Experimental and Modeling Study on the Solution Copolymerization Rate of Acrylonitrile and Itaconic Acid
1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai200237, China; 2. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620, China
Abstract: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.
Miao Jingen 1,WangShidong 1,Cheng Zhenmin 1 et al. Experimental and Modeling Study on the Solution Copolymerization Rate of Acrylonitrile and Itaconic Acid[J]. 化学反应工程与工艺, 2013, 29(4): 364-371.