三元无皂乳液共聚合动力学及其模型的研究.pdfVIP

高分子学报990504 高分子学报 ACTA POLYMERICA SINICA 1999年 第5期 No.5 1999 三元无皂乳液共聚合动力学及其模型的研究* 闫翠娥　程时远　封麟先 摘　要　以苯乙烯(St)和甲基丙烯酸甲酯(MMA)为主单体，以丙烯酸(AA)为功能单体 进行了无皂乳液批量共聚合.考察了功能单体浓度、引发剂过硫酸铵(APS)浓度及聚合 温度对其动力学行为的影响.建立了转化率-时间关系曲线的模型函数——Gamma积分 函数，用它拟合了转化率-时间关系曲线，获得了聚合过程的重要特征参数，如平均成 核速率(NV)，聚合最大速率(MV)和平稳期平均聚合速率(AV)及成核结束和聚合进入 完成期对应的转化率.同时对聚合速率与以上各聚合参数的关系数据进行了非线性拟 合，得到了它们之间的关系式.研究发现拟合误差很小，成核结束时转化率在15%以 内，成核及聚合速率均随以上参数增大而增大，引发剂过硫酸铵在聚合过程中起决定 作用. 关键词　三元无皂乳液共聚合，聚合动力学及其模型，非线性拟合，功能单体， Gamma函数 STUDY OF KINETICS AND MODEL OF TERNARY EMULSIFIER-FREE EMULSION COPOLYMERIZATION YAN Cuie, CHENG Shiyuan (School of Chemistry and Material Science, Hubei University,Wuhan　430062) FENG Linxian (Dept.of Polymer Science, Zhejiang University,Hangzhou　310027) Abstract　The emulsifier-free emulsion copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process. Effects of concentration of functional monomer AA, initiator concentration and polymerization temperature T on the kinetics of the copolymerizatuion were investigated. Model function of cumulative conversion vs. reaction time——Integrated Gamma Function was built up, and was empolyed to fit the samples of cumulative conversion versus reaction time.The maximum polymerization rate (MV),average polymerization rate (AV) in the steady stage, average nucleation rate (NV) and the corresponding cumulative conversions at moment of nucleation stage ceasing and at the steady stage completing were estimated by calculating extremums and inflexions of it •s fitted Gamma Function. Whereafter, the polymerization rate versus each single polymerization parameter was analyzed with non-linear fitting and the related e