内酯和环氧烷烃共聚合成聚酯-聚醚共聚物的研究进展

doi:10.11949/0438-1157.20200944

摘要/Abstract

摘要：

脂肪族聚酯作为一种高性能、多用途的生物可降解材料，被认为是具有吸引力的石油基聚合物替代品之一。现有的脂肪族聚酯存在的结构单一、亲水性差以及脆性较强等缺点，限制了其在医药卫生等领域的应用。因此，高效地实现聚酯的改性具有重要的理论研究意义和实际应用价值。其中，将醚类官能团与酯链段相结合得到聚醚-聚酯共聚物是提高聚酯性能的一类行之有效的改性方法。本文综述了内酯和环氧烷烃共聚合成聚酯-聚醚共聚物的研究进展。以共聚物的主链序列分类，分别介绍了嵌段、无规以及交替共聚物的合成方法以及相应聚合物的性质和性能。

关键词: 环氧烷烃, 内酯, 聚合, 聚酯-聚醚共聚物, 合成, 催化

Abstract:

As a high-performance, multi-purpose biodegradable material, aliphatic polyester is considered to be one of the attractive alternatives to petroleum-based polymers. However, they often suffer from drawbacks, such as hydrophobicity and brittleness due to their single structure nature, which limits its application in biomedical and pharmaceutical industries. Thus, the modification of polyester is of great theoretical significance and practical application, of which one efficient way is to incorporate the aliphatic polyethers segments into the main chain of polyesters. Herein, this review aims to describe the synthesis of polyester-polyether copolymers by the copolymerization of lactones and epoxides, including random, block, and alternating copolymers.

Key words: epoxide, lactone, polymerization, polyester-polyether copolymer, synthesis, catalysis

中图分类号:

TQ 317.3

高宏娟,任伟民. 内酯和环氧烷烃共聚合成聚酯-聚醚共聚物的研究进展[J]. 化工学报, 2021, 72(1): 440-451.

GAO Hongjuan,REN Weimin. Review on synthesis of polyether-co-polyester from copolymerization of epoxides and lactones[J]. CIESC Journal, 2021, 72(1): 440-451.

图/表 21

图1 LA与环氧烷烃的嵌段共聚反应

Fig.1 Block copolymerization of LA with epoxides

图2 环氧烷烃与内酯的嵌段共聚反应

Fig.2 Block copolymerization of epoxides with lactones

表1 不同催化剂催化内酯和环氧烷烃嵌段共聚的结果

Table 1 Block copolymerization results of lactones with epoxides catalyzed by various complexes

图3中催化剂	单体	投料摩尔比 (内酯/环氧烷烃)	时间/h	温度/℃	转化率^①/%		分子量^②	分子量分布^②	文献
图3中催化剂	单体	投料摩尔比 (内酯/环氧烷烃)	时间/h	温度/℃	内酯	环氧化物	分子量^②	分子量分布^②	文献
1	LA/EO	0.5	22	60	—	—	26100	6.2	[44]
2	LA/EO	0.5	22	60	—	—	17600	3.2	[44]
3	LA/CHO	1.0	—	—	45	75	7600	1.29	[45]
4	LA/CHO	1.0	3	24	98	69	37500	1.5	[46]
5	CL/EO	1.8	—	50	50	—	10400	1.08	[48]
6	CL/LA/EO	—	—	—	—	70	3500	1.12	[49]
7/8	LA/GPE	0.5	0.75	25	—	98	4600	1.13	[50]

图3 环氧烷烃与内酯嵌段共聚的催化剂

Fig.3 Catalysts for the block copolymerization of epoxides with lactones

图4 用于氧化还原调控聚合的催化剂

Fig.4 Iron-based redox-switchable catalyzed copolymerization of epoxide and LA

图5 GPE与LA的嵌段共聚反应

Fig.5 Block copolymerization of GPE with LA

图6 Lewis 酸碱对催化环氧烷烃与内酯的嵌段共聚

Fig.6 Block copolymerization of epoxides and lactones catalyzed by Lewis pairs

图7 内酯与环氧烷烃的无规共聚反应

Fig.7 Random copolymerization of lactones with epoxides

图8 LA和EO的无规共聚反应

Fig.8 Random copolymerization of LA with EO

表2 不同催化剂催化内酯和环氧烷烃无规共聚的结果

Table 2 Random copolymerization results of lactones with epoxides catalyzed by various complexes

图6、图8~图10、图12~图13中催化剂	单体	投料摩尔比 (内酯/环氧烷烃)	时间/ h	温度/ ℃	转化率^①/%	含量^②/%		分子量^③	分子量分布^③	T_g^④/℃	文献
图6、图8~图10、图12~图13中催化剂	单体	投料摩尔比 (内酯/环氧烷烃)	时间/ h	温度/ ℃	转化率^①/%	内酯	环氧烷烃	分子量^③	分子量分布^③	T_g^④/℃	文献
9	LA/EO	0.15	2	25	—	3.6	—	11100	1.14	—	[55]
10	LA/EO	1.0	5	90	—	—	—	20000	1.5	11	[52]
11	CL/BGE	2.33	—	80	—	—	28	18000	1.4	–54	[53]
12	LA/BO	1.0	24	45	—	0.25	—	29000	11.2	26	[54]
12	LA/PO	2.0	24	45	—	0.34	—	80000	6.5	18	[54]
12	CL/PO	2.0	24	45	—	0.51	—	45000	8.3	—	[54]
12	LA/ECH	2.0	24	45	—	0.22	—	16840000	1.5	–33	[54]
13/14	VL/PO	1.0	6	23	25	—	—	11100	1.2	—	[56]
15	CL/PO	1.0	4	50	33	—	—	14300	1.36	—	[57]

图9 CL和BGE的无规共聚

Fig.9 Random copolymerization of CL with BGE

图10 内酯和端位环氧烷烃的无规共聚

Fig.10 Random copolymerization of lactones and terminal epoxides

图11 TEB引发LA和EO无规共聚

Fig.11 Random copolymerization of LA and EO initiated by TEB

图12 PO和内酯的无规共聚

Fig.12 Random copolymerization of lactones with PO

图13 CL和PO的无规共聚反应

Fig.13 Random copolymerization of CL with PO

图14 内酯与环氧烷烃的交替共聚反应

Fig.14 Alternating copolymerization of lactones with epoxides

图15 五元环内酯和GPE的交替共聚

Fig.15 Alternating copolymerization of five-membered cyclolactones with GPE

图16 EMI催化芳香族六元内酯和环氧烷烃的交替共聚

Fig.16 EMI catalyzed alternating copolymerization of aromatic six-membered lactones and epoxides

表3 不同催化剂催化内酯和环氧烷烃嵌段共聚的结果

Table 3 Alternating copolymerization results of lactones with epoxides catalyzed by various complexes

图3、图9、图15~图18中催化剂	单体	投料摩尔比内酯/环氧烷烃	时间/ h	温度/ ℃	转化率^①/ %	分子量^②	分子量分布^②	文献
16	A^③/GPE	1.0	74	120	91	6600	1.6	[59]
17	DHNP/GPE	1.0	3	120	93	2400	1.9	[67]
18	DHCM/PO	0.5	6	—	88	15000	1.3	[68]
18	DHCM/CPO	0.5	24	—	70	18000	1.5	[68]
18	DHCM/CHO	0.5	6	—	58	7000	1.4	[68]
11	DHCM/EO	0.2	72	50	25	2500	1.29	[69]
6	DHCM/EO	0.8	22	60	＞99	2100	1.07	[70]
19	DHCM/EO	0.5	72	60	＞99	7500	1.09	[70]

图17 SalenCr(Ⅲ)催化DHCM和环氧烷烃的交替共聚

Fig.17 Alternating copolymerization of DHCM and epoxides catalyzed by SalenCr(Ⅲ)

图18 膦腈碱催化DHCM和环氧烷烃的交替共聚

Fig.18 Alternating copolymerization of DHCM and epoxides catalyzed by phosphazene

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