Pd(II)-catalyzed alternating copolymerization of carbon monoxide with olefins: comparative results for the olefins ethene and styrene
Pd(II)-catalyzed alternating copolymerization of carbon monoxide with olefins: comparative results for the olefins ethene and styrene
复制标题
Pd(II) 催化一氧化碳与烯烃的交替共聚：烯烃乙烯和苯乙烯的比较结果
DOI：
10.1002/marc.1993.030140501
复制
发表时间：
1993
期刊：
影响因子：
--
通讯作者：
M. Trifuoggi
中科院分区：
文献类型：
--
作者：
V. Busico;P. Corradini;L. Landriani;M. Trifuoggi
最近报道了CO和乙烯完美交替共聚的高效Pd （I1）基均相催化剂。更近的发现是能够促进CO与苯乙烯（和苯乙烯衍生物）交替共聚的严格相关的催化剂。苯乙烯的插入已被证明具有区域特异性（2-1链结3）和立体特异性（即共征性；uu三联体L 80070的部分）~ 9~)。聚（1-氧-2-苯基三甲基）和共二聚聚（1-氧-2-苯基三甲基）是半结晶的高熔点材料（熔点温度分别为260" C和280" C4,*）。单体的低成本和（反应性）羰基官能团链的存在也符合它们相关的实际兴趣。最近对CO/乙烷交替共聚的机理进行了深入的研究。另一方面，关于CO/苯乙烯交替共聚机理的信息不太详细。本文报道了我们实验室pd催化CO/苯乙烯共聚的实验结果，并将其与文献中CO/乙烯共聚的结果进行了比较，指出了两种催化过程在链起始和链终止步骤的性质上的显著差异。
Highly efficient Pd (I1)-based homogeneous catalysts for the perfectly alternating copolymerization of CO and ethene were recently reported'1. Even more recent was the disclosure of strictly related catalysts able to promote the alternating copolymerization of CO with styrene (and styrene derivatives) 2). The insertion of styrene has been proved to be regiospecific (2-1 enchainment3)) and stereospecific (ie syndiotactic; fraction of uu triads L 80070)~ 9~). Poly (1-0xotrimethylene) and syndiotactic poly (1-oxo-2-phenyltrimethylene) are semicrystalline, high-melting materials (melting temperature T,,,= 260" C and= 280" C4,*), respectively). The low cost of the monomers and the presence in the chain of the (reactive) carbonyl functionality also concur to their relevant practical interest.Thorough mechanistic studies on CO/ethane alternating copolymerization have lately become available'* 6). On the other hand, information on the mechanism of CO/styrene alternating copolymerization is less detailed 3* 7). In this communication, experimental results from our laboratory on the Pd-catalyzed CO/styrene copolymerization are reported and compared with literature results on CO/ethene copolymerization in particular, significant differences in the nature of the chain initiation and termination steps between the two catalytic processes are pointed out.