Functional monomers and polymers. XXXVIII. Postirradiation polymerization of 2,3-dimethylbutadiene in deoxycholic acid canal complexes

Postirradiation polymerization of 2,3-dimethylbutadiene in deoxycholic acid canal complexes was studied under various reaction conditions. The polymerization was carried out in degassed sealed tubes since the atmosphere had a large effect upon the polymer yield. Addition of 2,3-dimethylbutane led to a sharp drop in polymer yield, while hydroquinone showed little effect on the polymerization. The rate of postirradiation polymerization was found to increase with increase in reaction temperature and irradiation dose. The apparent activation energy was obtained as 13.7 kcal/mole in a temperature range between ?14 and 30°C. Existence of living free radicals having a long lifetime, the gradual change of the monomer into the polymer within the canals, and the effective spatial control in canals are discussed on the basis of the postirradiation polymerization behavior, nature of the adducts, and the structure of the polymers.