聚甲基丙烯酸甲酯大单体与苯乙烯共聚合动力学研究
Kinetics of the copolymerization of PMMA-MA macromers with styrene
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摘要: 合成了端基为甲基丙烯酸酯的四种不同分子量的聚甲基丙烯酸甲酯大单体(M_1),分别与苯乙烯(M_2)共聚,用GPC方法和称重法测定共聚数据,以Kelen—Tüd■s方法进行处理。结果表明,此体系不符合Mayo-Lewis方程。而共聚机理分析说明式r′_2=ln(M_2_0/M_2)/In(M_1_0/M_0)仍可描述此体系。由此式计算了r′_2,值。r′_2随大单体分子量、大单体初始浓度及反应温度等反应条件而变化(r′_2=0.79-1.3)。在大单体共聚反应中,存在着较大的扩散控制因素,扩散过程减慢将使r′_2增大。Abstract: PMMA-MA (MA: methacrylate)macromers (M_1) with different molecular weight were synthesized with radical polymerization and characterized with ~1H-NMR, VPO and sulphur analysis. The maeromers were copolymerized with styrene (M_2). The treatment with Kelen-T(?)d(?)s method of the copolymerization data obtained with GPC and gravimetric analysis indicate that Mayo-Lewis equation is invalid for this copolymerization system, while the equation r_2=1n(M_2_0/M_2)/1n(M_1_0/M_1) describes it according to analysis of the mechanism. With this equation, several values of r_2 were calculated out by using mean square regression, r_2 changes from 0.79 to 1.3 due to different reaction conditions, such as (?)_n and initial concentration of the macromers and the temperature. In this system exists an obvious diffusion factor. So r_2 increases as the diffusion process slows down.