Page 222 - 《精细化工》2023年第1期

第 40 卷第 1 期 精 细 化 工 Vol.40, No.1
20 23 年 1 月 FINE CHEMICALS Jan. 2023

黏合剂
沉淀法合成联苯基液晶环氧及强韧化体系的制备

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张新超，王小慕，马嘉浩，张军营 ，程 珏
（北京化工大学 碳纤维及功能高分子教育部重点实验室，北京 100029）

摘要：以 4,4'-联苯二酚和环氧氯丙烷为原料，通过“一步沉淀法”制备了 4,4'-联苯二酚二缩水甘油醚（DGEBP），
采用 FTIR、NMR、偏光显微镜（POM）和 XRD 对其进行了表征。选择 4,4'-二氨基二苯甲烷、4,4'-二氨基
二苯砜、甲基六氢苯酐、聚醚胺（D230、D400）、双氰胺分别固化 DGEBP，制备了 6 种三维交联网络固化
物。以双氰胺为固化剂，通过 DGEBP（P）改性双酚 A 环氧树脂（A）/聚酚氧树脂（H）二元共混树脂体
系，制备了多元改性体系（P x -A-H），其中，x 为 P 的含量（以 A 的质量为基准，下同）。对 P x -A-H 进行了
POM 和力学性能测试。结果表明，DGEBP 环氧值和结晶度分别为 0.635 mol/100 g 和 91%，不具备液晶行为，
但其在固化体系中表现出了液晶性，有液晶域出现，所得固化物均具有良好的热性能。随着 DGEBP 含量的
增大，固化物玻璃化转变温度和拉伸断裂能整体呈上升趋势，储能模量和冲击强度则先升高后下降。其中，
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P 10 -A-H 的拉伸强度为 87.39 MPa，P 5 -A-H 的拉伸断裂能和冲击强度分别达到了 2.17 J·g 和 16.67 kJ/m ，比
P 0 -A-H 分别提高了 24.7%和 20.8%，韧性明显提升。
关键词：液晶环氧树脂；一步沉淀法；固化剂；热性能；力学性能；黏合剂
中图分类号：TQ323.5 文献标识码：A 文章编号：1003-5214 (2023) 01-0214-10

Synthesis of biphenyl liquid crystal epoxy by precipitation reaction and
preparation of its strengthening and toughening system

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ZHANG Xinchao, WANG Xiaomu, MA Jiahao, ZHANG Junying , CHENG Jue
（Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical
Technology, Beijing 100029, Beijing, China）

Abstract: 4,4'-Dihydroxybiphenyl diglycidyl ether (DGEBP) was prepared by one-step precipitation
reaction of 4,4'-biphenol and epichlorohydrin and characterized by FTIR, NMR, polarizing microscope
(POM) and XRD. Six types of 3D crosslinking networks cured products were then synthesized from DGEBP
cured by 4,4'-diamino-diphenylmethane, 4,4'-diamino-diphenylsulfoxide, methylhexahydrophthalic anhydride,
polyether amine (D230, D400) and dicyandiamide, respectively. A multi-component modified system
(P x -A-H) was also fabricated via modification of bisphenol A epoxy resin (A)/polyphenol oxygen resin (H)
binary blending resin system by DGEBP (P), of which x represented the content of P (based on the mass of A,
the same below), and its POM and mechanical properties were further tested. The results showed that the
prepared DGEBP displayed an epoxy value of 0.635 mol/100 g and crystallinity of 91%, respectively.
Though it did not show liquid crystal behavior itself, DGEBP exhibited liquid crystal behavior in the cured
system with appearance of liquid crystal domains. The cured product had good thermal properties. As the
DGEBP content increased, the glass transition temperature and tensile fracture energy of the cured product
increased, while the energy storage modulus and impact strength increased first and then decreased.
Specifically, the tensile strength of P 10-A-H was 87.39 MPa, and the tensile fracture energy and impact
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strength of P 5-A-H were 2.17 J·g and 16.67 kJ/m , which were 24.7% and 20.8% higher than those of
P 0-A-H, respectively. Moreover, the toughness of P 5-A-H was obviously improved.
Key words: liquid crystal epoxy resin; one-step precipitation reaction; cured agents; thermal properties;

收稿日期：2022-05-08; 定用日期：2022-07-15; DOI: 10.13550/j.jxhg.20220447
作者简介：张新超（1995—），男，硕士生，E-mail：1468827723@qq.com。联系人：张军营（1963—），男，教授，E-mail：zhangjy@
mail.buct.edu.cn；程 珏（1965—），女，教授，E-mail：chengjue@mail.buct.edu.cn。