Abstract
High molar mass poly(N-vinylcaprolactam) (PVCa) was synthesized by free-radical bulk polymerization. Four narrowly distributed fractions of PVCa were obtained in the tetrahydrofuran/n-hexane mixture. A combination of static and dynamic laser light scattering led to a scaling between the translational diffusion coefficient (D) and molar mass (M), D (cm2/s) = 8.47 × 10-5Mw-0.503, with which we transferred the translational diffusion coefficient distribution of each fraction into a corresponding molar mass distribution. We also established a scaling between the weight average molar mass (Mw) and the radius of gyration (〈Rg〉), 〈Rg〉 (nm) = 2.94 × 10-2Mw0.54, for PVCa in water at 25 °C. Moreover, we found a novel way to estimate the ϑ-temperature (∼29.5 °C) from the temperature and concentration dependence of the hydrodynamic radius (〈Rh〉). The lower critical solution temperature (LCST, ∼31.5 °C) of linear PVCa chains in water determined from the variations of both 〈Rh〉 and scattering intensity is close to the ...
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