杯芳烃钕/二正丁基镁/六甲基磷酰胺催化4-乙烯基吡啶的均聚及其与苯乙烯的共聚

聚4-乙烯基吡啶P（4-VP）]是一种功能高分子，由于在吡啶环上有一个碱性的氮原子，它能进一步与酸反应生成各种盐，与卤代烃生成季铵盐以及与金属离子生成配合物，可用作高分子电解质，高分子试剂，高分子功能材料等，因此有不少文献对它的合成进行了报道，合成聚4-乙烯基吡啶及其与苯乙烯（St）的共聚物，除了用丁基锂作引发剂外，过渡金属的Ziegler-Natta催化剂，以及烷基铝和烷基锌等也常被用作催化剂，但用这些催化剂催化所得的聚4-乙烯基吡啶及其与苯乙烯的共聚物产率低，分子量小。

HOMOPOLYMERIZATION OF 4-VINYLPYRIDINE AND COPOLYMERIZATION OF 4-VINYLPYRIDINE WITH STYRENE BY CALIX [ 4 ] ARENE-NEODYMIUM CATALYST

Homopolymerization of 4-vinyl pyridine(4-VP) and copolymerization of 4-VP with styrene(St) were performed by catalyst systems composed of calix4]arene-neodymium complex 2,di-n-butylmagnesium and hexamethyl phosphoramide. The molecular weight of P(4-VP) was greatly affected by adding calix4]arene-neodymium complex,and high molecular weight of P(4-VP) was got by using calix4]arene-neodymium complex.The highest molecular weight of P(4-VP) was as high as 4.65×10~6 obtained by using a catalyst system with 2.0×10~(-4)?mol/L of calix4]arene-neodymium complex,while the molecular weight of P(4-VP) was only 5.62×10~5 without calix4]arene-neodymium complex. In addition,4-VP-St copolymers with different 4-VP contents were obtained in good yield.When styrene was polymerized first for a time period,and then 4-VP was added,4-VP-St copolymers with 4.85?mol%～23.3?mol% of 4-VP units were obtained,but when 4-VP and styrene were added at the same time the resultant 4-VP-St copolymers had 44.0?mol%～66.3?mol% of 4-VP units.