The polymerization of propargyl halides (Cl, Br) using M(CO)5PPh3/R x AlCl3-x (M=Mo,W) as catalysts

Propargylchloride (PCl) and propargylbromide (PBr) were polymerized in good yields using M(CO)5PPh3/RxAlCl3-x as catalysts (M=W, Mo). Mo was found to be more effective than W. The presence of chlorine atoms in co-catalyst was important for the activation of the catalyst. The obtained polymers were coloured, insoluble in all organic solvents and stable until 150°C. From their IR and ESR spectra is concluded that the polymers have highly conjugated structures. The oligomeric products were constituted mainly from cyclotrimers. In the case of Mo-catalyst only 1,2,4-cyclotrimer was obtained; a mixure of 1,2,4 and 1,3,5-derivatives were formed using W-catalysts.