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3 h,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22.1 kJ·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 %.