Fornaciari Charlotte, Lemaur Vincent, Pasini Dario, Coulembier Olivier
Laboratory of Polymeric and Composite Materials (LPCM), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons, Place du Parc, 20, Mons, 7000, Belgium.
Department of Chemistry, University of Pavia, Viale Taramelli, 10, Pavia, 27100, Italy.
Commun Chem. 2023 Oct 28;6(1):235. doi: 10.1038/s42004-023-01031-z.
Alternating copolymers are distinctly unique in comparison with other copolymers. Herein, an in-depth investigation of the oxyanionic ring-opening copolymerization of propylene oxide (PO) and allyl glycidyl ether (AGE) from benzyl alcohol (BnOH) activated with potassium acetate (KOAc) complexed by 18-crown-6 ether (18C6) is described. We demonstrate that the 18C6/KOAc complex is an efficient and benign catalytic system to promote copolymerization of both oxirane monomers, leading to well-defined polyethers with varied comonomer content and low dispersity values (Ɖ < 1.20). Kinetic analysis confirmed the controlled nature of the (co)polymerization process, and the determination of reactivity ratios revealed a quasi-alternating copolymerization profile, according to the Fineman-Ross method. The comparison between the quasi-alternating-type PO/AGE copolymerization and block or gradient copolymerization revealed significant differences, to confirm the different sequence incorporation in the different topological copolymers. These results highlight the great potential of 18C6/KOAc-mediated copolymerization process for the controlled sythesis of a series of copolymer topologies.
与其他共聚物相比，交替共聚物具有明显的独特性。本文描述了对环氧丙烷（PO）和烯丙基缩水甘油醚（AGE）在由18-冠-6醚（18C6）络合的醋酸钾（KOAc）活化的苄醇（BnOH）存在下进行的氧阴离子开环共聚反应的深入研究。我们证明，18C6/KOAc络合物是一种高效且温和的催化体系，可促进两种环氧乙烷单体的共聚反应，生成具有不同共聚单体含量和低分散度值（Ɖ < 1.20）的结构明确的聚醚。动力学分析证实了（共）聚合过程的可控性质，并且根据Fineman-Ross方法，反应活性比的测定揭示了准交替共聚反应特征。准交替型PO/AGE共聚反应与嵌段或梯度共聚反应之间的比较显示出显著差异，从而证实了不同拓扑共聚物中不同序列的引入情况。这些结果突出了18C6/KOAc介导的共聚反应过程在一系列共聚物拓扑结构的可控合成方面的巨大潜力。
