苯并环丁烯封端的液晶聚酯酰亚胺的制备与性能  

Preparation and Properties of Liquid Crystal Polyesterimides Terminated with Benzocyclobutene

作　　者：吴文虎 李洋[1] 余华光 刘继延[1] 黄祚刚 刘学清[1] Wen-hu Wu;Yang Li;Hua-guang Yu;Ji-yan Liu;Zuo-gang Huang;Xue-qing Liu(Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of Education,School of Optoelectronic Materials and Technology,Jianghan University,Wuhan 430056)

机构地区：[1]江汉大学光电材料与技术学院,光电化学材料与器件教育部重点实验室,武汉430056

出　　处：《高分子学报》2024年第9期1241-1250,共10页Acta Polymerica Sinica

基　　金：国家重点研发计划(项目号2022YFB3603702);江汉大学一流学科建设重大专项(项目号2023XKZ004)资助项目.

摘　　要：设计并合成了具有苯并环丁烯(BCB)结构的含酚羟基的酰亚胺2-(二环[4.2.0]辛-1,3,5-三烯-3-基)-5-羟基-1H-异吲哚-1,3(2H)-二酮(BCB-HP)和含芳酸的酰亚胺2,3-二氢-1,3-二氧-2-(二环[4.2.0]辛-1,3,5-三烯-3-基)-1H-异吲哚-5-羧酸(BCB-CP),与4-羟基苯甲酸(4-HBA)、6-羟基-2-萘甲酸(HNA)和N-(3-羧基苯基)-4-羟基邻苯二甲酰亚胺(3-CHP)通过溶液缩聚共聚合成了液晶聚酯酰亚胺(LCPEI).与不含热活性BCB基团的LCPEI比较,BCB型LCPEI具有更好的溶解度、较低的熔融温度(Tm=200℃),以及较高的玻璃化转变温度(Tg=149℃),具有良好的加工和应用潜力.LCPEI-22-BCB(含22 mol%CHP)制备的薄膜相较于LCPEI-22,弹性模量更高,介电常数相近(Dk=3.364@10 GHz),介电损耗更低(Df=0.0019),具有作为挠性覆铜板材料的应用前景.Combining features of liquid crystal polyester(LCP)and benzocyclobutene(BCB),two BCB-containing compounds,2-(dicyclo[4.2.0]oct-1,3,5-triene-3-yl)-5-hydroxy-1H-isoindole-1,3(2H)-diketone(BCB-HP)and 2,3-dihydro-1,3-dioxo-2-(dicyclo[4.2.0]oct-1,3,5-triene-3-yl)-1H-isoindole-5-carboxylic acid(BCB-CP),were designed and prepared as terminal capping compounds for LCP synthesis. Liquid crystal polyesterimides (LCPEIs) were synthesized by solution condensation copolymerization of the phenolic BCB-HP, the carboxylic BCB-CP, 4-hydroxybenzoic acid (4-HBA), and 6-hydroxy-2-naphthoic acid (HNA), along with N-(3-carboxyphenyl)-4- hydroxyphthalimide (3-CHP), in the presence of esterification reagents and conditions, diphenyl chlorophosphate (DPCP), LiCl and pyridine at room to reflux temperature, and subsequent methanol precipitation and drying as fine powder. Films of LCPEI-22/44-BCB (with 22 mol%/44 mol% 3-CHP) were generated by hot-pressing and curing procedures, and the curing temperature is around 270 ℃, which is favorably lower than those of 3-ethynylaniline (3-EA, 310 ℃ ) and 4-phenylethynylphthalic anhydride (PEPA, 370 ℃ ), two alkyne-type thermal reactive terminal groups used in literature. These BCB-type LCPEIs have good thermal stabilities (Td,5% = 416.7-454.8 ℃ ) in thermo-gravimetric analysis (TGA) under nitrogen gas. Compared with the commercially available Vectra A950 LCP and non-BCB-containing LCPEI-22/44, LCPEI-22/44-BCB have better solubility (4/1 V/V chloroform-pentafluorophenol), lower melting temperature (Tm, 200 ℃), higher glass transition temperature (Tg= 149-167 ℃ ), and lower isotropic temperature (Ti, 350 ℃ ), indicating processing convenience and application potential. Compared to LCPEI-22, film of LCPEI-22-BCB has a favorably lower linear thermal expansion coefficient (CTE, 41.13 versus 73.29×10-6 K-1), a higher storage modulus (E', 3.48 versus 0.53 GPa), higher elastic modulus (Er, 10.83 versus 9.40 GPa), and higher hardness (H, 0.66 versus 0.58 GPa). Film of LCPEI-22- BCB also has bet

关 键 词：液晶聚酯 聚酯酰亚胺 苯并环丁烯 低介电常数 

分 类 号：TQ323.7[化学工程—合成树脂塑料工业]