Piskun Yuliya A, Ksendzov Evgenii A, Resko Anastasiya V, Soldatov Mikhail A, Timashev Peter, Liu Hongzhi, Vasilenko Irina V, Kostjuk Sergei V
Research Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya St., 220006 Minsk, Belarus.
Department of Chemistry, Belarusian State University, 14 Leningradskaya St., 220050 Minsk, Belarus.
Polymers (Basel). 2023 Mar 3;15(5):1291. doi: 10.3390/polym15051291.
The bulk ring-opening polymerization (ROP) of ε-caprolactone using phosphazene-containing porous polymeric material (HPCP) has been studied at high reaction temperatures (130-150 °C). HPCP in conjunction with benzyl alcohol as an initiator induced the living ROP of ε-caprolactone, affording polyesters with a controlled molecular weight up to 6000 g mol and moderate polydispersity (Ð1.5) under optimized conditions ([BnOH]/[CL] = 50; HPCP: 0.63 mM; 150 °C). Poly(ε-caprolactone)s with higher molecular weight (up to M = 14,000 g mol, Ð1.9) were obtained at a lower temperature, at 130 °C. Due to its high thermal and chemical stability, HPCP can be reused for at least three consecutive cycles without a significant decrease in the catalyst efficiency. The tentative mechanism of the HPCP-catalyzed ROP of ε-caprolactone, the key stage of which consists of the activation of the initiator through the basic sites of the catalyst, was proposed.
在高温（130 - 150°C）下研究了使用含磷腈的多孔聚合物材料（HPCP）进行ε-己内酯的本体开环聚合（ROP）。HPCP与苄醇作为引发剂共同引发ε-己内酯的活性ROP，在优化条件下（[BnOH]/[CL] = 50；HPCP：0.63 mM；150°C），可得到分子量可控高达6000 g/mol且多分散性适中（Ð1.5）的聚酯。在130°C的较低温度下可得到分子量更高（高达M = 14,000 g/mol，Ð1.9）的聚（ε-己内酯）。由于其高热稳定性和化学稳定性，HPCP可连续重复使用至少三个循环，而催化剂效率无显著降低。提出了HPCP催化ε-己内酯ROP的初步机理，其关键阶段包括通过催化剂的碱性位点活化引发剂。
