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Date of Award


Access Type

Open Access Dissertation

Document type


Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering


Poly-α,p-dimethylstyrene, which was one of the first vinyl monomers reported to yield a crystalline polymer, was polymerized in a cationic system initiated with BF3 OEt2. In 1958 Thomas and Friedlander polymerized α,p-dimethylstyrene, α-methylstyrene, and styrene using BF3, BF3OEt2, BCl3OEt2 and SnCl4 and compared the degree of crystallinity that could be induced in these three polymers under identical conditions of preparation. Crystallinity could be developed in the polymers of α,p-dimethylstyrene , but only borderline crystallinity (as indicated by x-ray diffraction patterns) could be induced in α-methylstyrene polymers, and no crystallinity could be observed in styrene polymers. The purpose of the present study, therefore, has been to examine the cationic polymerization reactions of α-methylstyrene and substituted α-methylstyrene monomers in order to determine the differences in the structure of the polymers or in the polymerization mechanism which affect the formation of crystallinity.