间为60分钟。结果见表1。第六组实施例35
重复实施例1中的过程,但使用50mg的Et(H4Ind)2ZrMe2,40mg的[Me2PhN][BPh4 *],而反应时间为120分钟。结果见表1。实施例36
重复实施例4中的过程,但使用2.5mg的Et(H4Ind)2ZrMe2,9.2mg的[Me2PhN][BPh4 *],0.66mmol的TEA1,而反应时间为60分钟。结果见表1。
以下是上述使用本发明的方法所作的各次试验的结果。
表I
催化剂 致电离剂 烷基铝 反应时间试验号
umol(mg) umol(mg) mmol min
Et(Ind)2ZrMe2 [Ph3c][BPh* 4]1 159(60) 109(100) 0 602 159(60) 109(100) 0 303 159(60) 109(100) 0 604 159(60) 109(100) TMA 0.32 605 159(60) 109(100) TEAl 0.33 106 80(30) 54(50) 0.33 57 26.5(10) 17.3(16) 0.33 108 6.63(2.5) 8.64(8) 0.66 609 3.36(1.25) 8.64(8) 0.66 6010 6.63(2.5) 8.64(8) 0.66 3011 6.63(2.5) 8.64(8) 0.66 4012 13.3(5) 8.6(8) 0.33 3013 13.3(5) 8.64(8) 0.66 3014 6.63(2.5) 8.64(8) 0.66 6015 6.63(2.5) 4.3(4) 0.66 3016 6.63(2.5) 4.3(4) 0.99 3017 6.63(2.5) 26(24) 0.66 3018 6.63(2.5) 26(24) 2.00 30
Et(Ind)2HfMe2 [Ph3C][BPh* 4]19 53(20) 85(80) TMA 0.42 30
Et(Ind)2ZrMe2 [Me2PhN][BPh* 4]20 5.6(2.5) 8.7(7.0) 0 6021 6.6(2.5) 8.7(7.0) TEAl 0.66 522 6.6(2.5) 8.7(7.0) 0.66 2523 3.3(1.25) 4.35(3.5) 0.66 3024 3.3(1.25) 4.35(3.5) 0.66 6025 1.65(.0625) 2.175(1.75) 0.66 60
iPr(cp-l-Flu)zrMe2 [Ph3C][BPh* 4]26 102(40) 65(60) 0 6027 154(60) 109(100) 0 6028 154(60) 109(100) TMA 0.16 6029 154(60) 109(100) 0.48 6030 51(20) 65(60) 0.16 60
Et(H4Ind)2ZrMe2 [Ph1C][Bph* 4]31 40(15) 33(30) 0 6032 53(20) 44(40) 0 6033 80(30) 67(60) 0 534 7(2.5) 8.8(8.0) TEAl 0.66 60
Et(H4Ind)2ZrMe2 [Me2PhU][BPh* 4]35 133(50) 44(40) 0 12036 7(2.5) 10(9.2) TEAl 0.66 60
表I(续)试验号 聚合温度 产量 熔点
(℃) (gms) (℃)
1 50 19 137
2 50 11 125
3 70 8 126
4 70 270 124
5 70* 340 126
6 70* 432 No Melt
7 70* 260 118
8 70 319 129
9 70 89 132
10 70 117
11 70* 377 131
12 70 22 132
13 70 51 131
14 70* 357 127
15 70 9 132
16 70 11 134
17 70 149 131
18 70 62 130
19 70 51 131
20 70 - -
21 70* 106 125
22 70* 405 127
23 70* 434 127
24 70 385 131
25 70 253 131
26 80 2 -
27 70 51 -
28 70* 284 116
29 70* 268 117
30 70* 156 116
31 50 2 142
32 50 35 138
33 120 70 127
34 70 154 115
35 50 50 133
36 70 116 116*反应放热引起升温:反应温度提高了10℃以上。
本发明所描述的方法合成出在烯烃聚合反应中用作催化剂的阳离子。本发明制备催化剂的方法可制得高活性的催化剂,并减少可能抑制催化剂活性的副产物。这种新的合成方法也减少了存在于溶剂中而可能抑制催化剂活性的催化毒物。
试验证明,在离子金属茂催化剂体系中加入某种烷基铝,结果得到可重演,可控制,而且高效率的聚合反应。加入烷基铝,就提供了一种对催化毒物的清除剂。所加的烷基铝数量较少,而且烷基铝也较便宜。金属茂阳离子/烷基铝组合是比单独的阳离子更好的催化剂体系,并且始终有高活性。
显然,根据上面的学说,可以对本发明作各种改变或修正。因此应当理解,在所附权利要求的范围内,本发明能以这里具体描述之外的其它方式实施。
Claims (13)
1.一种链烯烃聚合的方法,其特征在于它包括:
(a)将通式为AlR3的烷基铝与一种烯烃混合,其中R是具有6个碳原子以下的烷基;
(b)制备一种金属茂催化剂,该催化剂是由中性金属茂化合物与一种致电离化合物生成的离子对,所述中性金属茂的通式为Cp2MR* 2,其中Cp是环戊二烯基或被取代的环戊二烯基,每个Cp可以相同或不同,M选自IVB族钛、锆和铪,R*是低级烃基;
而其中的致电离化合物选自四(五氟苯基)合硼酸三苯基碳或四(五氟苯基)合硼酸N,N-二甲基苯胺;
而中性金属茂化合物∶致电离化合物∶烷基铝的摩尔比在0.5∶1∶0.5至5∶1∶350范围内;
(c)将上述催化剂与烷基铝-烯烃混合物混合;
(d)将催化剂-烷基铝-烯烃混合物维持在实施液相聚合的条件下:
以及
(e)提取聚烯烃。
2.如权利要求1所述的方法,其特征在于其中金属茂:致电离化合物∶烷基铝的摩尔比的范围是由0.625∶1∶1.5到1.5∶1∶77。
3.如权利要求2所述的方法,其特征在于其中金属茂∶致电离化合物∶烷基铝的摩尔比是1∶1∶1。
4.如权利要求3所述的方法,其特征在于其中烷基铝选自由三乙基铝和三甲基铝构成的一组物质。
5.如权利要求4所述的方法,其特征在于其中烷基铝是三乙基铝。
6.如权利要求1所述的方法,其特征在于其中的链烯烃是丙烯。
7.如权利要求5所述的方法,其特征在于其中M是铪或锆。
8.如权利要求7所述的方法,其特征在于其中的中性金属茂化合物为其甲基衍生物,它选自下列下列一组物质:二甲基·亚乙基双(四氢茚基)合锆,二甲基·亚乙基双(茚基)合锆,二甲基·亚乙基双(茚基)合铪,和二甲基·异亚丙基(环戊二烯-1-芴基)合锆。
9.如权利要求8所述的方法,其特征在于其中致电离的离子化合物是四(五氟苯基)合硼酸三苯基碳。
10.如权利要求1所述的方法,其特征在于其中M为锆。
11.如权利要求8所述的方法,其特征在于其中的中性金属茂甲基衍生物选自下列一组物质:二甲基·亚乙基双(四氢茚基)合锆和二甲基·亚乙基双(茚基)合锆。
12.如权利要求11所述的方法,其特征在于其中的中性金属茂甲基衍生物是二甲基·亚乙基双(茚基)合锆。
13.如权利要求11或12所述的方法,其特征在于其中致电离的离子化合物是四(五氟苯基)合硼酸N,N-二甲基苯胺。
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-
1990
- 1990-10-09 ES ES90870175T patent/ES2086397T5/es not_active Expired - Lifetime
- 1990-10-09 EP EP90870175A patent/EP0426638B2/en not_active Expired - Lifetime
- 1990-10-09 DE DE69026679T patent/DE69026679T3/de not_active Expired - Fee Related
- 1990-10-09 CA CA002027122A patent/CA2027122C/en not_active Expired - Fee Related
- 1990-10-09 AT AT90870175T patent/ATE137247T1/de not_active IP Right Cessation
- 1990-10-10 KR KR1019900016067A patent/KR100196613B1/ko not_active IP Right Cessation
- 1990-10-29 JP JP2288600A patent/JP2939321B2/ja not_active Expired - Lifetime
- 1990-10-30 CN CN90108885A patent/CN1037686C/zh not_active Expired - Fee Related
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1992
- 1992-02-04 US US07/830,812 patent/US5519100A/en not_active Expired - Lifetime
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1994
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Also Published As
Publication number | Publication date |
---|---|
ES2086397T3 (es) | 1996-07-01 |
EP0426638A3 (en) | 1991-08-07 |
CN1051365A (zh) | 1991-05-15 |
CA2027122A1 (en) | 1991-05-01 |
EP0426638A2 (en) | 1991-05-08 |
US5519100A (en) | 1996-05-21 |
KR100196613B1 (ko) | 1999-06-15 |
ATE137247T1 (de) | 1996-05-15 |
CN1037685C (zh) | 1998-03-11 |
KR910007974A (ko) | 1991-05-30 |
DE69026679D1 (de) | 1996-05-30 |
JPH03207704A (ja) | 1991-09-11 |
JP2939321B2 (ja) | 1999-08-25 |
EP0426638B1 (en) | 1996-04-24 |
DE69026679T2 (de) | 1996-09-26 |
CN1111641A (zh) | 1995-11-15 |
EP0426638B2 (en) | 2005-03-02 |
CA2027122C (en) | 2002-12-10 |
DE69026679T3 (de) | 2005-10-06 |
ES2086397T5 (es) | 2005-07-16 |
US5614457A (en) | 1997-03-25 |
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