4,4’-偶氮二(4氰基戊酰对甲苯胺)的合成及其用作嵌段共聚合引发剂

SYNTHESIS OF 4,4’ AZOBIS (4 CYANOPENTANOYL p METHYLANILIDE) AND USE AS AN INITIATOR FOR RADICAL BLOCK COPOLYMERIZATION

合成了一类新型的含偶氮基和对甲苯基氨基甲酰基的多功能引发剂，４，４’偶氮二（４氰基戊酰对甲苯胺）．测定其偶氮键热分解反应为一级反应，分解活化能为１２４６ＫＪ·ｍｏｌ－１．利用引发剂中对甲苯氨基甲酰与Ｃｅ（ＩＶ）盐的氧化还原引发单体聚合，得到含有偶氮端的预聚物，它在６５℃热分解引发另一单体聚合生成嵌段共聚物．纯化后的共聚物。

A new kind polyfunctional initiator 4,4’ azobis (4 cyanopentanoyl p methyl anilide)(ACPMA) has been synthesized from 4,4' azobis (4 cyano pentanoic acid) via two steps reactions. The thermal decomposition rate of ACPMA in DMF was determined by nitrogen evolution technique at 65,70,75,80℃, respectively. It was found that the decomposition reaction follow first order kinetic and the activation energy was calculated to be 124 6 KJ mol -1 . The prepolymer containing azo end group can be obtained from the polymerization of monomer, such as acrylonitrile (AN), acrylamide (AAM) using Ce(IV) ion and ACPMA as a redox initiator. The p methylphenylaminocarbamoyl group would react with Ce(IV) ion to form a nitrogen center radical to initiate monomer polymerization and the azo group is reserved. When the prepolymer obtained was mixed with methyl methacrylate (MMA) in DMF reacted at 65℃, the decomposition of azo group took place and resulting macromolecular carbon center radical would initiate MMA to block copolymerization. The purified block copolymers were characterized by IR analysis.