Evolution Pathways and Suppression Strategies for Side Reactions in Aromatic Liquid Crystalline Copolyester Synthesis

Qing Yan; Wen-da Li; Shao-chun Shen; Si-zhi Wang; Ruo-yuan Tao

doi:10.11777/j.issn1000-3304.2026.25291

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Evolution Pathways and Suppression Strategies for Side Reactions in Aromatic Liquid Crystalline Copolyester Synthesis

更新时间：2026-03-11

- Evolution Pathways and Suppression Strategies for Side Reactions in Aromatic Liquid Crystalline Copolyester Synthesis
- Acta Polymerica Sinica Pages: 1-11(2026)
- 作者机构：
  
  中石油（上海）新材料研究院有限公司上海 200122
- 作者简介：
  
  Ruo-yuan Tao, E-mail: taoruoyuan@petrochina.com.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.25291
  CLC：
- CSTR：32057.14.GFZXB.2026.7557
- Received：27 December 2025，
  
  Accepted：23 January 2026，
  
  Online First：10 March 2026，
- 稿件说明：
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颜青, 李闻达, 沈少春, 王思智, 陶若渊. 芳香族液晶共聚酯的副反应演变路径及抑制策略. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.25291.

Yan, Q.; Li, W. D.; Shen, S. C.; Wang, S. Z.; Tao, R. Y. Evolution pathways and suppression strategies for side reactions in aromatic liquid crystalline copolyester synthesis. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.25291.
颜青, 李闻达, 沈少春, 王思智, 陶若渊. 芳香族液晶共聚酯的副反应演变路径及抑制策略. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.25291. DOI： CSTR： 32057.14.GFZXB.2026.7557.

Yan, Q.; Li, W. D.; Shen, S. C.; Wang, S. Z.; Tao, R. Y. Evolution pathways and suppression strategies for side reactions in aromatic liquid crystalline copolyester synthesis. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.25291. DOI： CSTR： 32057.14.GFZXB.2026.7557.

摘要

长期以来，芳香族液晶共聚酯(LCPES)的研究主要聚焦于对产物性能的分析和表征，而对聚合反应的动态变化，尤其是副反应产物随温度的动态变化研究较少，这制约了对聚合机制的深入理解和聚合工艺的优化. 本工作采用气相色谱-质谱(GC-MS)联用技术，对基于对羟基苯甲酸(HBA)和6-羟基-2-萘甲酸(HNA)的芳香族液晶共聚酯在熔融聚合过程中产生的副反应产物进行了动态监测，明确了包括苯酚、乙酸苯酯、邻羟基苯乙酮等7种特征副反应产物的生成及其随反应温度的演变趋势与规律. 在此基础上，提出了三段升温的熔融聚合策略：低温段(≤250 ℃)重点抑制4-乙酰氧基苯甲酸(ABA)升华以减缓投料配比的变化；延长中温段(250~300 ℃)以减少脱羧、脱乙烯酮、Fries重排等副反应；缩短高温段(>300 ℃)的酚解反应过程，并避免长时间高温导致的分子链断裂或交联等问题. 结果表明，这种三段升温策略较单段升温法具有显著优势，所得产物的热分解温度提高约11 ℃，液晶特性和力学性能得到显著改善. 由于LCPES聚合过程非常复杂且难以直接表征，本工作通过对反应过程中副反应产物的动态监测，从侧面反映聚合体系副反应及其演变规律，为反应过程工艺控制指明方向，从而有利于获得性能更优的LCPES聚合产物.

Abstract

For decades

research on aromatic liquid crystalline copolyesters (LCPES) has primarily focused on analyzing and characterizing product properties

while the dynamic changes during polymerization

especially the temperature-dependent evolution of side-reaction products

have remained understudied

thereby hindering the in-depth elucidation of LCPES polymerization mechanisms and the rational optimization of polymerization processes. To address this issue

gas chromatography-mass spectrometry (GC-MS) was employed to dynamically monitor the side reaction products generated during the melt polymerization of LCPES based on 4-hydroxybenzoic acid (HBA) and 6-hydroxy-2-naphthoic acid (HNA). This clarified the formation and temperature-dependent evolution trends of seven characteristic side-reaction products

including phenol

phenyl acetate

and 2-hydroxyacetophenone. Based on these findings

a three-stage heating strategy for melt polymerization was proposed: the low-temperature stage (≤250 ℃) focused on suppressing the sublimation of 4-acetoxybenzoic acid (ABA) to minimize deviations in the feed ratio; the medium-temperature stage (250-300 ℃) was prolonged to reduce side reactions such as decarboxylation

ketene elimination

and Fries rearrangement; and the high-temperature stage (>300 ℃) was shortened to mitigate the phenolysis process and avoid issues such as molecular chain scission or cross-linking caused by long-term high temperatures. The experimental results demonstrated that this three-stage heating strategy has significant advantages over the single-stage heating process. The thermal decomposition temperature of the product increased by approximately 11 ℃

with notable improvements in the liquid crystalline characteristics and mechanical properties. Given the high complexity and difficulty in directly characterizing the LCPES polymerization process

dynamic monitoring of side-reaction products indirectly reveals the side reactions and their evolution patterns within the polymerization system

providing guidance for process control and facilitating the preparation of high-performance LCPES products.

关键词

Keywords

references

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