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采用称量法和GPC,研究了以二甲基乙酰胺为溶剂,偶氮二异丁腈为引发剂,自由基溶液聚合制备含芳酰胺结构的新型甲壳型液晶高分子聚[乙烯基对苯二甲酸二(4-甲氧基苯胺)](PMPACS)的聚合反应动力学.研究发现,(1)MPACS的聚合反应在60℃时主要为双基偶合终止,所以反应后期聚合物分子量明显增大,分子量分布变窄;(2)该反应的聚合反应速率方程为Rp=kp[M][I]1/2,表观活化能Eα=44 kJ/mol,在60℃时的聚合反应常数kp=1.04 L·mol-1·h-1;(3)相同聚合条件下,单体的转化率和数均分子量随单体初始浓度[M]0的增加而增大,当引发剂浓度[I]0增加时,聚合物的分子量随之降低,分子量分布增大;(4)该研究虽采用普通自由基聚合,所得聚合物的分子量分布却较窄,仅为1.1～1.4.
A new type of shell-type liquid crystal polymer poly (vinyl p-phenylene ether) with aromatic amide structure was prepared by free radical polymerization using dimethylacetamide as solvent and azobisisobutyronitrile as initiator. The polymerization kinetics of bis (4-methoxyaniline) (PMPACS) showed that (1) the polymerization of MPACS terminated mainly at 60 ℃ and the molecular weight of the polymer in the late stage of reaction was significantly increased (2) The polymerization rate equation of the reaction is Rp = kp [M] [I] 1/2, the apparent activation energy Eα = 44 kJ / mol, and the polymerization reaction constant at 60 ° C. kp = 1.04 L · mol-1 · h-1. (3) Under the same polymerization conditions, the conversion and the number average molecular weight of the monomers increased with the increase of the initial monomer concentration [M] (I) 0, the molecular weight of the polymer decreases and the molecular weight distribution increases. (4) The average molecular weight distribution of the polymer obtained by the conventional free radical polymerization is relatively narrow, only 1.1-1.4.