The investigator's new interpretation for charge-transfer polymerization involves tetramethylene zwitterions and diradicals as the key intermediates. To support this concept, he will generate the respective tetramethylenes in novel ways, and will examine their behavior as initiators. Potential sources include thermolysis of cyclobutanes, cyclic sulfones, and cyclic azo precursors. Cyclobutanes containing leaving groups will be used to generate cationic initiating species. Lewis acids will be used to catalyze the formation of tetramethylenes both diradical and zitterionic, depending on the Lewis acid. This will be a powerful new tool for control of initiation. Appropriate gegenionic leaving groups in electrophilic or nucleophilic olefin initiators will control the propagation reaction as well as the initiation. This concept will be used in both coordinated cationic and anionic polymerizations. The concept will be broadened to the study of other polymethylenes, in particular trimethylenes, pentamethylenes, and hexamethylenes. This research is part of the Polymers Program's effort to understand the fundamentals of polymer synthesis so as to be able to control the structure of polymers.
