Abstract
The results reported herein established the complexity of the alkyllithium-initiated anionic homopolymerization, styrene copolymerization and styrene block copolymerization of 1,3,5-hexatriene in comparison to the controlled, predictable behavior observed with dienes. As a result of 1,6- and 1,2-enchainment, conjugated diene units are formed along the polymer backbone which can react with the living carbanionic centers to produce branched polymers as indicated in Equation (1). The general effect of solvent on microstructure, as indicated by infrared spectral analyses, is analogous to that of dienes in that 1,2-addition is increased in polar versus hydrocarbon solvents. The observation of branching reactions suggests that conjugated trienes may be useful as branching agents for copolymerizations or linking reactions analogous to the behavior of divinylbenzenes.