Synthesis and Solution Properties of Semi-rigid Polyelectrolytes and Polyampholytes
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The incorporation of substituted stilbenes in copolymers affects the resulting solution properties and their controlled radical polymerizations. Substituted stilbene monomers readily polymerize in an alternating fashion with acceptor comonomers such as maleic anhydride and maleimide. These sterically crowded polymer backbones are classified as semi-rigid. As this is an uncommon category of polymer backbone rigidity, examples of semi-rigid and rigid polyzwitterions in the literature were reviewed as well as stilbene-containing semi-rigid polymers. Using a deprotection strategy, anionic polyelectrolytes and polyampholytes of stilbene-maleic anhydride copolymers were synthesized and characterized by first synthesizing organic-soluble polymer precursors. Solution shear rheology and statistical segment length measurements reveal that carboxylated polyanions containing stilbene and maleic acid remain semi-rigid in aqueous solutions. It was found that these semi-rigid polyanions exhibited excellent anti-HIV activity possibly due to their more extended polymer chains. This was the first time that intrinsic polymer rigidity was introduced as a possible design parameter for microbicidal applications. Reversible addition fragmentation chain transfer (RAFT) polymerization techniques were used to copolymerize 4-diethylaminostilbene with maleic anhydride. These new semi-rigid copolymers were incorporated into double hydrophilic block copolymers (DHBCS) containing semi-rigid and flexible segments. The subsequent solutions properties of these DHBCs were evaluated with respect to pH and salt responsiveness. Notably, the DHBCs exhibited a "like-charge" attraction as ionic strength increased which was attributed to the semi-rigid character of the polyampholyte block copolymer.
- Doctoral Dissertations