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机构地区:[1]福建师范大学化学系,福州350007 [2]福建师范大学高分子研究所,福州350007
出 处:《化学学报》1999年第7期831-838,共8页Acta Chimica Sinica
基 金:福建省自然科学基金资助课题
摘 要:根据IR,ESR,XPS和电导率的测试结果推定,在催化剂聚丙烯酰胺-CuCl_2膜表面上,1个Cu^(2+)与聚丙烯酰胺4个链节单元配位,产生σ配位键而交联,形成疏水性的聚丙烯酰胺-Cu(Ⅱ)配位聚合物膜.从该膜的X射线光电子能谱中的Shake-up效应得知,膜表面的Cu^(2+)具有高自旋态电子构型,其缺位处与醋酸乙烯酯,Na_2SO_3配位活化,并产生自由基氢,从而在室温Na_2SO_3水溶液体系(pH=7)中能催化引发醋酸乙烯酯按自由基加聚反应历程进行聚合,诱导期3min 20s,得率75%.The coordination of Cu ( II ) by PAAm was studied by IR, ESR, XPS and electrical conductivity methods. It is concluded that a hydrophobic PAAm-CuCl2 coordination polymer was formed and in the coordination polymer the metal ion is coordinated with four N atoms of four PAAm chains. From the Shake-up peak observed on XPS spectra of the coordination polymer it can be readily shown that PAAm-CuCl2 coordination polymer is in high spin state. The surface of the PAAm-CuCl2 coordination polymer film activated by Na2SO3 can initiate polymerization of VAc in water phase at room temperature. The free radical mechanism for catalytic polymerization of VAc is discussed. The induction period for polymerization is three minutes and twenty seconds. The yield of PVAc is equal to about 75 % .
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