聚酯链结构定制及其构效关系

doi:10.11949/0438-1157.20201101

摘要/Abstract

摘要：

聚酯材料的物理性能与可生物降解性为其聚集态结构所决定，而聚合物链的化学组成、序列和拓扑结构又是决定聚合物聚集态结构的最关键因素。为此，本文从基于聚合过程调控的聚酯链结构定制出发，总结了嵌段、长支链、梳状、星型、超支化与树枝状结构聚酯的定制方法；评述了链结构与聚酯热与力学性能之间的构效关系，探讨了链结构对聚酯降解性能的影响规律，前人的研究表明共聚物嵌段长短影响着结晶聚集态结构，长支链的存在有助于聚酯结晶温度与结晶度的提高；链的结晶能力、链长及亲疏水性决定了聚酯的降解性能。文中还对高性能可生物降解聚酯材料的开发进行了展望。

关键词: 聚酯, 链结构, 结晶, 力学性能, 降解

Abstract:

The physical properties and biodegradability of polyester materials are determined by its aggregate structure. The chemical composition, sequence and topological structure of the polymer chain are the most critical factors that determine the polymer aggregate structure. We herein summarize the methods for precisely tailor polyester chains, including block, long chain branch, comb, star, hyperbranch and dendrimer, with the aid of polymerization process control. We also review the relationships between the chain structures and polyester thermal and mechanical properties, and discuss the effect of the chain structures on degradation performances of polyesters. Previous studies have shown that the copolymer block length determines the crystalline structure, the presence of long chain branches contributes to the increase of crystallization temperature and crystallinity of polyester, and the crystallization ability, length, and hydrophobicity of the chains determine the degradation performance of polyester. Meanwhile, we prospect the development of high-performance biodegradable polyesters.

Key words: polyester, chain structure, crystallization, mechanical property, degradation

中图分类号:

TQ 311

王松林, 吴海强, 姜冰雪, 赵志超, 欧阳杰, 徐志玉, 徐锦龙, 刘平伟, 王文俊. 聚酯链结构定制及其构效关系[J]. 化工学报, 2021, 72(2): 852-862.

WANG Songlin, WU Haiqiang, JIANG Bingxue, ZHAO Zhichao, OUYANG Jie, XU Zhiyu, XU Jinlong, LIU Pingwei, WANG Wenjun. Tailoring chain structures of polyesters and their effect on physical and degradation properties[J]. CIESC Journal, 2021, 72(2): 852-862.

图/表 6

图1 酸酐、环氧和内酯共聚合成嵌段聚酯[39]

Fig.1 Copolymerization of anhydride, epoxy, and lactone to synthesize block polyesters[39]

图2 以季戊四醇为支化剂合成长支链PBST[50]

Fig.2 Synthesis of long chain branched PBSTs using pentaerythritol as a branching agent[50]

图3 Novozym 435催化合成超支化聚酯[58]

Fig.3 Synthesis of hyperbranched polyesters using Novozym 435 as catalyst[58]

图4 多代树枝状聚合物[61]

Fig.4 Different generations of pseudodendrimers[61]

表1 不同支化剂用量的长支链PLA的热性能[64]

Table 1 Thermal properties of long chain branched PLAs synthesized at various concentrations of COP[64]

支化剂用量/%	冷却速度3℃/min					冷却速度30℃/min
支化剂用量/%	T_c/℃	T_g/℃	T_m/℃	ΔH_m/(J/g)	X_c /%	T_c/℃	T_g/℃	T_m/℃	ΔH_m(J/g)	X_c /%
0	100.0	61.3	169.1	29.9	31.9	—	60.5	163.5/169.2	36.1	2.2
0.1	116.3	60.4	167.8	37.1	39.6	—	60.2	160.8/167.7	35.7	4.6
0.3	130.2	60.8	166.5	37.9	40.4	96.3	61.0	165.8	35.9	17.8
0.5	134.4	60.5	165.6	40.0	42.7	103.9	60.0	160.8/165.5	34.8	34.0
0.7	132.6	60.7	165.1	39.8	42.5	102.4	60.4	160.6/165.3	33.9	31.6

图5 在37℃、pH = 7.4的PBS缓冲液中PDLLA 和PLLA的质量损失[91]

Fig.5 Mass loss of PDLLAs and PLLAs in phosphate buffered saline (PBS, pH = 7.4) at 37 °C[91]

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