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结合活性负离子聚合与原子转移自由基聚合(ATRP),采用机理转移法制备了一系列窄分布且分子量可控的星形梳状聚丁二烯-g-聚甲基丙烯酸甲酯接枝共聚物(SC-(PB-g-PMMA)).首先通过阴离子聚合,制备星形聚丁二烯,后经甲酸-过氧化氢原位环氧化对链中部分双键进行环氧化,再与原位生成2-溴异丁酸发生酯化反应,得到具有链中活性溴的星形大分子引发剂(SPB-Brn).然后,利用该大分子引发剂,采用CuCl/CuCl2/PMDETA催化体系,通过ATRP聚合单体MMA,合成出星形梳状SC-(PB-g-PMMA)聚合物.通过GPC,1H-NMR和FTIR等分析手段对合成的星形大分子引发剂及星形梳状聚合物进结构表征,证实得到目标产物,并同时研究了聚合物的热力学性质与溶液性质.
A series of narrowly distributed and molecularly controlled star comb polybutadiene-g-polymethylmethacrylate graft copolymers were prepared by a combination of living anionic polymerization and atom transfer radical polymerization (ATRP) (SC- (PB-g-PMMA)) .At first, the star-shaped polybutadiene was prepared by anionic polymerization and epoxidized some of the double bonds in the chain by in situ epoxidation with formic acid-hydrogen peroxide. The esterification of 2-bromoisobutyric acid was carried out in situ to obtain a star-shaped macro-initiator (SPB-Brn) with active bromine in the chain.Then, using this macroinitiator, CuCl / CuCl2 / PMDETA catalyst system , The star comb SC- (PB-g-PMMA) polymer was synthesized by ATRP polymerization monomer MMA.The synthesized star polymer initiator and star comb were analyzed by GPC, 1H-NMR and FTIR, The structure of the polymer was characterized and confirmed to obtain the target product. Meanwhile, the thermodynamic properties and the solution properties of the polymer were also studied.