In this work, various types of chain-transfer agents (CTAs) were investigated in the reversible addition-fragmentation chain-transfer (RAFT) polymerization of isopropenyl boronate pinacol ester (IPBpin) toward not only precise synthesis of poly(IPBpin) but also elucidation of its feature as a monomer. CTAs suitable for conjugated monomers were found to be more compatible than those for nonconjugated monomers, likely due to the moderate stabilization of the growing radical by boron. This trend was supported by density functional theory-based calculations for energy balance between the growing IPBpin radical and the chain-transfer species to the CTA. The CTA-derived group at the ω-terminus of the obtained poly(IPBpin) was quantitatively converted into olefin under cobalt catalysis leading to improved stability, enabling evaluation of its well-defined structure by MALDI-TOF-MS and its thermal properties by DSC.

在这项工作中，在异丙烯基硼酸酯频哪醇酯（IPBpin）的可逆加成-断裂链转移（RAFT）聚合中，研究了各种类型的链转移剂（CTA），不仅可以精确合成聚（IPBpin），而且可以阐明作为单体的特征。发现适合于共轭单体的CTA比非共轭单体的CTA更相容，这可能是由于硼对生长中的自由基具有中等稳定性的缘故。这一趋势得到了基于密度泛函理论的计算的支持，该计算方法用于计算不断增长的IPBpin自由基与CTA的链转移物种之间的能量平衡。在钴催化下，将获得的聚（IPBpin）ω端的CTA衍生基团定量转化为烯烃，从而提高了稳定性，