《2-(N,N-二乙基二硫代氨基甲酰氧基)乙酸苄酯存在下苯乙烯光聚合》.pdfVIP

高分子学报990510 高分子学报 ACTA POLYMERICA SINICA 1999年 第5期 No.5 1999 2-(N，N-二乙基二硫代氨基甲酰氧基)乙酸苄酯 存在下苯乙烯光聚合* 田士英　董建华　丘坤元 摘　要　研究了2-N，N-二乙基二硫代氨基甲酰氧基乙酸苄酯(BzDCA)引发的苯乙烯光 聚合反应，发现单体转化率和数均分子量(M )都随反应时间而增加，在反应时间相同 n 时随着BzDCA浓度的增加单体转化率升高而M 降低.聚苯乙烯(PS)的M同单体转化率 n n 成线性关系并同理论计算值符合得较好.以2-甲基-2-亚硝基丙烷(MNP)为捕捉剂用 (EPR)技术对聚合反应机理进行了研究.认为BzDCA引发的St光聚合是一个“活性”聚合 过程. 关键词　引发转移终止剂，“活性”自由基聚合，2-N，N-二乙基二硫代氨基甲酰氧 基乙酸苄酯，苯乙烯，电子顺磁共振谱 PHOTOPOLYMERIZATION OF STYRENE WITH BENZYL N,N-DIETHYLDITHIOCARBAMYLACETATE TIAN Shiying, DONG Jianhua, QIU Kunyuan (Department of Polymer Science and Engineering, Peking University,Beijing　 100871) Abstract　Photopolymerization of styrene(St) with benzyl N,　N-diethyldithio- carbamylacetate(BzDCA) was studied.It was found that the number-average molecular weight(Mn)of polystyrene and the conversion increase with the increasing of reaction time, respectively.The conversion also increased with the concentration of BzDCA,while Mn decreased with the increasing of BzDCA concentration.When /=874,the Mn of PS had a linear relationship with the conversion,and agreed well with that calculated from the initial St and BzDCA concentrations and the conversions.The mechanism of the polymerization was proposed and the polymerization proceeded via a “living ” radical polymerization mechanism.Under UV irradiation,BzDCA dissociates into two kinds of radicals:carbon- Centered radical and sulfur-centered radical.The primary carbon-centered radical can initiate monomer polymerization and the sulfur-centered radical can reversibly terminate with propagating radical and form a diethyldithiocarbamate(DC) end group. Key w