Abstract
AbstractThe mechanism and kinetics of the γ‐ray‐initiated postpolymerization of octadecyl methacrylate and acrylate in lamellar crystals were investigated by a simple model. This model assumes that the initiation points are distributed as in a checkerboard and that polymerization probability of the monomer molecules decreases conically around each initiation point. The two‐dimensional polymerization can be characterized in this cone model by two parameters, a and r; a represents the polymerizability of the monomer for a given condition, and r depends on the number of initiation points per unit area. G values for the initiation reaction of octadecyl methacrylate and acrylate were estimated as 0.8 and 1.6, respectively. The two‐dimensional postpolymerization of long‐chain compounds proceeds in two stages. The rate of polymerization is very high and zero order with respect to monomer concentration in the first stage. It is lower and obeys first‐order kinetics in the second stage. The rate constants of the zero‐and first‐order polymerizations were kp0 = 1.73 molecule sec‐1 and kp1 = 0.93 sec−1, respectively, for octadecyl acrylate at 20°C.
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