Thermoresponsive statistical copolymers of N-vinylcaprolactam and N-vinylpyrrolidone of controlled average molar masses and composition were synthesized by RAFT / MADIX polymerization. The cloud point temperature was finely tuned in the range of temperature 36-70°C. DSC measurements combined with statistical calculations suggest that the whole polymer chain is involved in the hydration/dehydration process rather than short polymer sequences. At high concentration, these polymers enable the formation of thermoresponsive hydrogels. Cryo-SEM analysis of these solutions s showed the presence of globular substructures, with a looser 3-D network at higher VP content. This decrease of density of entanglements in the gel network could explain the decrease of mechanical properties and faster rehydration kinetics of the thermogelling polymer
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