聚合反应介质对丙烯腈/衣康酸共聚物结构与性能的影响  

Structures and Properties of Acrylonitrile(AN) and Itaconic Acid(IA)Copolymers Affected by Polymerization Reaction Medium

作　　者：曾照坡[1] 张珍珍[1] 肖茹[1] 吕永根[1] 

机构地区：[1]高性能纤维及制品教育部重点实验室,东华大学材料科学与工程学院,上海201620

出　　处：《高分子学报》2016年第9期1229-1237,共9页Acta Polymerica Sinica

基　　金：国家重点基础研究发展计划(973计划,项目号2011CB605602,2011CB605603)资助项目

摘　　要：利用混合溶剂沉淀聚合法研究了水/环丁砜(H_2O/TMS)等4种不同聚合反应介质对丙烯腈/衣康酸(AN/IA)共聚物的转化率、重均分子量(Mw)及分布(D)、表面微观形貌、竞聚率及链结构、聚合物热性能和纺丝性能的影响.结果表明,P(AN/IA)聚合物转化率随着混合溶剂中H_2O含量的增加,呈先升高后降低的趋势.P(AN/IA)的Mw与水/溶剂比例成线性增加的关系,其中,以H_2O/TMS作为混合反应介质所制备P(AN/IA)的Mw最大,D最小(小于2).AN与IA以H_2O/TMS为聚合介质时倾向于理想共聚,2IA链段分布几率仅为2.87%.以H_2O/TMS为聚合体系所制备P(AN/IA)结构疏松、颗粒粒径较小且易溶解,预氧化时环化反应放热速率低、放热区间宽,热稳定化阶段形成耐热梯形结构反应所需能垒小.P(AN/IA)/TMS纺丝溶液的表观黏度低,TMS为PAN的良溶剂.P（AN/IA） copolymers were obtained in a mixture solution of tetramethylene sulfone （TMS）/water and other four different polymerization mediums and polymer conversion rate, weight average molecular weight （Mw） and molecular weight distribution （D）, surface micro-topography, monomer reactivity ratios, chain structure, thermal property and spinning performance were investigated. The results showed that with an increase of H2O in the mixed solvent mixture, the polymer conversions were increased firstly and then decreased. The experimental results showed that there were good linear relationships between the weight average molecular weight （Mw） and the ratio of H2O/TMS as well as the other four different polymerization mediums. But MW and D （less than 2） of P（AN/IA） polymer obtained in HEO/TMS mixture reached the maximum and the minimum, respectively, compared with the other polymerization systems. AN copolymerized with IA in H2O/TMS mixture tended to ideal polymerization, according to statistical predication, the distributing probability of 2IA segment was only 2.83%. Looser structure, smaller particle size, more soluble, lower heat release rate, wider heat release range, smaller reaction energy barrier were required by thermal stabilized ladder-like structure during cyelization reaction of PAN copolymer which could be obtained in HEO/ TMS mixture. The apparent viscosity of spinning dope was lower and TMS was an excellent solvent for PAN.

关 键 词：丙烯腈 衣康酸 混合溶剂 热稳定性 可纺性 

分 类 号：O631.11[理学—高分子化学]