CN1025038C - 新颖催化剂组合物和使乙烯与一氧化碳共聚的方法 - Google Patents
新颖催化剂组合物和使乙烯与一氧化碳共聚的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 21
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title description 8
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 4
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 4
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Abstract
用于乙烯和一氧化碳共聚合反应的新颖催化剂组合物，其中含有a/选自钯，钴和镍的第VIII族金属的化合物，b/pKa小于6的酸的阴离子，以及c/通式为R1R2-M-R-M-R3R4的二齿配位体，其中，M代表磷，砷或锑，R为在桥中含有二个或三个碳原子的二价有机桥键基，R1，R2，R3和R4为可含有或不含极性取代基的烃基，但在R1，R2，R3和R4四个烃基中至少有一个烃基中的至少一个氢原子为极性取代基所取代。
Description
本发明涉及可用于制备一氧化碳和乙烯共聚物的新颖催化剂，若适宜的话，也可用作制备一氧化碳与乙烯和其它一个或多个不饱和烯烃共聚物的催化剂。
单体单元以交替排列出现的一氧化碳和乙烯的高分子量线形聚合物（此聚合物由结构式为-CO-（C2H4）-的单元所组成）可用已知工艺的催化剂组合物来制备。此催化剂组合物含有：
（a）选自钯，钴和镍的第Ⅷ族金属的化合物。
（b）pKa小于6的酸的阴离子，以及
（c）通式为R1R2-M-R-M-R3R4的二齿配位体，其中M代表磷，砷或锑，R为在桥中含有二个或三个碳原子的二价有机桥键基，R1，R2，R3和R4表示烃基。
把这些催化剂组合物用于单体混合物（此混合物除一氧化碳和乙烯以外还包括一个或多个其它可聚合的烃类（A）），可生成含结构式为-CO-（C2H4）-的单元以及通式为-CO-A-的单元的聚合物。其中单元-CO-A-是随机地分布在聚合物链上的。二元共聚物和三元共聚物结构的不同之处仅仅在于三元共聚物中的-A-基团在聚合物链上无规地取代了-（C2H4）-。
上面提到的聚合物制备中，反应速率和所生成的聚合物分子量都起重要作用。一方面，希望制备聚合物时，取得尽可能高的反应速率;另一方面，从聚合物潜在的应用范围来看，具有较高分子量的聚合物更有价值。反应速率和分子量都会受到聚合反应过程中温度的影响。遗撼的是，温度对反应速率的影响和对分子量的影响是相反的。在其它反应条件类似的情
况下，反应温度的增加使反应速率增加，但降低了所生成聚合物的分子量。考虑到这些聚合物的可能的应用场合，在实践中，可通过选择反应温度来解决这一问题。在所取的反应温度下，对相应的应用来说，聚合物具有足够高的分子量，而反应速率只好任其自然。
本专利申请人惊奇地发现，通过用极性取代基取代二齿配位体中的R1、R2，R3和R4四个烃基中至少一个烃基内的至少一个氢原子，能使上述催化剂的性能得到增强。将原来的在R1，R2，R3和R4中只含有碳和氢的催化剂组合物的性能和经改进的在R1，R2，R3和R4中至少有一个基团带有至少一个极性基团的催化剂组合物的性能作比较表明，两种催化剂在相似的反应速率下，用经改进的催化剂可制得较高分子量的聚合物，反之，如果两种催化剂组合物制成具有相同分子量的聚合物，则经改进的催化剂具有较高的反应速率。
由此可见，经改进的催化剂组合物是新颖的。
本专利申请就涉及新颖的催化剂组合物，它含有：
（a）选自钯，钴和镍的第Ⅷ族金属的化合物。
（b）pKa小于6的酸的阴离子，以及
（c）通式为R1R2-M-R-M-R3R4的二齿配位体，其中M代表磷，砷或锑，R表示在桥中带有二个或三个碳原子的二价有机桥键基，R1，R2，R3和R4为烃基，这些烃基可能含极性取代基，也可能不含极性取代基，但在R1、R2、R3和R4中至少有一个烃基中的至少一个氢原子为极性取代基所取代。
本专利申请还涉及这些催化剂组合物在一氧化碳与乙烯的聚合物制备中的应用。如果适宜的话，还涉及一氧化碳与乙烯和一个或多个其它不饱和烯烃聚合物制备中的应用。
用于该催化剂组合物中的第Ⅷ族金属的化合物以钯化合物为宜。最适合的钯化合物是羧酸的钯盐，尤其是醋酸钯。pKa小于6的适宜酸（在
18°的水溶液中测定）有各种磺酸（如甲磺酸、三氟甲磺酸和对-甲苯磺酸）以及各种羧酸（如三氯醋酸，二氟醋酸，三氟醋酸，一氯醋酸，二氟丙酸，醋酸，酒石酸，2，5-二羟基苯甲酸，氢氯酸，氢氟酸和氢溴酸。在所有这些酸类中，以pKa小于4为佳，pKa小于2的更佳。最优酸类是对-甲苯磺酸和三氟醋酸。在催化剂成分中，pKa小于6的酸的阴离子适宜量为每克原子第Ⅷ族金属0.5到200当量，尤其是1.0到100当量。在二齿配位中M最好是磷。催化剂组合物中二齿配位体的适宜含量为每摩尔第Ⅷ族金属化合物0.1-2摩尔，尤其以0.9-1.1摩尔为佳。二价有机桥键基R以在桥中含有三个碳原子为宜。
二齿配位体中的烃基R1，R2，R3和R4以含有6到14个碳原子为宜。R1，R2，R3和R4四个烃基中的每一个均含有芳基，且此芳基又直接与M原子相连的二齿配位体更佳。R1，R2，R3和R4四个烃基中应至少有一个烃基内的至少一个氢原子为一个极性取代基所取代。除其它极性取代基外，适宜的极性取代基为卤素以及通式为R5-O-、R5-S-、R5-CO-、R5-CO-O-、R5-CO-NH-、R5-CO-NR6-、R5R6-N-CO-、R5-O-CO-NH-和R5-O-CO-NR6-等基团，其中R5和R6代表同种或不同种烷基或芳基。R1，R2，R3和R4中带有的极性取代基以烷氧基，尤其是甲氧基的二齿配位体为佳。进一步说，R1，R2，R3和R4四个烃基中的每一个均含有一个极性取代基的二齿配位体为佳。最后，R1，R2，R3和R4四个基团均相同的二齿配位体更好。非常适合的二齿配位体是1，3-双（二-4-甲氧基苯基膦）丙烷和2-甲基-2-（甲基二-4-甲氧基苯基膦）-1，3-双（二-4-甲氧基苯基膦）丙烷。作为一个化合物，前一个配位体是广义双膦类之一，这些都是新颖的，于是也就成了本发明的一部分。此双膦类具有通式（R6）2P-R7-P（R6）2，其中R6为在对磷而言的对位带有极性取代基的芳基，R7为桥中带有三个碳原子的有机桥键基。新颖化合物内这一基团的其它例子为那些
从R8-S-，R8-COO-，R8R9N-，R8-CO-NR9-和R10-O-中选择的极性取代基，其中，R8和R9可以是相同或不同的烃基，R10是带有2个或多个碳原子的烃基，且以烷基为好。仅次于甲氧基的烷氧取代基为乙氧基、正丙氧基、异丙氧基、2-丁氧基、叔丁氧基和正戊氧基等。
用本发明的催化剂组合物进行的聚合反应最好在液体稀释剂内进行。较适宜的液体稀释剂有低级醇类，如甲醇和乙醇。制备聚合物时催化剂组合物的用量可在很宽的范围内变化。对每一摩尔待聚合的不饱和烯烃，催化剂组合物的用量最好使其中含有10-7-10-3，尤其是10-6-10-5克原子第Ⅷ族金属。用本发明的催化剂组合物制备聚合物的适宜温度为20-150℃，压力为1-200巴，尤其以30-100℃，20-100巴为宜。
本发明的催化剂组合物可用于制备一氧化碳和乙烯的聚合物，也可制备一氧化碳和乙烯以及一个或多个其它不饱和烯烃的聚合物。这些不饱和烯烃最好具有通式CHR1＝CHR2，其中R1和R2基团含有的碳原子总数小于18，且R1、R2中有一个是烃基，而另一个是氢或者也是烃基。在后一种情况下，R1和R2一起可成为环状结构的一部分，如在单体环戊烯和环己烯中那样。当R1和R2是烃基时，以烷基为宜，在单体内的R1和R2中最好有一个是氢，而另一个是烷基，此烷基尤以甲基为佳。在待聚合的混合物中，不饱和烯烃与一氧化碳的分子比宜为10∶1-1∶5尤其以5∶1-1∶2为佳。
由于按本发明制备的聚合物具有较高的分子量，因而聚合物的特性粘数一般说来也较高。为测定按本发明制备的聚合物的特性粘数，在100℃下以四种不同的浓度把聚合物溶于间甲酚中，制备四份溶液。然后用粘度计测定100℃下四种溶液相对于100℃下间甲酚粘度的粘度值。如用T。代表间甲酚的流过时间，Tp代表聚合物溶液的流过时间，则相对粘度ηrel可由下式决定：
ηrel＝ (Tp)/(To)
特性粘度ηinh可用ηrel根据下式计算
ηinh＝lnηrel/c
式中c代表聚合物浓度，为每100毫升溶液中聚合物的克数。画出4种聚合物溶液各自的特性粘度（ηinh）和相应的聚合物浓度（c）的关系图，然后外推到浓度等于零，从而得出特性粘数[η]，单位为分升/克。下文不再用特性粘数（intrinsic viscosity）这一词而用国际纯化学和应用化学联合会（International Union of Pure and Applied Chemistry）所推荐的特性粘数（LVN）（Limiting Viscosity Number（LVN））这一词。按本发明制备的聚合物的LVN值通常在0.2到5.0分升/克之间。LVN值在0.3到4.5分升/克之间的聚合物较好，尤其以LVN在0.4到4.0分升/克之间的聚合物为佳。
下面用实例说明本发明：
实例1（供比较用）
用下述方法制备一氧化碳/乙烯共聚物。将200毫升甲醇加到容量为300毫升的机械搅拌的压热釜内。用一氧化碳对压热釜加压直至50巴，然后卸压。同样操作，重复两次，以排除空气。釜内物料达到65℃后，将1∶1的一氧化碳和乙烯混合物加入压热釜中，直到釜内压力达到55巴。然后将催化剂溶液加入釜中。催化剂溶液含有：6毫升甲醇，0.02毫摩尔醋酸钯，0.02毫摩尔1，3-双（二苯基膦）丙烷以及0.04毫摩尔对-甲苯磺酸。通过加入1∶1的一氧化碳和乙烯混合物，维持釜压55巴。3小时后，将反应混合物的温度降到室温，并卸压以终止反应。过滤共聚物，用甲醇洗涤，在70℃下干燥。用这一方法制备出LVN值为0.95分升/克的共聚
物，反应速率为1.3公斤共聚物/克钯/小时。
实例2（供比较用）
用和例1基本相同的方法制备一氧化碳/乙烯共聚物。不同的是反应温度不是65℃而是85℃。所制得的共聚物的LVN值是0.52分升/克，反应速率为5.0公斤共聚物/克钯/小时。
实例3
用和例1基本相同的方法制备一氧化碳/乙烯共聚物，不同的是本实例用1，3-双（二-对-甲氧基苯基膦）丙烷而不是用1，3-双（二苯基膦）丙烷。制得的共聚物的LVN值为1.4分升/克，反应速率为0.8公斤共聚物/克钯/小时。
实例4
用和例1基本相同的方法制备一氧化碳/乙烯共聚物，不同之处如下：a）反应温度是85℃而不是65℃，b）用1，3-双（二-对-甲氧基苯基膦）丙烷而不是1，3-双（二苯基膦）丙烷。制得的共聚物的LVN值为1.0分升/克，反应速率为3.2公斤共聚物/克钯/小时。经13C核磁共振分析表明根据例1-4所制备的共聚物具有线形交替结构，并由结构式为-CO-（C2H4）-的单元所组成。此共聚物的熔点是257℃。例1-4中，只有例3和例4是根据本发明的实例。例1和例2不在本发明范围内，把它们包括在内只是作为比较。
将例1和例2作比较（所用催化剂组合物内的二齿配位体中的R1，R2，R3和R4都是烃基）以及将例3和例4作比较（所用催化剂组合物内的二齿配位体中的每一个基团R1，R2，R3和R4都含有作为极性取代基的甲氧基），表明温度对反应速率和所制得的聚合物分子量的影响。按例1和例4制备的聚合物具有大致相同的分子量，但例4中用的是本发明的催化剂组合物，因此反应速率与例1的相比要高得多。
Claims (5)
1、一种催化剂组合物，该组合物含有
a).一种选自钯、钴和镍的第Ⅷ族金属的化合物，
b).一种pka值小于6的酸的阴离子，和
c).通式为R1R2-M-R-M-R3R4的二齿配位体，其中M代表磷、砷或锑，R为在桥上有2个或3个碳原子的二价有机桥机，R1、R2、R3、R4为带有或不带有极性取代基的烃基，
其特征在于：R1、R2、R3和R4这四个基团中至少有一个基团的至少一个氢原子被极性取代基所取代。
2、根据权利要求1的催化剂组合物，其特征在于出现在烃基R1、R2、R3和R4里的极性取代基是烷氧基，例如甲氧基。
3、根据权利要求1或2的催化剂组合物，其特征在于二齿配位体是1，3-双（二-对-甲氧基苯基膦）丙烷。
4、根据权利要求1或2所定义的催化剂组合物的用途，用于使含一氧化碳和乙烯的混合物（如果适宜的话，该混合物中还含有一种或多种其它链烯类不饱和烃）聚合制备聚合物。
5、权利要求3所定义的催化剂组合物的用途，用于使含一氧化碳和乙烯的混合物（如果适宜的话，该混合物中还含有一种或多种其它链烯类不饱和烃）聚合制备聚合物。
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- 1986-11-12 FI FI864601A patent/FI90556C/fi not_active IP Right Cessation
- 1986-11-12 JP JP61269501A patent/JPH082959B2/ja not_active Expired - Lifetime
- 1986-11-12 BR BR8605593A patent/BR8605593A/pt not_active IP Right Cessation
- 1986-11-12 DK DK541686A patent/DK541686A/da not_active Application Discontinuation
- 1986-11-12 HU HU864674A patent/HU204208B/hu not_active IP Right Cessation
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1995
- 1995-05-31 JP JP7133886A patent/JP2755922B2/ja not_active Expired - Lifetime
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