非金属催化剂在环氧化物和环状酸酐共聚中的研究进展

doi:10.11949/0438-1157.20230662

摘要/Abstract

摘要：

环氧化物与环状酸酐的开环共聚是一种新型的脂肪族聚酯合成技术，其技术核心之一是催化剂的选择与应用。与金属催化剂相比，非金属催化剂在简易性、低毒性、单体适应性、经济性等方面表现出潜在优势，得到迅速发展。针对非金属催化剂在环氧化物和环状酸酐共聚领域的研究进展进行了综述，总结并评述了近年来有机碱、Lewis酸碱对以及其他非金属催化剂在开环共聚反应中的工作机制认识和催化实施效果，对其发展方向和工业化应用潜力进行了展望。

关键词: 非金属催化剂, 环氧化物, 环状酸酐, 共聚

Abstract:

The ring-opening copolymerization of epoxides and cyclic anhydrides is a new type of aliphatic polyester synthesis technology. One of its core technologies is the selection and application of catalysts. Metal-free catalysts exhibit potential advantages compared to metal catalysts with respect to simplicity, low toxicity, monomer adaptability and economy, and have developed rapidly. This article reviews the research progress of metal-free catalysts in the copolymerization of epoxides and cyclic anhydrides, which summarizes the understanding of the working mechanisms and catalytic implementation effects of organic bases, Lewis acid-base pairs, and other metal-free catalysts in the ring-opening copolymerization recently, and proposes prospects for the development direction and industrial application potential of the catalyst.

Key words: metal-free catalysts, epoxides, cyclic anhydrides, copolymerization

中图分类号:

TQ 032.4

张强, 王宪飞, 王凯, 骆广生, 路忠凯. 非金属催化剂在环氧化物和环状酸酐共聚中的研究进展[J]. 化工学报, 2024, 75(1): 60-73.

Qiang ZHANG, Xianfei WANG, Kai WANG, Guangsheng LUO, Zhongkai LU. Advances in metal-free catalysts in copolymerization of epoxides and cyclic anhydrides[J]. CIESC Journal, 2024, 75(1): 60-73.

图/表 10

图1 环氧化物和环状酸酐共聚中的主要非金属催化剂

Fig.1 Mainly used metal-free catalysts in copolymerization of epoxides and cyclic anhydrides

图2 PPNCl催化CO2脱保护的CHO/PC/PA可切换三元共聚[19]

Fig.2 CO2 deprotection-mediated switchable terpolymerization of CHO/PC/PA catalyzed by PPNCl[19]

图3 1,3,5-三嗪磷腈C3N3-Me-P3和C3N3-Py-P3[25]

Fig.3 1,3,5-Triazine-phosphazenes C3N3-Me-P3 and C3N3-Py-P3[25]

图4 Bnz-OCA/PA/NBGE/LA的自切换四元聚合[30]

Fig.4 Self-switchable quadri-polymerization of Bnz-OCA/PA/NBGE/LA[30]

图5 以PMDA为支化剂的PO/PA/CO2三元共聚中网络的形成[32]

Fig.5 Formation of networks in the PO/PA/CO2 terpolymerization with PMDA as a branching agent[32]

图6 Et3B/DBU对催化PO、PA和rac-LA混合物的高选择性三元共聚[40]

Fig.6 Et3B/DBU pair catalyzed highly selective terpolymerization of mixtures of PO, PA and rac-LA[40]

图7 t-BuP1/TEB对催化环状酸酐和t-BGA的开环交替共聚[52]

Fig.7 Ring-opening alternating copolymerization of cyclic anhydrides and t-BGA catalyzed by a t-BuP1/TEB pair[52]

图8 CTPB/脲催化PA与各种环氧化物的ROAC[76]

Fig.8 Illustration of ROAC of PA with various epoxides by using CTPB/urea as catalyst[76]

图9 高活性有机硼催化剂和实验单体[78]

Fig.9 The highly active organoboron catalysts and tried monomers[78]

图10 PA、PO和LA混合单体与HEMIMB的三元共聚途径[83]

Fig.10 The terpolymerization pathways from mixed monomers of PA, PO, and LA with HEMIMB[83]

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