A comparison between hydrophobically end-gapped poly(ethylene oxide) with ether and urethane bonds

Two models of HEUR (hydrophobically modified ethylene oxide urethane) associative polymers (AP) are compared. The two polymers are polyethyleneoxides simply end-capped with dodecyl groups, one through an ether bond H25C12-O-(CH2CH2O)(304)-C12H25 (AP14, M-w = 13,700) and the other through an urethane bond H25C12-NHCOO-(CH2CH2O)(304)-CONH-C12H25 (AP14-NCO, M-w is about the same as for AP14). The results indicate that this subtle difference in polymer architecture dramatically influences the initial association and the clouding of the polymer in water, so that AP14NCO starts to aggregate earlier but has a higher clouding temperature. However, at more elevated polymer contents (above 2-3 wt%) the differences in solution behavior and transport dynamics between the two polymers seems less significant. These conclusions are drawn through fluorescence, dynamic light scattering, NMR self-diffusion, turbidimetry, and viscosity measurements. (C) 1997 Academic Press.