M-H催化的新型聚对苯乙烯类材料的绿色合成与研究

The poly(p-phenylene vinylene) PPVs are the first class of conjugated polymers to be used in commercial polymer light-emitting diode and they are well known for the luminescent properties in the conjugated polymers. They are still form the most widely studied class of electroluminescent polymers and they also offer the most scope for synthetics effort to optimize their properties. .Base on the strategy of the dimerization reaction of styrene catalyzed by M-H catalyst, in which a 1, 1-disubsituted terminal alkene was obtained by tail-tail hydroalkenylation reaction of terminal olefin. The prepolymer containing terminal double bond in its polymer chain can be easily gained by using styrene and its conjugated derivatives as monomer and catalyzing by M-H catalyst. The terminal double bond of prepolymer modified by simple chemical reaction like double bond migration reaction to provide the very common poly(p-phenylene vinylene) PPVs polymers. Different molecular weight and molecular weight distribution prepolymers are also afforded from low-cost and easiest available monomers of p-divinylbenzene and its derivatives under the regulation and control of M-H catalyst and polymerization reaction conditions. Diverse novel poly(p-phenylene vinylene)s PPVs are generated by introducing all kinds of new functional group in these prepolymers as new electroluminescence materials .

聚对苯乙烯类聚合物是第一代的被用于工业开发并商业化的发光二极管类共轭聚合物，是发光共轭聚合物中非常出名的一类聚合物，也是被广泛研究的聚合物。人们在合成聚对苯乙烯类聚合物中花费了很大的精力并提出了各种各样的合成方法来合成不同类型的聚对苯乙烯类聚合物来提高其发光性能。.本项目基于M-H催化剂催化苯乙烯反应中，端基烯烃通过Tail-Tail的烯烃化反应方式得到1,1-二取代的端基烯烃的方法。以苯乙烯类共轭衍生物为单体，在M-H催化剂催化作用下，催化苯乙烯类共轭单体聚合生成含端基烯烃的初聚物。初聚物的端基烯烃经过简单的双键迁移等化学反应，生成常见的聚对苯乙烯类(PPVs)聚合物。廉价易得的对二乙烯基苯类衍生物类单体，在M-H催化剂及反应条件的调控，获得不同分子量的聚对苯乙烯类材料的初聚物。以这些初聚物为基础，引进新型官能团，衍生化出各种类型的新型聚对苯乙烯类聚合物，形成新型聚对苯乙烯类材料。

本项目基于Ni-H催化剂催化苯乙烯反应中，端基烯烃通过Tail-Tail的烯烃化反应方式得到1,1-二取代的端基烯烃的方法，建立了建立了高效、绿色、原子经济性催化反应体系。以苯乙烯类共轭衍生物为单体，在Ni-H催化剂催化作用下，催化苯乙烯类共轭单体聚合生成含端基烯烃的初聚物。初聚物的端基烯烃经过简单的双键迁移等化学反应，生成常见的聚对苯乙烯类(PPVs)聚合物。廉价易得的对二乙烯基苯类衍生物类单体，在Ni-H催化剂及反应条件的调控下，获得不同分子量的聚对苯乙烯类材料的聚合物。以这些初聚物为基础，衍生化出了新型聚对苯乙烯共轭高分子聚合物，形成新型聚对苯乙烯类材料。