芴酮-甲基丙烯酸N,N-二甲氨基乙酯引发丙烯腈光聚合的研究

二苯酮(BP)-脂肪叔胺体系作为光氧化还原引发体系引发烯类单体的光聚合已有许多研究。甲基丙烯酸N,N-二甲氨基乙酯(DMAEM)是含有脂肪叔胺基的丙烯酸酯类。由于含有叔胺基,它不仅能参与和芳香酮类构成的光氧化还原引发体系,其本身还参与聚合反应。 三川等报道了DMAEM在BP存在下的本体光聚合,并指出氧对此聚合体系有加

A STUDY ON THE PHOTOPOLYMERIZATION OF ACRYLONITRILE SENSITIZED BY FLUORENONE-N,N-DIMETHYLAMINOETHYL METHACRYLATE

Photopolymerization of acrylonitrile sensitized by aryl ketones combining with aliphatic tertiary amines or aryl amines has been studied. Among fluorenon-9(FL), acenaphthenequinone. anthraquinone, p-benzoquinone and benzophenone, fluorenon is the most effective when it combines with aliphatic tertrary amine or DMAEM to form the photo-redox system for the acrylonitrile (AN) photopolymerization. From the kinetic study for the photopolymer ization of AN sensitized by FL-DMAEM system, the polymerization rate is proportional to 0.27th power of DMAEM concentration, 0.27th power of FL concentration and 0.64 th, 1.74 th power of AN concentration performed in DMF, benzene as solvent respectively. The overall activation energy for the polymerization was obtained as 6.6 kcal/mol. The mechanism of the photopolymerization of AN sensitized by using FL-DMAEM system as photo-sensitizer may be via the formation of 9-hydroxy-9-fluorenyl free radical and DMAEM free radical under the UV irradiation. The latter would cause the polymerization mainly.