Free-radical ring-opening polymerization of macrocyclic aryl ether thioether ketone oligomers

被引:34
作者
Wang, YF [1 ]
Chan, KP [1 ]
Hay, AS [1 ]
机构
[1] MCGILL UNIV,DEPT CHEM,MONTREAL,PQ H3A 2K6,CANADA
关键词
D O I
10.1021/ma9517409
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A facile free-radical ring-opening, polymerization of macrocyclic aryl ether thioether ketone oligomers is described. Polymerization of the cyclic oligomers via a transthioetherification reaction to high molecular weight linear polymers is achieved both in the melt and in solution in the presence of a catalytic amount of elemental sulfur or 2,2'-dithiobis(benzothiazole) (DTB). The free-radical nature of the polymerization reaction is indicated by electron paramagnetic resonance spectroscopy(EPR). The ring-opening polymerization reaction is unusual in that the molecular weight of the polymers obtained increases as the conversion of cyclic oligomers increases. The ring-chain equilibrium dramatically favors the formation of linear polymer, in which only low levels of cyclic materials are present after polymerization, even though the reaction is not enthalpically driven. also a facile process during polymerization. This intermolecular transthioetherification is demonstrated by using a low molecular weight arylene thioether, e.g., thiobis((phenylene-4-oxy)-4-benzoylbenzene), to control the molecular weight of the polymer formed via ring-opening polymerization.
引用
收藏
页码:3717 / 3726
页数:10
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