Polar Tetramethylene Biradicals in "Charge Transfer" Cycloaddition and Polymerization Reactions

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9817239HallIn earlier studies it has been shown that "charge transfer" reactions can be used to initiate vinyl homo- and copolymerizations. The homopolymerizations were cationic and, of course, the copolymerizations were free radical. This project will extend this chemistry to demonstrate that anionic polymerizations can also be brought about by "charge transfer" reactions of donor and acceptor olefins and their resulting cyclobutanes. As a second topic knowledge and capabilities regarding "charge transfer" interactions will be used to control free radical addition polymerizations. The involvement of "charge transfer" complexes in alternating copolymerizations has been long and rather inconclusively discussed. This project will investigate the effect on alternating copolymerizations of added non-polymerizable donor or acceptor molecules which will competitively complex one of the comonomers. By such interactions, the steady state concentrations of free radical will be raised or lowered leading to control of the sequence distribution and composition of the resulting copolymers in ways not accessible today.%%%Valuable educational experience will be gained by the graduate students and postdoctoral associates carrying out this program. They will experience all the aspects of organic synthesis including the latest reaction techniques and reagents. Deliberate polymerizations will be carried out with free radical, and ionic initiators to demonstrate that these are satisfactory monomers. The polymeric products will be separated, isolated and thoroughly characterized, giving the researchers useful knowledge in synthetic polymer chemistry.