Combinations of microphase separation and terminal multiple hydrogen bonding in novel macromolecules

The synthesis and characterization of terminal multiple hydrogen-bonded (MHB) polymers, such as poly(styrene) (PS), poly(isoprene) (PI), and microphase separated PS-b-PI block copolymers, possessing controlled molecular weights and narrow molecular distributions are described. Hydroxyl-terminated polymeric precursors were prepared using living anionic polymerization and subsequent quantitative termination with ethylene oxide. MHB polymers were synthesized in a controlled fashion via end-group modification of these well-defined macromolecular alcohols with excess isophorone diisocyanate and subsequent derivatization of the isocyanate-terminated polymeric intermediate with methyl isocytosine. The glass transition temperatures of the terminal MHB polymers were reproducibly higher than both nonfunctionalized and hydroxyl-terminated polymers at nearly equivalent number average molecular weights. Thin-layer chromatography analysis indicated that the interaction of terminal MHB polymers with silica was stronger as compared to both nonfunctionalized and hydroxyl-terminated polymers. Rheological characterization indicated that the melt viscosity at constant shear rate for various MHB polymers was more than 100 times higher than those for nonfunctionalized and hydroxyl-terminated polymers. Interestingly, the melt viscosity of MHB polymers was higher than those of nonfunctionalized polymers with twice the number average molecular weight. In addition, DSC and rheological characterization also suggested that terminal MHB polymers formed aggregates and not simple dimers in the melt state, and the aggregates were observed to completely dissociate at 80°C.