Tuning the stimuli-response of hyperbranched polymers prepared by RAFT

POLY 509

Brent S. Sumerlin and Andrew P. Vogt. Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, PO Box 750314, Dallas, TX 75275-0314
Highly branched polymers of styrene and N-isopropylacrylamide (NIPAM) were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization with a polymerizable chain transfer agent (CTA). An acryloyl trithiocarbonate was prepared by copper-catalyzed 1,3-dipolar cycloaddition, an example of “click chemistry,” with an azido-functionalized trithiocarbonate and propargyl acrylate. Due to their increased contribution in the hyperbranched structures, the end groups of the poly(NIPAM) polymers provided a convenient means to selectively tune lower critical solution temperature (LCST) in aqueous media. As compared to the conventional value of 32 °C expected for linear poly(NIPAM), reduced LCSTs were observed for branched polymers with hydrophobic end groups, while hydrophilic chain termini caused the LCST to significantly increase.