液晶聚酯制备的乙酰化过程研究

陈妍如; 张艺; 姜苏俊; 肖中鹏; 张家谦; 黄险波; 曹民

doi:10.11777/j.issn1000-3304.2024.24262

您当前的位置：

首页 >

文章列表页 >

液晶聚酯制备的乙酰化过程研究

研究论文 | 更新时间：2025-04-01

- 液晶聚酯制备的乙酰化过程研究
- Study on the Acetylation Process of Liquid Crystal Polyester
- 高分子学报 2025年56卷第4期页码：623-631
- 作者机构：
  
  1.中山大学化学学院聚合物复合材料及功能材料教育部重点实验室广东省高性能有机聚合物光电功能薄膜工程技术研究中心广州 510275
  2.金发科技股份有限公司企业技术中心广州 510663
  3.广东省特种工程塑料企业重点实验室广州 510663
  4.珠海万通特种工程塑料有限公司珠海 519000
- 作者简介：
  
  E-mail: chenyanru@kingfa.com.cn
- 基金信息：
  
  广东省重点领域研发计划项目(2020B010179001);珠海市产学研合作项目(ZH22017001200004PWC);广东省科技计划专项(2023B1212070027)
- DOI：10.11777/j.issn1000-3304.2024.24262
  中图分类号：
- CSTR：32057.14.GFZXB.2024.7326
- 收稿日期：2024-10-28，
  
  录用日期：2024-12-04，
  
  网络出版日期：2025-02-26，
  
  纸质出版日期：2025-04-20
- 稿件说明：
移动端阅览
陈妍如, 张艺, 姜苏俊, 肖中鹏, 张家谦, 黄险波, 曹民. 液晶聚酯制备的乙酰化过程研究. 高分子学报, 2025, 56(4), 623-631

Chen, Y. R.; Zhang, Y.; Jiang, S. J.; Xiao, Z. P.; Zhang, J. Q.; Huang, X. B.; Cao, M. Study on the acetylation process of liquid crystal polyester. Acta Polymerica Sinica, 2025, 56(4), 623-631
陈妍如, 张艺, 姜苏俊, 肖中鹏, 张家谦, 黄险波, 曹民. 液晶聚酯制备的乙酰化过程研究. 高分子学报, 2025, 56(4), 623-631 DOI： 10.11777/j.issn1000-3304.2024.24262. CSTR： 32057.14.GFZXB.2024.7326.

Chen, Y. R.; Zhang, Y.; Jiang, S. J.; Xiao, Z. P.; Zhang, J. Q.; Huang, X. B.; Cao, M. Study on the acetylation process of liquid crystal polyester. Acta Polymerica Sinica, 2025, 56(4), 623-631 DOI： 10.11777/j.issn1000-3304.2024.24262. CSTR： 32057.14.GFZXB.2024.7326.

摘要

工业上制备芳香族液晶聚酯(LCP)大多需要将含有酚羟基的单体酰化后再熔融聚合，其中酰化后的体系组成对后续反应及最终产物性能具有重要影响. 基于此，本研究系统考察了催化剂种类及用量、酰化剂用量和酰化时长对2种不同类型含酚羟基单体：不对称官能团单体-对羟基苯甲酸(PHBA)和对称双官能团单体-联苯二酚(BP)乙酰化的影响. 研究发现2种单体的乙酰化程度随酰化时间增加均呈现先增大后平衡的趋势. 对于PHBA，在酰化条件下，酰化单体间已自聚且自聚程度会达到某一平衡，不同催化剂种类和酰化剂用量下平衡程度不同，而催化剂用量对其影响较小. 当以醋酸锌为催化剂时，PHBA同时具有高乙酰化和自聚程度，而以氮甲基咪唑(NMI)为催化剂时， PHBA的自聚程度显著降低. 对于BP，其酰化过程中存在少量单端酰化物，随着反应程度的提高逐渐消失，NMI对其乙酰化的催化效率高于金属盐类催化剂.

Abstract

In the industrial field

the preparation of aromatic liquid crystal polyester (LCP) usually contains the acylation of monomers with phenolic hydroxyl group followed by melt polymerization. The composition of the acylated system has a crucial influ

ence on the subsequent reactions and the properties of the final products. Based on this

this paper systematically investigated the effects of catalyst type and dosage

acylation agent dosage

and acylation duration on the acetylation of two different types of phenolic hydroxyl-containing monomers: the asymmetric functional group monomer

p-hydroxybenzoic acid (PHBA)

and the symmetric bifunctional group monomer

biphenol (BP). It was found that the degree of acetylation of both monomers increased first and then reached an equilibrium with the increase of acylation time. For PHBA

under the acylation conditions

self-polymerization occurred among the acylated monomers and the degree of self-polymerization reached a certain equilibrium. The equilibrium degree varied with different catalyst types and acylation agent dosages

while is little affected by the dosage of the catalyst. When zinc acetate was used as the catalyst

PHBA had both high degrees of acetylation and self-polymerization. However

when

-methylimidazole (NMI) was used as the catalyst

the degree of self-polymerization of PHBA was significantly reduced. For BP

a small amount of single-acylation BP substances existed during the acylation process and gradually disappeared with the increase of the reaction degree. The catalytic efficiency of NMI for the acetylation of BP was higher than that of metal salt catalysts.

关键词

Keywords

references

Bhowmik P. K. ; Han H. Fully aromatic thermotropic liquid crystalline polyesters of 3-phenyl-4,‍4 '-biphenol with 4 , 4 '-benzophenone dicarboxylic acid. J. Polym. Sci. A Polym. Chem., 1995, 33 ( 3 ), 415 - 426 . doi: 10.1002/pola.1995.080330309 http://dx.doi.org/10.1002/pola.1995.080330309

Atli A. ; Simon S. ; Cadete Santos Aires F. J. ; Cardenas L. ; Ehret E. ; Lourdin P. A new strategy to activate liquid crystal polymer samples for electroless copper deposition . J. Appl. Polym. Sci. , 2017 , 134 ( 1 ), e 44397 . doi: 10.1002/app.44397 http://dx.doi.org/10.1002/app.44397

董莉 . 热致液晶芳香族聚酯的性能研究及应用 . 纺织科技进展 , 2023 , ( 8 ), 15 - 18 . doi: 10.3969/j.issn.1673-0356.2023.08.007 http://dx.doi.org/10.3969/j.issn.1673-0356.2023.08.007

Evstatiev O. ; Evstatiev M. ; Fakirov S. ; Friedrich K. Manufacturing and characterisation of microfibrillar reinforced composites from liquid crystalline polymers and poly(phenylene ether) . Plast. Rubber Compos. , 2004 , 33 ( 8 ), 353 - 364 . doi: 10.1179/174328904X22297 http://dx.doi.org/10.1179/174328904X22297

Ji Y. ; Bai Y. ; Liu X. B. ; Jia K. Progress of liquid crystal polyester (LCP) for 5G application . Adv. Ind. Eng. Polym. Res. , 2020 , 3 ( 4 ), 160 - 174 . doi: 10.1016/j.aiepr.2020.10.005 http://dx.doi.org/10.1016/j.aiepr.2020.10.005

周其凤 , 王新久 . 液晶高分子 . 北京 : 科学出版社 , 1994 .

Han H. ; Bhowmik P. K. Wholly aromatic liquid-crystalline polyesters . Prog. Polym. Sci. , 1997 , 22 ( 7 ), 1431 - 1502 . doi: 10.1016/s0079-6700(96)00028-7 http://dx.doi.org/10.1016/s0079-6700(96)00028-7

周美胜 , 张文龙 , 丁冬雁 , 李明 . 液晶聚合物薄膜在高频电子封装中的应用进展 . 材料导报 , 2012 , 26 ( 3 ), 15 - 19 . doi: 10.3969/j.issn.1005-023X.2012.03.003 http://dx.doi.org/10.3969/j.issn.1005-023X.2012.03.003

殷卫峰 , 曾耀德 , 杨中强 , 张记明 , 刘锐 , 霍翠 , 颜善银 . 液晶高分子聚合物的类型、加工、应用综述 . 材料导报 , 2022 , 36 ( S1 ), 536 - 540 .

Wei P. ; Lou H. J. ; Yan J. F. ; Li L. L. ; Zhang Y. F. ; Xia Y. M. ; Wang Y. P. ; Wang Y. M. Synthesis and properties of high performance aromatic thermotropic liquid crystal copolyesters based on naphthalene ring structure . Polymer , 2022 , 240 , 124472 . doi: 10.1016/j.polymer.2021.124472 http://dx.doi.org/10.1016/j.polymer.2021.124472

Park G. T. ; Lee W. J. ; Chang J. H. ; Lim A. R. Dependence of the physical properties and molecular dynamics of thermotropic liquid crystalline copolyesters on p -hydroxybenzoic acid content . Polymers , 2020 , 12 ( 1 ), 198 . doi: 10.3390/polym12010198 http://dx.doi.org/10.3390/polym12010198

肖中鹏 , 麦堪成 , 曹民 , 姜苏俊 , 曾祥斌 , 蔡彤旻 , 许柏荣 . 热致液晶聚合物的研究进展 . 广州化工 , 2013 , 41 ( 3 ), 9 - 12 . doi: 10.3969/j.issn.1001-9677.2013.03.004 http://dx.doi.org/10.3969/j.issn.1001-9677.2013.03.004

Suenaga J. I. ; Kinugawa M. Effects of monomer sequence alignment on properties of p-hydroxybenzoic acid/poly(ethylene terephthalate) copolyester . Polym. J. , 1993 , 25 ( 3 ), 315 - 318 . doi: 10.1295/polymj.25.315 http://dx.doi.org/10.1295/polymj.25.315

Choe E. W. ; Borzo M. Synthesis and randomization of well-defined sequence, wholly aromatic copolyester/esteramides . J. Appl. Polym. Sci. , 1994 , 53 ( 5 ), 621 - 632 . doi: 10.1002/app.1994.070530513 http://dx.doi.org/10.1002/app.1994.070530513

Muhlebach A. ; Johnson R. D. ; Lyerla J. ; Economy J. Diad sequence distribution in copolyesters of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid . Macromolecules , 1988 , 21 ( 10 ), 3115 - 3117 . doi: 10.1021/ma00188a035 http://dx.doi.org/10.1021/ma00188a035

Lodha A. ; Ghadage R. S. ; Ponrathnam S. Polycondensation reaction kinetics of wholly aromatic polyesters . Polymer , 1997 , 38 ( 25 ), 6167 - 6174 . doi: 10.1016/s0032-3861(97)00183-3 http://dx.doi.org/10.1016/s0032-3861(97)00183-3

Paul S. ; Nanda P. ; Gupta R. ; Loupy A. Ac 2 O-Py/basic alumina as a versatile reagent for acetylations in solvent-free conditions under microwave irradiation . Tetrahedron Lett. , 2002 , 43 ( 23 ), 4261 - 4265 . doi: 10.1016/s0040-4039(02)00732-3 http://dx.doi.org/10.1016/s0040-4039(02)00732-3

MacKenzie H. A. E. ; Winter E. R. S. Kinetic studies in the solvents acetic acid and acetic anhydride . part I.—Properties of the solvo-system. Trans. Faraday Soc. , 1948 , 44 ( 0 ), 159 - 171 . doi: 10.1039/tf9484400159 http://dx.doi.org/10.1039/tf9484400159

Yerli̇kaya Z. ; Aksoy S. ; Bayramli E. Synthesis and characterization of fully aromatic thermotropic liquid-crystalline copolyesters containing m-hydroxybenzoic acid units . J. Polym. Sci. Part A Polym. Chem. , 2001 , 39 ( 19 ), 3263 - 3277 . doi: 10.1002/pola.1309 http://dx.doi.org/10.1002/pola.1309

Babacan V. ; Aksoy S. ; Yerlikaya Z. ; Altinok H. Thermal and morphological properties of thermotropic liquid-crystalline copolyesters containing poly(ethylene terephthalate) , 4 -hydroxyphenylacetic acid and main-chain rigid aromatic units . Polym. Int., 2010, 59 ( 6 ), 749 - 755 . doi: 10.1002/pi.2779 http://dx.doi.org/10.1002/pi.2779

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

碱木质素的乙酰化及其球形胶束的制备