Abstract
AbstractBicyclo[2.2.1]hepta‐2,5‐diene, in the presence of free‐radical initiators, homopolymerizes to a low molecular weight, soluble polymer containing both 3,5‐disubstituted nortricyclene and 5,6‐disubstituted bicyclo [2.2.1] hept‐2‐ene units in the polymer backbone. When the bicycloheptadiene (M2) is copolymerized with vinyl chloride, vinylidene chloride, acrylonitrile, ethyl acrylate, and methyl methacrylate, only the transannular product, 3,5‐disubstituted nortricyclene, is found in the high molecular weight copolymers. Reactivity ratios for the above mentioned copolymerizations at 50°C. are: r1 = 0.74, r2 = 0.35; r1 = 1.41, r2 = 0.08; r1 = 0.67, r2 = 0.08; r1 = 3.05, r2 = 0.01; r1 =10.0, r2 = 0; respectively. From these data, the Q and e values for bicyclo[2.2.l]hepta‐2,5‐diene average 0.09 and −1.04, respectively.
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