Feng Zhiheng, Wu Li, Dong Huan, Liu Boping, Cheng Ruihua
School of Chemical Engineering, East China University of Science and Technology Meilong Road 130 Shanghai 200237 China
College of Materials and Energy, South China Agricultural University Guangzhou 510642 China.
RSC Adv. 2021 May 26;11(31):19021-19028. doi: 10.1039/d1ra02417e. eCollection 2021 May 24.
Aliphatic polyesters are biocompatible materials that can be used in biomedical applications. We report here the use of tetrabutylammonium phthalimide--oxyl catalyst (TBAPINO), as a thermally stable organocatalyst for the ring-opening polymerization (ROP) of cyclic esters under mild conditions. In the solution ROP of ε-caprolactone (ε-CL), quantitative conversion and of ∼20 000 g mol are achieved in a wide temperature range from -15 to 60 °C. Under bulk condition, the conversion of ε-CL reaches over 85% at 120 °C within 2 h. The living ROP character of l-lactide (l-LA) catalyzed over TBAPINO is proved by multiple additions of monomer in the bulk polymerization. The catalyst shows comparable selectivity towards the ring-opening polymerization of l-LA and ε-CL. Their copolymerization over TBAPINO is carried out in one-pot bulk condition in terms of the reaction time, monomer feed ratio, and sequence of addition. The colorless poly(ε-caprolactone--lactide) (PCLA) is obtained with considerable conversion of both monomers with the over 22 000 g mol.
脂肪族聚酯是可用于生物医学应用的生物相容性材料。我们在此报告使用四丁基铵邻苯二甲酰亚胺氧基催化剂（TBAPINO），作为一种热稳定的有机催化剂，用于在温和条件下进行环状酯的开环聚合（ROP）。在ε-己内酯（ε-CL）的溶液ROP中，在-15至60°C的宽温度范围内实现了定量转化和约20000 g/mol的分子量。在本体条件下，ε-CL在120°C下2小时内转化率达到85%以上。通过在本体聚合中多次添加单体，证明了TBAPINO催化的丙交酯（l-LA）的活性ROP特性。该催化剂对l-LA和ε-CL的开环聚合表现出相当的选择性。就反应时间而言，它们在TBAPINO上的共聚在一锅本体条件下进行，包括单体进料比和添加顺序。得到无色的聚（ε-己内酯-丙交酯）（PCLA），两种单体都有相当高的转化率，分子量超过22000 g/mol。
