Polymerization of vinyl monomers by organoaluminum initiators

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Abstract
Triethyl aluminum, triisobutylaluminum, and diisobutylaluminum hydride have been utilized to polymerize vinyl acetate, methyl methacrylate, and styrene at temperatures from −80 to 25°C. Linear high polymers were obtained in reasonable yields. Based on kinetic experiments studied in dilatometers, it was possible to observe: (a) the rate decreased steadily with time from an initially high value; (b) the initial rate depended upon catalyst concentration and upon the square of the monomer concentration; (c) the overall energy of activation was 13 kcal./mole, and the energy of activation for the degree of polymerization was about 2 kcal./mole. The copolymerization of methyl methacrylate and styrene produced a polymer that was rich in methyl methacrylate. The polymerization is not clearly free‐radical nor ionic, and some form of coordination may take place.

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