Polyglycidols of tunable degree of branching (DB) have been synthesized via ring-opening multibranching polymerization (ROMBP) of glycidol in the absence of any initiators using heterogeneous double metal cyanide (DMC) catalysts. Semi-branched polyglycidols of low DB (less than 0.3) are obtained using simple solvent-free batch polymerizations, whereas hyperbranched analogues of high DB (more than 0.5) are achieved employing semi-batch (or slow monomer addition) polymerizations. The rate of DMC-catalyzed ROMBPs of glycidol shows the first-order dependences on monomer and catalyst concentrations, suggesting that the ROMBPs proceed via a coordinative mechanism. The formation of propagating species and the resultant microstructural units are clarified using a conversion versus time analysis in the NMR-scale.

中文翻译：

---

非均相双金属氰化物催化开环多支化缩水甘油的动力学和机理研究

在不存在任何引发剂的情况下，使用非均相双金属氰化物（DMC）催化剂，通过缩水甘油的开环多支化聚合（ROMBP）合成了可调节支化度（DB）的聚缩水甘油。低DB（小于0.3）的半支化多糖苷使用简单的无溶剂分批聚合法获得，而高DB（大于0.5）的超支化类似物通过半分批（或缓慢的单体加成）聚合获得。DMC催化缩水甘油的ROMBP的速率显示出对单体和催化剂浓度的一阶依赖性，这表明ROMBP通过协调机制进行。使用NMR规模的转化率与时间的关系分析，可以清楚地说明繁殖物种的形成和所得的微结构单元。