液晶聚酯制备的乙酰化过程研究  

Study on the Acetylation Process of Liquid Crystal Polyester

作　　者：陈妍如 张艺 姜苏俊 肖中鹏 张家谦 黄险波 曹民 Yan-ru Chen;Yi Zhang;Su-jun Jiang;Zhong-peng Xiao;Jia-qian Zhang;Xian-bo Huang;Min Cao(PCFM Lab,Guangdong Engineering Technology Research Centre for High-performance Organic and Polymer Photoelectric Functional Films,School of Chemistry,Sun Yat-sen University,Guangzhou 510275;National-certified Enterprise Technology Center,Kingfa Science and Technology Co.,LTD.,Guangzhou 510663;Guangdong Provincial Key Laboratory of Special Engineering Plastics Enterprise,Guangzhou 510663;Zhuhai Vanteque Specialty Engineering Plastics Co.Ltd.,Zhuhai 519000)

机构地区：[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

出　　处：《高分子学报》2025年第4期623-631,共9页Acta Polymerica Sinica

基　　金：广东省重点领域研发计划项目(项目号2020B010179001);珠海市产学研合作项目(项目号ZH22017001200004PWC);广东省科技计划专项(项目号2023B1212070027)资助.

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.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 influence 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,selfpolymerization 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 N-methylimidazole(NMI)was used as the catalyst,the degree of self-polymerization of PHBA was significantly reduced.For BP,a small amount of singleacylation 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：液晶聚酯 乙酰化 自聚 对羟基苯甲酸 4 4'-联苯二酚 

分 类 号：O631.3[理学—高分子化学]