Off-campus UMass Amherst users: To download campus access dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.

Non-UMass Amherst users: Please talk to your librarian about requesting this dissertation through interlibrary loan.

Dissertations that have an embargo placed on them will not be available to anyone until the embargo expires.

Date of Award


Access Type

Open Access Dissertation

Document type


Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering


In 1956 Roberts and co-workers synthesized 3-methylenecyclobutene and prepared three polymers by cationic, anionic and free radical methods. Based on IR spectra or the polymers, they concluded that the bulk cationic polymerization of 3-methylenecyclobutene gave predominantly the 1,5-structure, while anionic polymerization by KNH2 in liquid ammonia produced primarily 1,2-addition repeating units. In the free radical homopolymerization of this cyclic diene, they proposed that all types of 1,2-addition, 3,5-addition and 1,5-addition mechanisms were operative. Since this initial brief study, no further investigation of the polymerization of 3-methylenecyclobutene has been reported to date in the literature. It is, therefore, the objective of this project to examine in greater detail the polymer structures obtained by different types of initiators and thus to help elucidate the polymerization mechanisms involved, through the use of high resolution NMR and IR spectroscopy. In the course of this study, it was observed that poly-3-methylenecyclobutene prepared cationically was susceptible to very rapid autoxidation and crosslinking reactions, which complicated the polymer characterization.