Preparation and Properties of Polyallenes III. Polymerization of Allenes Induced by Al-i-Bu₃-VOCl₃Catalyst

Abstract

Abstract The polymerization activity of several allenes under the influence of Al-i-Bu3-VOCl3, and structure and properties of the solid polymers obtained, have been studied. Allene; butadiene-1, 2; hexadiene-1, 2; 3-methylbutadiene-1, 2; 3-methylpentadiene-1, 2; and pentadiene 2, 3 could be converted into soluble, solid polymers. 2-Methylpentadiene-2, 3; tetramethylallene; and tetraphenylallene did not react under the polymerization conditions applied. The following order of polymerization activity seems to be valid: CH2˭C˭CH2 > R1CH˭C˭CH2 > R1R2C˭C˭CH2 ≥ R1CH˭C˭CHR2, > R1R2C˭C˭CHR3 ≥ R1R2C˭C-CR3R4. The polymers of the homologues of allene were obtained as amorphous solids with the exception of poly(3-methyl-butadiene-1, 2), which was fairly crystalline.