聚苯醚合成机理的研究进展

Research Progress in Synthesis Mechanism of Polyphenylene Oxide

聚苯醚是当今世界五大通用型工程塑料之一,广泛应用于各行各业。聚苯醚从首次合成出来距今已有半个多世纪,但是关于聚苯醚的合成机理至今仍然没有完全阐明。本文主要介绍了合成聚苯醚氧化偶合反应的三种可能机理:苯氧自由基协同配合物偶合机理、单电子转移偶合机理和一步双电子转移偶合机理。其中,一步双电子转移偶合机理是目前学术界所普遍接受的,并进一步阐述了聚苯醚合成过程中醌缩酮中间体再分配和醌缩酮中间体重排两种合成聚苯醚的链增长机理。

Polyphenylene oxide, one of the five major universal engineering plastics in the world, was widely used in all walks of life. It has been more than half a century since polyphenylene ether was first synthesized. However, the synthesis mechanism of polyphenylene oxide was still not fully elucidated. In the paper, three possible mechanisms of the oxidative coupling in synthesizing polyphenylene oxide were introduced, including coupling mechanism of phenoxy radicals coordinated to catalyst complex, coupling mechanism of free phenoxy radicals and coupling mechanism of one-step two electron transfer. Of the three mechanism, coupling mechanism of one-step two electron transfer was generally accepted in the academic circles. Also, the chain extension mechanism including redistribution and rearrangement of quinine ketal intermediate was further elaborated.