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机构地区:[1]中国纺织大学化学纤维研究所
出 处:《中国纺织大学学报》1993年第6期24-31,共8页Journal of China Textile University
摘 要:对于硝酸(HNO_3)溶剂中以过硫酸铵—乙酰基丙酮—硝酸高铁[(NH_4)_2S_2O_8—CH_3COCH_2COCH_3-Fe(NO_3)_3]氧化还原体系为引发剂的丙烯腈—丙烯酸甲脂—甲叉丁二酸[AN-MA-IA]的三元共聚反应进行了研究。在反应动力学的实验基础上对反应机理作了分析,得出如下结论:聚合反应速率与单体浓度的1.5次方及过硫酸铵[(NH_4)_2S_2O_8]浓度的0.5次方成正比,与乙酰基丙酮(CH_3COCH_2COCH_3)及硝酸高铁[Fe(NO_3)_3]浓度关系不大;分子量与单体浓度的0.5次方成正比,与(NH_4)_2S_2O_8浓度的0.5次方成反比,与Fe(NO_3)_3浓度无关。CH_3COCH_2COCH_3是链转移剂,其浓度的增大会使分子量下降,在可能的反应历程推导的基础上建立了速率方程。The AN-MA-IA ternary copolymerization in HNO_3 solvent system with (NH_4)_2S_2O_8CH_3COCH_2COCH_3-Fe(NO_3)_3 redox system used as initiator is studied in this paper. On the basis of reaction kinetics experiments, the polymerization mechanism is analysed in detail. The following conclusions are obtained: the polymerization rate is proportional to the 1.5 power of monomer concentration and to the 0.5 power of (NH_4)_2S_2O_8 concentration, but independent of the concentrations of CH_3COCH_2COCH_3 and Fe(NO_3)_3, concentration, the molecular weight of the copolymer obtained is proportional to the 0.5 power of monomer concentration and to the —0. 5 power of (NH_4)_2S_2O_8 concentration,independent of Fe(NO_3)_3 concentration. Because CH_3COCH_2COCH_3 is a chain tansfer agent, the molecular weight obtained decreases with its increasing concentration. On the basis of possible reaction equtions and processes, the rate equation of AN-copolymerization is obtained.
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