CN1033859C - 含路易斯酸和烷基铝的金属茂催化剂及其制备方法 - Google Patents

含路易斯酸和烷基铝的金属茂催化剂及其制备方法 Download PDF

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CN1033859C
CN1033859C CN90109368A CN90109368A CN1033859C CN 1033859 C CN1033859 C CN 1033859C CN 90109368 A CN90109368 A CN 90109368A CN 90109368 A CN90109368 A CN 90109368A CN 1033859 C CN1033859 C CN 1033859C
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lewis acid
catalyst system
aluminum alkyls
zirconium
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约翰·尤恩
迈克尔·J·埃尔德
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Abstract

本发明是关于一种催化剂体系，它含有中性的金属茂化合物，烷基铝和路易斯酸。路易斯酸的酸度必须足以使中性的金属茂化合物离介生成阳离子金属茂催化剂。路易斯酸的配位体应当是不与金属茂阳离子反应的。任何一种有与一个过渡金属相连的两个环戊二烯环的金属茂催化剂化合物均对本发明有用。

Description

含路易斯酸和烷基铝的金属茂催化剂及其制备方法
本发明一般说是关于一种改进的催化剂体系以及该催化剂体系的制备方法，具体地说，是关于一种含路易斯酸和烷基铝的金属茂化合物的催化剂体系及其制备方法。
用金属茂化合物作为烯烃聚合的催化剂是众所周知的。德国专利申请No.2608863公开了种用于乙烯聚合的催化剂体系，它由二烷基双(环戊二烯基)钛、三烷基铝和水组成。德国专利申请No.2608933公开了一种乙烯聚合催化剂体系，它由通式为(环戊二烯基)nZrY4－n′的锆金属茂组成，式中Y代表R1CH2AlR2、CH2CH2AlR2和CH2CH(AlR2)2其中R为烷基或金属取代的烷基，n是1-4的数；该金属茂催化剂与三烷基铝助催化剂和水结合起来使用。
用金属茂作为乙烯和其它α-烯烃共聚合催化剂也是现有技术中众所周知的。美国专利No.4542199中Kaminsky等人公开了一种烯烃的聚合方法，特别是聚乙烯的制备方法以及乙烯和其它α-烯烃共聚物的制备方法。所公开的催化剂体系包括通式为(环戊二烯基)2meHRal的一种催化剂，式中R为卤素，环戊二烯基或C1-C6的烷基，me是过渡金属，特别是锆，Hal是卤素，特别是氯。该催化剂体系也包括一种铝氧烷，其通式(对线型分子)为Al2OR4(Al(R)-O)n和/或(对环状分子)为(Al(R)-O)n＋2，式中n是4-20的一个数，R是甲基或乙基。在美国专利4404344中也公开了一种类似的催化剂体系。
美国专利No.4530914公开了一种具有宽分子量分布，特别是双峰值或多峰值分子量分布的乙烯-聚乙烯聚合的催化剂体系。该催化剂体系至少含有两种不同的金属茂和一种铝氧烷。该专利所公开的金属茂在两个环戊二烯基的环之间可以有一个桥，这个桥使那些环具有立体刚性。
欧洲专利公开No0185918公开了一种用于烯烃聚合的立体刚性的手性锆金属茂催化剂。该申请中没有说明铪可以代替锆用来生产有用的聚合产品。该申请所公开的两个环戊二烯基之间的桥是一种C1-4的或C3-6的环型烃。
烯烃的聚合主要是用Zeigler-Natta催化剂。有一类Zeigler-Natta催化剂是周期表第IV族金属的金属茂化合物，并用甲基铝氧烷(MAO)作为助催化剂。用钛或锆的金属茂催化剂和铝氧烷助催化剂生产全同立构聚丙烯的一种体系，已在J.Am.Chem.Soc.Vol，106，pp6355-64，1984“在用可溶性4B族金属茂/甲基铝氧烷催化剂的丙烯聚合中立体化学控制机理”一文中作了阐述。该文章指出，用乙烯-桥茚基衍生物的外消旋对映体的手性催化剂所得的是按常规结构的等规立构聚丙烯，这种结构可用对映位置的立体化学控制模型予测。然而，用内消旋非手性型乙烯-桥接的钛茚基非对映体和非手性的锆茂衍生物所生产的聚丙烯具有纯无规结构。
MAO使金属茂活化而使其能促进α-烯烃的聚合。其它铝的有机金属化合物，例如三甲基铝(TMA)或二甲基卤化铝，都是众所周知它们自己不会促进聚合反应的。不管是烷基铝还是二甲基卤化铝，它们都不能单独作为有效的助催化剂。
将TMA和二甲基氟化铝(DMF)组合起来作为一种助催化剂来代替MAO，现在已被证明是有效的。DMF是一种路易斯酸。这样的组合，在以下这篇文章中有报导，即“丙烯的等规聚合：以4族金属的茂化合物为基础没有甲基铝氧烷的均相催化剂”，AZambelli.P.Longo和A.Grassi.Macromolecules，Vol.22.P.2186-2189，1989。用TMA/DMF制备的聚合物，其立体化学结构与用MAO制备的聚合物很相似。但是用TMA/DMF混合物所得到的聚合产率均大大低于用MAO所得的产率。
含氯化镁的金属茂化合物所形成的一种催化剂体系具有二甲基双(环成二烯基)钍，它对乙烯聚合是有效的这也已有报导。这样的组合，报导在下面这篇文章中，即“〔(CH3)5C5〕2Th(CH3)2表面化学和催化。在mgcl2上表面烷基化和乙烯插入/聚合的NMR光谱直接观察”，D.Heddin和T.J.Marks，J，Am，Chem.Soc，Vol.110，No.5.1988。从环戊二烯基化合物中提取甲基形成阳离子。甲基与镁配位形成镁阴离子。氯化镁是一种路易斯酸。
在没有清除剂(如甲基铝氧烷)存在的情况下，金属茂催化剂很易中毒。聚合反应要求高的离子浓度，并常常发生反应失控或根本没有生成聚合物而终止的情况。
本发明提供一种有路易斯酸和烷基铝的金属茂化合物的催化剂体系，以及一种使用该改进的催化剂体系进行链烯烃聚合的方法。按照本发明，可以生产由α-烯烃聚合得到的均聚物或共聚物。聚合物链的增长是在金属茂化合物的中性烷基衍生物存在下进行的，该金属茂化合物已经与路易斯酸和烷基铝接触。任何金属茂催化剂化合物只要有两个与过渡金属配位的环戊二烯环，都可用于本发明。
将该催化剂与路易斯酸接触，烷基铝与烯烃接触。这两种混合物在聚合条件下相互接触。
本发明是关于一种含金属茂催化剂，路易斯酸和烷基铝的催化剂体系，及其制备方法。
金属茂催化剂的通式是：
                     Cp2MRp其中Cp是环戊二烯基或取代的环戊二烯基，每个Cp是相同的或不相同的，M是III.IV.V或VI族金属，R是氢化物，卤素，酰胺或烃基，每个R相同或不相同(除了只有一个R是氢化物之外)，而p是1-4。M优选的是IV族金属，如钛、锆或铪，最好是锆。R优选的是有20个以下碳原子的烷基、芳基、链烯基、烷芳基或芳烷基。R最好是6个以下碳原子的烷基或烷氧基，或者10个以下碳原子的芳基。金属茂的中性衍生物优选的是二甲基双(四氢茚基)锆或二甲基亚乙基双(茚基)锆，最好是二甲基亚乙基双(茚基)锆。
本发明用的路易斯酸是能接受电子对的任何物质，其酸度足以使中性的金属茂离解成阳性金属茂催化剂。另外，路易斯酸的配位体不能与金属茂的阳离子反应。优选的路易斯酸是含硼的或是氯化镁(MgCl2)，最好是三(五氟苯基)硼。
烷基铝的通式是AlR3，其中R是卤素、氧、氢化物、烷基、烷氧基或芳基，每个R是相同或不相同的，而且至少一个R是烷基。较佳的烷基铝是三甲基铝(TMA)或三乙基铝(TEAL)，最佳的烷基铝是三乙基铝。
本发明在实施时，烷基铝与烯烃是混合的。将路易斯酸溶解在非极性溶剂中，或在非极性溶剂中拌成浆。将中性的金属茂催化剂分开溶解在相同的溶剂中。再将该路易斯酸混合物和催化剂混合物合并。合并后的混合物与烯烃和烷基铝的共混物相接触。金属茂∶路易斯酸∶烷基铝的摩尔比范围从0.01∶1∶0.1至5∶1∶350，较佳的是从0.5∶1∶0.5至4∶1∶25，最佳的摩尔比范围，对于溶解在非极性溶剂中的路易斯酸是0.02∶1∶1，对于在非极性溶剂中形成浆状的路易斯酸是0.01∶l∶1。
用金属茂催化剂对烯烃的聚合可通过任何已知的烯烃聚合方法来完成，例如本体聚合，淤浆聚合或气相聚合。对于聚丙烯，聚合温度范围从-80℃到150℃，优选25℃-90℃。最优选50℃-80℃。
在加和不加烷基铝以及加和不加路易斯酸的条件下对以下的催化剂体系进行了评价。1.iPr(Cp-1-Flu)ZrMe2/F15/TEAl(TMA)2.iPr(Cp-1-Flu)ZrMe2/MgCl2/TEAl3.Et(Ind)2ZrMe2/F15/TEAl4.Et(Ind)2ZrMe2/MgCl2/TEAlEt(Ind)2ZrMe2是二甲基亚乙基双(茚基)锆，
iPr(Cp-1-Flu)ZrMe2是二甲基异亚丙基(环戊二烯基-1-芴基)锆和F15是三(五氯苯基)硼。
烷基铝和路易斯酸结合使用，这对于聚合反应的再现，控制及提高效率来说，均是必要的。
以上已对本发明作了一般的说明，现给出以下一些例子作为本发明的具体实施方案，用它们来证明本发明的可行性和优点。当然这是以举例说明本发明的方法来给出实施例，而不是想把说明书或权利要求限制到一定要按什么方式实施。第一组                    例1
将0.16毫摩尔三乙基铝(TEAl)溶解在5ml的甲苯中并在5psig[3.4×104pa(表压)]的氮压下将它加到2升的Zipperclave反应器中。反应器的温度调到70℃，将1升的丙烯泵入反应器。该混合物在1200rpm速度下搅拌10分钟。
将35毫克ipr(Cp-1-Flu)Zrme2溶解在10毫升的二甲苯中。将该催化剂加到一个每端都装球形阀的40毫升不锈钢弹性储气瓶中。把400毫升丙烯通过此瓶泵入反应器内。该反应器的温度维持在70℃并对反应器内的物料搅拌30分钟。聚合反应结束后，冷却反应器并从反应器中排出未反应的丙烯。此实施例中没有反应产物。结果示于表I。
                        例2
将0.33毫摩尔的三乙基铝(TEAl)溶解在5毫升甲苯中并加到一个Zipperclave反应器中。反应器温度调至70℃时加入1.0升丙烯。将该混合物在1200rpm速度下搅拌15分钟。
在5毫升二甲苯中溶解78.6毫克三(五氟苯基)硼使之形成无色溶液。将60毫克ipr(Cp-1-Flu)ZrMe2溶解在10毫升二甲苯中形成黄色溶液。这两种溶液混合在一起形成红色的溶液，该溶液在室温下混合5分钟。
将该催化剂混合物加到一个50毫升不锈钢弹状储气瓶中。把200毫升丙烯通过此瓶泵入反应器内。反应器内的物料搅拌30分钟。反应器温度升至90℃。
将未反应的丙烯从反应器中排出，用丙酮洗涤反应产物并在真空中干燥。
分析测定聚合物的溶点和分子量。熔点是由差示扫描量热法(DCS)测得。用凝胶渗透色谱(Gpe)分析法计算得到分子量。结果示于表I。
                例3
重复例2的方法，使用0.33毫摩尔三乙基铝(TEAl)，27毫克三(五氟苯基)硼和20毫克ipr(Cp-1-Flu)-ZrMe2。反应器中的物料搅拌30分钟，结果示于表I。
                例4
重复例2的方法，使用0.16毫摩尔三乙基铝(TEAL)，46毫克三(五氟苯基)硼和15毫克ipr(Cp-1-Flu)-ZrMe2。反应器中的物料搅拌30分钟。结果示于表I。
                例5
重复例2的方法，使用0.10毫摩尔三乙基铝(TEAL)，46毫克三(五氟苯基)硼和35毫克ipr(Cp-1-Flu)ZrMe2。反应器中的物料搅拌30分钟。结果示于表I。
                例6
重复例2的方法，使用0.16毫摩尔三乙基铝(TEAL)，46毫克三(五氟苯基)硼和35毫克ipr(Cp-1-Flu)-ZrMe2。反应器的物料搅拌30分钟。结果示于表I。
                例7
重复例2的方法，使用0.33毫摩尔三乙基铝(TEAL)，46毫克三(五氟苯基)硼和35毫克ipr(Cp-1-Flu)-ZrMe2。反应器的物料搅拌30分钟。未反应的丙烯从反应器中排出。没有反应产物。结果示于表I。
                例8
重复例2的方法，使用0.16毫摩尔三乙基铝(TEAL)，46毫克三(五氟苯基)硼和35毫克ipr(Cp-1-Flu)-ZrMe2。反应器中的物料搅拌30分钟。结果示于表I。第2组                    例9
将0.16毫摩尔的三乙基铝(TEAl)溶解在5毫升甲苯中，并在5psig[3.4×104Pa(表压)]氮压下将它加到一个2升的Zipperclave反应器中。
反应器温度调至60℃后泵入1升丙烯。该混合物在1200rpm速度下搅拌10分钟。
将86毫克MgCl2在5毫升甲苯中调成浆。将18毫克ipr(Cp-1-Flu)ZrMe2，通入MgCl2浆液中。将该混合物搅拌12小时得到一种暗紫色的悬浮液。
将该催化剂混合物加到一个50毫升的不锈钢弹状储气瓶中，将200毫升丙烯通过该瓶泵入反应器中。反应器内物料搅拌30分钟。将未反应的丙烯从反应器中排出，然后用稀HCl的甲醇溶液反应产物，再在真空烘箱中干燥。
分析测定该聚合物的熔点和分子量。熔点是从差示扫描量热法(DCS)测得。分子量用凝胶渗透色谱(GPC)分析法计算得到。结果示于表I。第3组                    例10
将1升丙烯加到Zipperclave反应器中。反应温度调至70℃。将78.6毫克三(五氟苯基)硼溶解在5毫升甲苯中，58毫克Et(Ind)2ZrMe2溶介在18毫升甲苯中。把这两种溶液混合在一起在室温下混合5分钟。
将该催化剂混合物加到一个50毫升不锈钢弹状储气瓶中。通过该瓶泵入反应器200毫升丙烯。反应器温度保持在70℃，并搅拌反应器中物料35分钟。将未反应的丙烯从反应器中排出。没有反应产物。结果列于表I。
                例11
将0.33毫摩尔三乙基铝(TEAL)溶解在5毫升非配位溶剂中并把它加到一个Zipperclave反应器中。反应器定点温度调到70℃并往反应器加入1.0升丙烯。将该混合物在1200rpm转速下搅拌10分钟。
将78.6毫克三(五氟苯基)硼溶解在5毫升甲苯中形成无色溶液。58毫克Et(Ind)2ZrMe2溶解在10毫升甲苯中形成淡黄色溶液。将这两种溶液混在一起形成透明的暗黄溶液，在室温下混合5分钟。
将该催化剂混合物加到一个50毫升不锈钢弹状储气瓶中。通过此瓶往反应器中泵入200毫升丙烯。把反应器温度升至95℃以上并将反应器内物料搅拌6分钟。从反应器排出未反应的丙烯。用丙酮洗涤反应产物并在真空中干燥。
分析测定该聚丙烯反应产物的熔点和分于量。熔点是从差示扫描量热法(DCS)测得。分子量用凝胶渗透色谱(GPC)分析法计算得到。结果示于表I。
                例12
重复例11的方法，使用0.66毫摩尔TEAL，27毫克三(五氟苯基)硼和20毫克Et(Ind)2ZrMe2。反应器中物料搅拌22分钟。结果示于表I。
                例13
重复例11的方法，使用0.33毫摩尔TEAL，2.5毫克三(五氟苯基)硼和2.5毫克Et(Ind)2ZrMe2。反应器内物料搅拌30分钟。结果示于表I。
                例14
重复例11的方法，使用0.66毫摩尔TEAL，102毫克三(五氟苯基)硼和2.5毫克Et(Ind)2ZrMe2。将反应器中物料搅拌30分钟。结果示于表I。
                例15
重复例11的方法，使用0.66毫摩尔TEAL，154毫克三(五氟苯基)硼和2.5毫克Et(Ind)2ZrMe2。反应器中物料搅拌30分钟。结果示于表I
                例16
重复例11的方法，使用0.66毫摩尔TEAL，308毫克三(五氟苯基)硼和2.5毫克Et(Ind)2ZrMe2。反应器的物料搅拌30分钟。结果示于表I。第4组                例17
重复例9的方法，用352毫克氯化镁，40毫克Et(Ind)：ZrMe2，0.66毫摩尔TEAL，搅拌时间30分钟。结果示于表I。
                例18
重复例9的方法，用352豪克氯化镁，10毫克Et(Ind)2ZrMe2，0.66毫摩尔TEAL，搅拌时间30分钟。结果列于表I。
                例19
重复例9的方法，用124毫克氯化镁，40毫克Et(Iad)2ZrMe2，0.66毫摩尔TEAL，搅拌时间30分钟。结果示于表I。
对于F15催化剂体系，将B∶Zr摩尔比提高到大大超过1∶1时，得到较高催化效率。这意洁着低效率的部分原因是由于没有被F15完全离子化。
从以上的认识，本发明的许多改进和各种各样的变更显然都是可能的。因此可以理解到，本发明所提的权利要求范围之内，除了在说明书中特别说明之外，都是可以实施的。
上述例中，Zipperclave反应器为：一不锈钢制的批量反应器，通常装上汽套使用蒸汽、热水或用于控制温度的冷水，带有电磁搅拌器及控制压力的进出汽口。常用于实验室中，以测试催化剂和聚合条件。例号  催化剂                 路易斯酸     烷基铝 反应时间#    umol(mg)               umol(毫克)   毫摩尔   分钟
 ipr(Flu)(Cp)ZrMe2  B(C6F5)3  TEAL    301    89.8(35)               0             0.162    153(60)                153(78.6)     0.33    303    51.2(20)               52.73(27)     0.33    304    38.4(15)               89.8(46)      0.16    305    89.5(35)               89.8(46)      0.10    306    89.5(35)               89.8(46)      0.16    307    89.5(35)               89.8(46)      0.33    30
                                      TMA8    89.5(35)               89.8(46)      0.16    30
                        MgCl2        TEAL9    45(18)                 900(86)       0.66    30
 Et(Ind)2ZrMe2        B(C6F5)310   154(58)                154(78.6)     0       35例号   催化剂             路易斯酸     烷基铝     反应时间#     umol(mg)           umol(毫克)   毫摩尔      分钟11    154(58)            154(78.6)    0.33         612    53(20)             53(27)       0.66        2213    6.6(2.5)           6.6(2.5)     0.33        3014    6.6(2.5)           200(102)     0.66        3015    6.6(2.5)           300(154)     0.66        3016    6.6(2.5)           600(308)     0.66        30
  Et(Ind)2ZrMe2    MgCl2      TEAL17    106(40)            3700(352)    0.66        3018    27(10)             3700(352)    0.66        3019    106(40)            1300(124)    0.66        30例号  聚合温度 产量  熔点   分子量  分子量#        ℃          ℃    X1000    分布1        70     0     -      -       -2        70    123          57.6    1.93        70     7    110    64.3    2.04        70     585        70     5    105    39      2.06        70    168   105    61      1.97        70    110   123    55      2.08        70    1679        60     6    131    57      2.010       70     0     -      -       -11       70    117   113    15      4.212       70     70   122    17.5    3.513       70     014       70     1    127    26      2.815       70     90   130    20      5.116       70     33   129    25      3.717       70     49   133    31      1.918       70     47   130    29      2.419       70     8    130    30      2.0

Claims (21)

1.一种催化剂体系，其特征在于，所述催化剂体系含有：
a)一种中性金属茂化合物；
b)一种烷基铝；
c)一种路易斯酸；
其中中性金属茂化合物的通式为：
                     Cp2MRP
式中Cp是环戊二烯基或取代的环戊二烯基，每个Cp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，除了只有一个R是氢化物之外，每个R相同或不相同，P是1-4，
其中路易斯酸为选自含硼和氯化镁的路易斯酸。
2.一种如权利要求1所述的催化剂体系，其特征在于，其中R是选自由烷基、芳基、链烯基、烷芳基和芳烷基组成的组中有20个以下碳原子的烃基。
3.一种如权利要求2所述的催化剂体系，其特征在于，其中R是6个以下碳原子的烷基或烷氧基，或者10个以下碳原子的芳基。
4.一种如权利要求1所述的催化剂体系，其特征在于，其中M是IV族金属选自由钛、锆和铪组成的组。
5.一种权利要求4所述的催化剂体系，其特征在于，其中金属茂的中性甲基衍生物选自由二甲基亚乙基(茚基)锆和二甲基异亚丙基(环戊二烯基-1-芴基)锆组成的组。
6.一种如权利要求1所述的催化剂体系，其特征在于，其中烷基铝选自三乙基铝和三甲基铝。
7.一种如权利要求6所述的催化剂体系，其特征在于，其中烷基铝是三乙基铝。
8.一种如权利要求1所述的催化剂体系，其特征在于，其中中性金属茂化合物∶路易斯酸∶烷基铝和摩尔比范围从0.01∶1∶1至5∶1∶350。
9.一种如权利要求8所述的催化剂体系，其特征在于，其中，所述金属茂∶路易斯酸∶烷基铝的摩尔比范围从0.5∶1∶0.5至4∶1∶25。
10.一种制备催化剂的方法，其特征在于，该方法包括：
a)将一种路易斯酸与一种中性金属茂化合物混合；和
b)使该路易斯酸与该中性的金属茂化合物之间进行接触；
其中金属茂的中性衍生物的通式中：
                      Cp2MRP
式中Cp是环戊二烯基或取代的环戊二烯基，每个Cp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，除了只有一个R是氢化物之外每个R相同或不相同，P是1-4。
11.如权利要求10所述的方法，其特征在于，其中的烯烃是丙烯。
12.如权利要求10所述的方法，其特征在于，其中R是选自由烷基、芳基、链烯基、烷芳基和芳烷基组成的组中有20个以下碳原子的烃基。
13.如权利要求10所述的方法，其特征在于，其中M是选自由钛、锆和铪组成的组中的第IV族金属。
14.如权利要求13所述的方法，其特征在于，其中M是锆。
15.如权利要求14所述的方法，其特征在于，其中金属茂的中性衍生物是从二甲基亚乙基(茚基)锆和二甲基异亚丙基(环戊二烯基-1-芴基)锆中选择。
16.如权利要求10所述的方法，其特征在于，其中路易斯酸是从含硼和含氯化镁的所有路易斯酸中选择。
17.如权利要求16所述的方法，其特征在于，其中路易斯酸是三(五氟苯基)硼。
18.如权利要求1所述的催化剂体系，其特征在于，其中，金属茂∶路易斯酸∶烷基铝的摩尔比范围为从0.1∶1∶1至5∶1∶350。
19.如权利要求18所述的催化剂体系，其特征在于，其中，所述金属茂∶路易斯酸∶烷基铝的摩尔比范围从0.1∶1∶0.5至4∶1∶25。
20.如权利要求19所述的催化剂体系，其特征在于，其中，所述金属茂∶路易斯酸∶烷基铝的摩尔比范围为0.02∶1∶1。
21.如权利要求19所述的催化剂体系，其特征在于，其中，所述金属茂∶路易斯酸∶烷基铝的摩尔比范围为0.01∶1∶1。
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