芳氧基钇在DMF中引发丙烯腈聚合的动力学研究  

KINETICS OF ACRYLONITRILE POLYMERIZATION INITIATED BY Y(OAr)_3 in DMF

作　　者：郑豪[1] 张一烽[2] 沈之荃[2] 

机构地区：[1]浙江大学化学系 [2]浙江大学高分子科学研究所,杭州310027

出　　处：《高分子学报》2006年第3期429-431,共3页Acta Polymerica Sinica

基　　金：国家自然科学基金重点(基金号20434020);浙江省科委资助项目

摘　　要：用单组分三(2,6-二叔丁基4甲基苯氧基)钇配合物[Y(OAr)3]引发丙烯腈聚合,发现介质对聚合反应的影响很大,在介电常数较大的极性溶剂N,N-二甲基甲酰胺(DMF)中,AN聚合反应的活性较高,在50℃下聚合3h,丙烯腈聚合反应转化率达到94%,所得聚丙烯腈(PAN)含52%间规结构.在DMF中聚合反应速率与单体、引发剂的浓度分别呈一级关系,丙烯腈聚合反应的表观活化能为22.1kJ·mol-1.It was found that yttrium tris（2,6-di-tert-butyl-4-methyl phenolate） could be an effective initiator for polymerization of acrylonitrile.The study of influence of solvent showed that DMF with high dielectric constant gave higher conversions（ 〉 94 % ） at 50℃,3 h. The kinetics of acrylonitrile polymerization using Y（OAr）3 in DMF was investigated by the weight method. The results indicated that the rate of polymerization showed a first order relationship with respect to both the monomer（AN） concentration and the initiator [Y（OAr）3 ] concentration, respectively, and the overall activation energy of polymerization reaction was 22.1 kJ·mol^-1 according to the Arrhenius equation. J3C-NMR studies showed that the PAN prepared had a syndiotactic triad （rr） content of 52 %.

关 键 词：丙烯腈 芳氧基钇 聚合反应动力学 

分 类 号：O631[理学—高分子化学]