巯基/(甲基)丙烯酸(甲基)烯丙酯光固化特性  

The Photopolymerization of Thiol-(meth) allyl (meth) acrylates

作　　者：张净[1] 龙贺年 王跃川[1] 

机构地区：[1]四川大学高分子科学与工程学院高分子材料工程国家重点实验室,成都610065

出　　处：《高分子学报》2014年第11期1526-1531,共6页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20974067)资助项目

摘　　要：通过对羧酸盐法改进后合成同时含有高活性的丙烯酸酯型C=C和低自由基活性的烯丙基型C=C的烯类单体(甲基)丙烯酸(甲基)烯丙酯,以实现(甲基)丙烯酸酯类紫外光固化与巯/烯光聚合结合在二元体系中;并以1173为光引发剂,利用实时红外(RT-IR)跟踪此类烯烃与三羟甲基丙烷三(3-巯基丙酸酯)(TMMP)光固化过程,探究烯烃结构、光强和引发剂用量对含有两类碳碳双键的烯类单体与巯基化合物二元体系的光固化行为的影响.研究发现,这类二元巯-烯光聚合反应中均有(甲基)丙烯酸酯双键的反应活性最大,(甲基)烯丙基次之,巯基的反应活性最小;甲基取代在烯烃的不同C=C上,对巯-烯光固化特性影响不同,甲基取代在烯丙基C=C上比甲基取代在丙烯酸基C=C上对巯-烯光固化行为影响更大;巯基最终转化率随甲基取代基数目增多而减少;丙烯酸甲基烯丙酯体系中两类双键(丙烯酸型/甲基烯丙基型)反应活性几乎相同且均具有高的转化率.To achieve （meth）acrylate UV-curing and thiol-ene photopolymerization combined in binary systems, vinyl monomers with high reactivity （meth）acryl carbon carbon double bonds and low radical reactivity （meth）allyl carbon carbon double bonds, specifically, methallyl acrylate, allyl acrylate and methallyl methacrylate,have been synthesized by an optimized carboxylate method. The photopolymerizations between trimethylolpropane tris （3-mercaptopropionate） （TMMP） and vinyl monomers, using 1173 as photoinitiator, are investigated by real-time FTIR to understand the effects of chemical structure of alkene, light intensity and amount of initiator on the photopolymerization behavior of thiol-vinyl binary systems,in which vinyl monomers contain two kinds of carbon carbon double bonds. It is discovered that,in all of these binary systems, （meth） - acryl carbon carbon double bond reactivity is the highest,followed by （meth）allyl carbon carbon double bond reactivity,while thiol group reactivity is the lowest. Methyl substituents on different carbon carbon double bonds of vinyl monomers have different effects on the thiol-vinyl photopolymerization. Methyl substituents on allyl carbon carbon double bonds have much greater influence on behavior of thiol-vinyl photopolymerization than the methyl substituents on acryl carbon carbon double bonds. The conversion of thiol decreases with increasing methyl substituent. In methallyl acrylate photopolymerization system,two types of carbon carbon double bonds （acryl and methallyl） present almost equal reactivity and achieve high conversion.

关 键 词：巯基/乙烯基 紫外光固化 (甲基)丙烯酸(甲基)烯丙酯 结构 合成 

分 类 号：O623.624[理学—有机化学]