沉淀法合成联苯基液晶环氧及强韧化体系的制备  

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

作　　者：张新超 王小慕 马嘉浩 张军营[1] 程珏[1] 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)

机构地区：[1]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

出　　处：《精细化工》2023年第1期214-223,232,共11页Fine Chemicals

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,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^(2),比P_(0)-A-H分别提高了24.7%和20.8%,韧性明显提升。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 strength of P_(5)-A-H were 2.17 J·g and 16.67 kJ/m^(2),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.

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 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]