Polymerization of Ethylene and 1,3-Butadiene Using Methylaluminoxane-Phosphine Catalyst Systems

Although transition metal catalysts have been used extensively for the polymerization of hydrocarbon monomers, several cationic aluminum catalysts have been also known to promote polymerization of ethylene and 1,3-butadiene. Transition-metal catalyzed polymerization generally proceeds via coordination and insertion of the monomer on one metal center. In contrast, in ethylene polymerization using aluminum catalysts, a bimolecular chain growth mechanism, including the reaction between neutral aluminum species and the monomer activated by cationic aluminum species, is proposed. Although previously reported aluminum catalysts are based on a monoaluminum complex, a dialuminum complex is expected to catalyze the polymerization more efficiently, considering the proposed mechanism. In this work, we found that a combination of diphosphines and MAO promotes polymerization of ethylene and 1,3-butadiene. The 1,4-bis(diphenylphosphino)butane (DPPB)/methylaluminoxane (MAO) system showed a much higher activity toward ethylene polymerization than other monophosphine or diphosphine/MAO systems. NMR analysis of a mixture of diphosphine and MAO indicates the formation of cationic dialuminum species in the presence of DPPB, whereas the formation of cationic monoaluminum species occurs in the presence of other diphosphines. The 2,2′-bis(diphenylphosphino)-1,1′-biphenyl (BIPHEP)/MAO system promoted 1,3-butadiene polymerization to give polybutadiene having a cis-1,4 selectivity of up to 93.8%.