Commercial brominated poly(isobutylene‐co‐isoprene) (BIIR) rubber has been directly used for the initiation of atom transfer radical polymerization (ATRP) by utilizing the allylic bromine atoms on the macromolecular chains of BIIR. The graft copolymerization of methyl methacrylate (MMA) from the backbone of BIIR which was used as a macroinitiator was carried out in xylene at 85 °C with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as a catalytic complex. The polymerization conditions were optimized by adjusting the catalyst and monomer concentration to reach a higher monomer conversion and meanwhile suppress macroscopic gelation during the polymerization process. This copolymerization followed a first‐order kinetic behavior with respect to the monomer concentration, and the number‐average molecular weight of the grafted poly(methyl methacrylate) (PMMA) increased with reaction time. The resultant BIIR‐graft‐PMMA copolymers showed phase separation morphology as characterized by atomic force microscopy, and the presence of PMMA phase increased the polarity of the BIIR copolymers. This study demonstrated the feasibility of using commercial BIIR polymer directly as a macromolecular initiator for ATRP reactions, which opens more possibilities for BIIR modifications for wider applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43408.

中文翻译：

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通过原子转移自由基聚合反应从溴化聚异丁烯-异戊二烯中接枝甲基丙烯酸甲酯

商业溴化聚（异丁烯-共-异戊二烯）（BIIR）橡胶已被直接用于原子转移自由基聚合（ATRP）的通过利用上BIIR的大分子链的烯丙基溴原子的启动。来自BIIR骨架的甲基丙烯酸甲酯（MMA）用作大分子引发剂的接枝共聚反应是在85°C的二甲苯中与CuBr / N，N，N '，N '' ，N进行的”-五甲基二亚乙基三胺作为催化络合物。通过调节催化剂和单体的浓度以达到更高的单体转化率并同时抑制聚合过程中的宏观凝胶化来优化聚合条件。该共聚遵循关于单体浓度的一级动力学行为，并且接枝的聚甲基丙烯酸甲酯（PMMA）的数均分子量随反应时间而增加。最终的BIIR移植物‐PMMA共聚物表现出通过原子力显微镜表征的相分离形态，并且PMMA相的存在增加了BIIR共聚物的极性。这项研究证明了将商业BIIR聚合物直接用作ATRP反应的大分子引发剂的可行性，这为更广泛的应用领域的BIIR修饰开辟了更多可能性。©2016 Wiley Periodicals，Inc. J. Appl。Polym。科学 2016，133，43408。