丙烯腈-衣康酸溶液共聚反应行为研究  

Experimental and Modeling Study on the Solution Copolymerization Rate of Acrylonitrile and Itaconic Acid

作　　者：缪金根[1] 王世栋[1] 程振民[1] 周美华[2] 潘鼎[2] 

机构地区：[1]华东理工大学化学工程联合国家重点实验室,上海200237 [2]东华大学高性能纤维及制品教育部重点实验室,上海201620

出　　处：《化学反应工程与工艺》2013年第4期364-371,共8页Chemical Reaction Engineering and Technology

基　　金：上海市科委资助项目(07DJ14002;09DZ1100203)

摘　　要：在溶剂二甲基亚砜中以偶氮二异丁腈为引发剂引发丙烯腈与衣康酸进行间歇共聚,分别结合基于末端基和隐性前末端基模型的均相二元共聚反应速率方程,在全转化范围内研究了单体含量与配比、反应温度和引发剂含量等工艺条件对共聚速率的影响。结果表明,升温能有效提高低转化率阶段的共聚速率,但在高转化阶段易出现死端聚合的趋势:总单体含量为22%以下时,单体含量对共聚速率的影响可以忽略,反应受扩散控制不明显;衣康酸含量增加将显著降低共聚速率,其自阻聚效应归因子衣康酸具有较大的空间位阻而非发生了衰减链转移反应。利用基于自由体积理论的半经验模型修正引发效率后,末端基和隐性前末端基链增长速率模型均能很好地描述本体系的表观共聚速率特性。Free radical copolymerization of acrylonitrile and itaconic acid （IA） was performed in the solvent of dimethylsulphoxide with 2,2＇-azobisisobutyronitrile as an initiator. Over the whole range of conversion, the copolymerization rate dependences on conditions including monomer feed amount and composition, temperature and initiator concentration were investigated by the terminal and implicit penultimate models respectively. It is shown that higher temperature leads to higher copolymerization rate at low-to-moderate conversion stage and higher tendency of ＂dead-end polymerization＂ at high conversion stage. The effect of monomer feed amount on the overall conversion is negligible and the diffusion-controlled termination reactions are not important, when the initial overall monomer weight fraction is less than 22%. IA may retard the copolymerization significantly because of its reluctance to homopolymerize, which is attributed to the steric hindrance of two carboxyl groups in IA rather than the degradative chain transfer reaction to itself. It is also observed that both terminal and implicit penultimate models can interpret the apparent copolymerization rate of this system after modifying the initiator efficiency using the free volume theory.

关 键 词：丙烯腈 衣康酸 溶液共聚 聚丙烯腈 碳纤维 反应动力学 

分 类 号：TQ342.31[化学工程—化纤工业]