超支化聚酯酰胺的合成及在聚碳酸酯加工中的应用  

Synthesis of Hyperbranched Poly(ester amide)s and Their Application in Polycarbonate as Rheological Modification Agent

作　　者：汪羽翎[1] 李武松 刘聪聪 黄卫[3] 颜德岳[3] 康宏强 

机构地区：[1]上海交通大学材料科学与工程学院,上海200240 [2]威海晨源分子新材料有限公司,威海264211 [3]上海交通大学化学化工学院,上海200240

出　　处：《高分子学报》2017年第8期1304-1311,共8页Acta Polymerica Sinica

基　　金：国家重点基础研究发展计划(973计划;项目号2012CB821500);国家自然科学基金(基金号91127047)资助项目

摘　　要：以1,2,4-偏苯三羧酸酐(BTAA)和乙醇胺(EMA)为原料,分别采用"二步法"和"一步法"熔融缩聚制备了端羧基超支化聚酯酰胺(HBPEA).第1步利用官能团非等活性原理,在乙醇溶剂中由BTAA中高活性的酸酐基团与EMA中高活性的氨基反应原位生成含1个羟基和2个羧基的AB_2中间体,蒸除乙醇后,再第2步熔融缩聚得到超支化聚酯酰胺,可避免聚合过程中发生凝胶.为便于工业化应用,还采用BTAA与EMA经"一步"熔融缩聚制备了端羧基超支化聚酯酰胺.分别采用核磁共振(NMR)、乌氏黏度计、示差扫描量热仪(DSC)、热失重分析仪(TGA)以及阿贝折射仪等对2种方法所制备的目标产物化学结构和特性黏度等各项性能进行了表征,结果表明:所得聚酯酰胺具有超支化结构,特性黏数为0.12~0.15 d L/g,支化度为0.64~0.65,在350oC之前未发生热失重,玻璃化转变温度为125~126oC,折射率为1.57~1.58,与聚碳酸酯(PC)相近.因此将其作为加工助剂用于PC塑料体系的加工.超支化聚酯酰胺的加入,不仅能改善PC的加工流动性,同时还能改善制品的机械性能和表面光洁度,且不会引起PC色泽的变化.Due to highly branched three-dimensional sphere-like molecular architecture, hyperbranched polymers have shown very different properties such as intramolecular cavities, low viscosity, high solubility and a large number of terminal functional groups if compared with their linear analogues. They can be facilely synthesized via a one-pot polymerization through different methods according to the type of monomers, including polycondensation of ABn monomers, self-condensing vinyl polymerization, self-condensing ring-opening polymerization and so on. Here, hyperbranched poly（ester amide）s（HBPEAs） with terminal carboxyl groups are prepared from benzene-1,2,4-tricarbonylic acid-1,2-anhydride（BTAA） and ethanolamine（EMA） via two-step and one-step melt polycondensation, respectively. In two-step method, the anhydride group in BTAA first reacted with the amino group in EMA to form a AB2 intermediate with one hydroxyl groups and two carboxyl groups in ethanol according to the principle of non-equal reactivity of functional groups. After ethanol evaporated, the AB2 intermediate was melted at 220 oC to polymerize to produce HBPEA without gelation. Furthermore, HBPEA was also synthesized from BTAA and EMA at 220 oC through one-step melt polycondensation, more convenient in the industry. The resulting HBPEAs were characterized by 1H-NMR analysis, Ubbelohde viscometer, differential scanning calorimeter（DSC）, thermo gravimetric analyzer（TGA） and refractive index measurements. their DBs are about 0.64 and intrinsic viscosities are about 0.120 ~ 0.146 d L/g. Their Tgs are about 125 ℃ and refraction indexes are about 1.57 ~ 1.58, which is similar to those of PC. The temperature of 5 wt% weight loss is above 350 ℃. Therefore, HBPEAs can be used as modification agent to process polycarbonate. When HBPEAs were added into PC or PC/CaCO3, not only the process ability of PC or PC/CaCO3 was improved, but also the colour of PC was kept unchanged. In addition, the mechanical properties and the surface roughness of P

关 键 词：超支化聚酯酰胺 熔融聚合 加工助剂 聚碳酸酯 

分 类 号：TQ323.41[化学工程—合成树脂塑料工业]