混合溶剂配比对丙烯腈共聚物结构和预氧化性能的影响  

Effect of mixed solvent ratio on structure and pre-oxidation performance of acrylonitrile copolymer

作　　者：党延金 杨梦雪 吴倩倩 丁盼盼 李昌垒 巨安奇[1] DANG Yanjin;YANG Mengxue;WU Qianqian;DING Panpan;LI Changlei;JU Anqi(State Key Laboratory of Fiber Material Modification,School of Materials Science and Engineering,Donghua University,Shanghai 201620;Weifang Xinlong Biological New Materials Co.,Ltd.,Weifang 261100)

机构地区：[1]东华大学材料科学与工程学院纤维材料改性国家重点实验室,上海201620 [2]潍坊欣龙生物新材料有限公司,山东潍坊261100

出　　处：《合成纤维工业》2023年第1期1-7,共7页China Synthetic Fiber Industry

基　　金：上海市高性能纤维复合材料协同创新中心开放课题基金(X12812101/013)。

摘　　要：以3-酰胺基-3-丁烯酸甲酯(ABM)为共聚单体,以不同配比的二甲基亚砜(DMSO)/去离子水混合溶液为溶剂,通过自由基聚合反应制备高相对分子质量聚(丙烯腈-3-酰胺基-3-丁烯酸甲酯)共聚物(P(AN-co-ABM)),研究了混合溶剂配比对聚合反应的单体转化率(η),以及P(AN-co-ABM)的黏均相对分子质量(M_(η))、结构和预氧化性能的影响。结果表明:随着混合溶剂中去离子水含量的增加,聚合反应的η从64.32%下降至24.51%,P(AN-co-ABM)的M_(η)从1.54×10^(5)增加至8.71×10^(5);ABM通过离子机理引发环化反应,使得P(AN-co-ABM)的环化起始引发温度(T_(i))较丙烯腈均聚物降低约40℃,放热峰宽化,避免了集中放热;随着混合溶剂中DMSO含量的增加,P(AN-co-ABM)的预氧化程度增加,T_(i)降低约16℃;混合溶剂中DMSO/去离子水质量比为60/40时,P(AN-co-ABM)的放热速率最低,为4.33 J/(g·℃),并且具有较低的T_(i)(200.03℃),有利于制备高性能碳纤维。High-relative molecular weight mass poly(acrylonitrile 3-amido-3-butenoic acid methyl ester)copolymer(P(AN-co-ABM))was prepared by free radical polymerization using 3-amido-3-butenoic acid methyl ester(ABM)as comonomer and dimethyl sulfoxide(DMSO)/deionized water mixed solution with different ratios as solvent.The effects of the mixed solvent ratio on the monomer conversion(η)of polymerization reaction and the viscosity average relative molecular weight mass(M_(η)),structure and pre-oxidation performance of P(AN-co-ABM)were studied.The results showed thatηof the polymerization reaction decreased from 64.32% to 24.51%,Mηof P(AN-co-ABM)increased from 1.54×10^(5) to 8.71×10^(5) with the increase of deionized water content in mixed solvent;ABM initiated the cyclization reaction through ionic mechanism,so that the initial initiation temperature(T_(i))of P(AN-co-ABM)cyclization was about 40℃lower than that of acrylonitrile homopolymer and the exothermic peak was widened,avoiding concentrated exothermic reaction;the preoxidation degree of P(AN-co-ABM)increased and T_(i) decreased by about 16℃ with the increase of DMSO content in the mixed solvent;and P(AN-co-ABM)had the lowest exothermic rate of 4.33 J/(g·℃)and a lower T_(i)(200.03℃),which was conducive to the preparation of high-performance carbon fibers,when the mass ratio of DMSO/deionized water in the mixed solvent was 60/40.

关 键 词：聚丙烯腈纤维 3-酰胺基-3-丁烯酸甲酯 丙烯腈共聚物 混合溶剂 自由基聚合 结构 预氧化性能 

分 类 号：TQ342.31[化学工程—化纤工业]