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以聚乙烯醇(PVA)与氯化铜络合得到含铜量为0.114mmolg-1的配位聚合物(PVA-Cu(Ⅱ)),用IR、TG等分析方法证明聚乙烯醇和铜(Ⅱ)之间存在配位键。用该配位聚合物与亚硫酸钠水溶液组成的催化体系可引发甲基丙烯酸甲酯(MMA)和苯乙烯(St)的共聚合;用1H-NMR方法测定了共聚物的组成,采用Kelen-Tüd鰏方程求得两种单体的竞聚率在35℃下分别为rM=5.23,rS=0.07;测得单体的最高转化率为37%,并考察了温度对竞聚率的影响。
Abstract：A polymer-metal complex (PVA-Cu(Ⅱ)) was prepared at room temperature by a reaction between hydrated copper chloride and poly(vinyl alcohol ) in the presence of a few drops of ammonia. The copper content in the complex was 0.114mmolg-1. The polychelates was characterized by IR, TG and 1H-NMR. The system of PVA-Cu(Ⅱ)/Na2SO3 can initiate the copolymerization of MMA and styrene. In addition, the monomer reactivity ratios of MMA and St copolymerized at different temperatures were evaluated by using Kelen-T黡鰏 equation based on the composition data acquired by the help of 1H -NMR spectra. The obtained values of reactivity ratio rS=0.07 and rM=5.23 at 308K are different from those determined by conventional free radical copolymerisations at the same conditions. The highest total conversion of the two monomers was 37%. The effects of reaction temperature on the monomer reactivity ratios were also examined, it shows that, the two monomer reactivity ratios will incline to 1 with the rise of the reaction temperature, it means the copolymerization tend towards ideal copolymerization.
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基本信息:
中图分类号:O643.3;O631.5
引用信息:
[1]肖猛,路建美,张正彪,朱秀林.聚乙烯醇-铜(Ⅱ)络合物催化甲基丙烯酸甲酯和苯乙烯共聚合的研究[J],2004(05):611-616.
基金信息:
国家自然科学基金资助(20076031);; 江苏省自然科学基金资助(BK 2002042)。