Catalytic Chain-Transfer in Polymerization of Methyl Methacrylate. I. Chain-Length Dependence of Chain-Transfer Coefficient

Free-radical polymerization of methyl methacrylate has been conducted in the presence of a new catalytic chain-transfer agent at different temperatures. The new catalyst exhibits a strong chain transfer characteristic, and the chain-transfer coefficient varies from 2.8 × 10⁴ to 6.6 × 10⁴ and depends on chain length and temperature. The chain-transfer coefficients decrease with increasing chain length but reach a limiting value for chains more than 8 units in length. The activation energy for the chain transfer coefficient is -10.1 kJ/mol for this catalyst.