Polymerization of methyl methacrylate by tri-n-butylborane in the presence of amino acid esters

The polymerization of methyl methacrylate by tri-n-butylborane in the presence of amino acid esters was investigated. The binary systems of tri-n-butylborane and amino esters were found to be more effective for initiating the polymerization than tri-n-butylborane alone. Co-catalytic effects of amino acid esters were in the order: tyrosinate > glutamate > aspartate ? phenyl alaninate > serinate > glycinate. The rate of polymerization in a mixture of dimethylsulphoxide and toluene was proportional to the square root of the concentration of the initiator system, to the monomer concentration, and to the concentration of dimethylsulphoxide in the solvent. The overall energy of activation was estimated to be 4.6 kcal/mol for the tri-n-butylborane/methyl tyrosinate system. Copolymerization curves gave a typical free-radical character.