采用茂金属化合物(n-BuCp)2TiCl2,还原剂(Sn)及引发剂4,4’-亚甲基二(N,N-二缩水甘油基苯胺(I4))组成的催化体系,引发苯乙烯活性自由基聚合,合成了星状羟基功能化无规聚苯乙烯。考察了聚合温度、时间、投料比等反应条件对苯乙烯聚合的影响。用沸丁酮对所得聚合物进行抽提,并采用凝胶渗透色谱(GPC)和核磁共振(^13C-NMR)对沸丁酮可溶部分的结构和性能进行了表征。GPC分析证明催化体系(n-BuCp)2TiCl2/Sn/I4引发苯乙烯聚合属于活性聚合;^13C-NMR结果证明所得聚苯乙烯链段为无定型态。实验表明所得聚合物为星状羟基功能化无规聚苯乙烯。
Star-like hydroxyl functionalized atacticpolystyrene was synthesized via living radical polymerization promoted by the catalyst system (n-BuCp)2TiCl2/Sn/I4.Among the components of the catalyst system,Sn used as the reducing agent and 4,4’-methylenebis(N,N-diglycidylaniline)(I4) as the initiator.The effect of polymerization conditions,such as temperature,time,as well as the ratio of initiator to monomer on the polymerization performance was investigated.The obtained polymer was characterized by gel permeation in chromatography(GPC) and 13C nuclear magnetic resonance spectrum(^13C-NMR).The GPC result indicates that a linear dependence of M-n on the monomer conversion is observed and a narrow polydispersity (Mw^-/Mn^-) of the resultant polymer is exhibited even the ratio of initiator to monomer ([I4]/[St] = 1/250,1/500,1/750) is changed,which confirmes that the polymerization behavior is of living radical polymerization.The ^13C-NMR result indicates that the obtained polymer features atactic structure.