Polymerization of Methylacetylene Catalyzed by Nickel Complexes

Abstract

Study was made on the effect of valence states of nickel (0) and (I) complexes catalysts on the polymerization products of methylacetylene.
Bis (1, 5-cyclooctadiene) nickel, bis (zr-ally1) nickel, bis (acrylonitrile) nikel, bis (t-butyl isocyanide) - nickel and their derivatives were used as the catalyst of nickel (0) complex and (ir-ally1) nickel halides were used as that of nickel (I) complex.
Oligomer of methylacetylene was mainly obtained by using nickel (0) complex. The structural analyses of dimers and trimers showed the presence of two linear dimers (2-methyl1-penten-3-Sine, 2-hexen-4-yne), two cyclic and two linear trimers (1, 3, 5- and 1, 2, 4-trimethylbenezene, 2, 4-dimethyl-1, 3-heptadien-5-yne, 5-methyl-2, 4-octadien-6-yne) in the reaction products.
Methylacetylene catalyzed by nickel (I) complex forms single polymer (close upon eicosamer of methylacetylene). Molecular weight and yield of the polymer were effected by halogen atom in (r-a1ly1) nickel halides. The polymer obtained using (r-cinnamyl) nickel chloride instead of (r-ally1) nic61 chloride, was found to contain phenyl group. Thus, the polymeriza- tion was probably initiated by 7r-cinnamyl group in (z-cinnamyl) nickel chloride.