高玻璃化转变温度抗冲击透明聚酯的研究进展

doi:10.16085/j.issn.1000-6613.2022-2069

摘要/Abstract

摘要：

高玻璃化转变温度（T_g）、抗冲击透明聚酯具有高耐热、高透明和优异的力学性能等优点，广泛应用于厨电产品、汽车制造等领域，但目前存在原料不可再生、耐热温度不够高和品种单一等问题。本文根据刚性二元酸或刚性二元醇单体来源的不同，介绍了石油基高耐热聚酯和生物基高耐热聚酯的研究进展，其中石油基高耐热聚酯包括基于2,6-萘二甲酸、4,4'-联苯二甲酸和2,2,4,4-四甲基-1,3-环丁二醇等刚性单体聚酯；生物基高耐热聚酯包括基于呋喃二甲酸、木质素衍生物二酸、天然樟脑及其衍生单体、酒石酸、樟脑醇、异己糖醇等刚性单体聚酯。指出生物基呋喃二甲酸和异山梨醇聚酯是未来高耐热聚酯商业化的重要选择，而原料来源可持续、更高的耐热温度、优异的韧性是未来高T_g、抗冲透明聚酯的主要发展方向。

关键词: 高玻璃化转变温度, 聚酯, 石油基, 生物基

Abstract:

The polyesters with high glass transition temperature (T_g), excellent impact resistance and transparent were used in many fields, such as machine in kitchen and automobile manufacturing. However, the development of high thermal resistance polyesters also faces some problems, such as the monomers derived from petroleum, the insufficient T_g and only single variety. In this work, the petroleum and bio-based polyesters were introduced based on the different rigid diacids or diols monomers. For petroleum based polyesters, they were synthesized from 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid and 2,2,4,4-tetramethyl-1,3-cyclobutanediol. For bio-based polyesters, they were synthesized mainly from 2,5-furandicarboxylic acid, diacid derived from lignin, camphoric acid and L-tartaric acid, galactosyl acid, betulinol and alien sugar alcohol. In the future, the high glass transition temperature, excellent impact resistance and transparent polyesters derived from 2,5-furandicarboxylic acid or isosorbide would be successful mostly in commerce. The main development direction of high T_g and impact resistant transparent polyester in the future research could be focused on the monomers from renewable materials, higher heat resistance temperature and excellent toughness.

Key words: high glass transition temperature, polyester, petroleum-based, bio-based

中图分类号:

戴行, 高瑞雪, 李奕国, 朱锦, 王静刚. 高玻璃化转变温度抗冲击透明聚酯的研究进展[J]. 化工进展, 2023, 42(5): 2555-2565.

DAI Hang, GAO Ruixue, LI Yiguo, ZHU Jin, WANG Jinggang. Research progress on the synthesis of excellent impact and transparency polyesters with high glass transition temperature[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2555-2565.

图/表 18

图1 PEN和PCN聚酯结构式[3]

图2 联苯二甲酸二甲酯高耐热聚酯合成[7]（1mmHg=133.32Pa）

图3 CBDO与环己烷二甲酸二甲酯合成的高Tg聚酯[12]

图4 2,5-FDCA合成路线[13]

图5 PETF共聚酯的合成[19]

图6 双呋喃二甲酸二甲酯合成路线[20]

图7 Me-RDVAs单体合成路线[23]

图8 聚二氢阿魏酸（PHFA）和聚阿魏酸（PFA）聚酯合成[24]

图9 肉桂酸制备刚性二元羧酸TA与刚性二元醇TDO的合成路线[26]

图10 通过樟脑制备樟脑二甲酸的合成路线[27]

图11 TCDM基高耐热聚酯合成[32]

图12 樟脑醌与甘油制备CaG二元醇的合成路线[34]

图13 L-酒石酸制备Thx二甲酯和二元醇的合成路线[37]

图14 2,3:4,5-二-O-亚甲基-半乳糖基聚酯的合成示意图[39]

图15 白桦脂醇的结构[42]

图16 异山梨醇、异甘露糖醇及异艾杜糖醇[44]

图17 乙酰化改性的IS基聚酯合成[48]

图18 生物基异甘露糖二甲醇的合成路线[50]

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