In an attempt to clarify issues related to the molecular weight dependence of the phase transition of poly(N-isopropylacrylamide) (PNIPAM) in water,we prepared a library of PNIPAM samples of well-controlled molecular ...In an attempt to clarify issues related to the molecular weight dependence of the phase transition of poly(N-isopropylacrylamide) (PNIPAM) in water,we prepared a library of PNIPAM samples of well-controlled molecular weight (7000 to 45000 g/mol) bearing identical groups on each chain end.The polymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) with a bifunctional chain tranfer agent and further end group modification.The effects of the end group chemical structure,hydroxyethyl (HE),propargyl (Pr),chloroethyl (CE),n-butyl (nBu),n-hexyl (nHe),and isobutylsulfanylthiosulfanyl (IBS) on the phase transition temperature of aqueous PNIPAM solutions were investigated by high-sensitivity differential scanning calorimetry (HS-DSC),yielding the enthalpy ΔH and the endotherm maximum temperature (T M),and turbidimetry,providing the cloud point (T CP) of each solution.The T CP and T M of the PNIPAM sample of lowest molar mass (M n 7,000 g/mol,0.5 g/L) ranged,respectively,from 38.8 to 22.5 °C and 42.2 to 26.0 °C,depending on the structure of the end-group,whereas H showed no strong end-group dependence.The phase transition of all polymers,except,-di(n-butyl-PNIPAM),exhibited a marked dependence on the polymer molar mass.展开更多
基金supported by a grant of the Natural Sciences and Engineering Council of Canadaby a FY2009 Japan Society for the Promotion of Science Invitation Fellowship Program for Research in Japan(Long-term)
文摘In an attempt to clarify issues related to the molecular weight dependence of the phase transition of poly(N-isopropylacrylamide) (PNIPAM) in water,we prepared a library of PNIPAM samples of well-controlled molecular weight (7000 to 45000 g/mol) bearing identical groups on each chain end.The polymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) with a bifunctional chain tranfer agent and further end group modification.The effects of the end group chemical structure,hydroxyethyl (HE),propargyl (Pr),chloroethyl (CE),n-butyl (nBu),n-hexyl (nHe),and isobutylsulfanylthiosulfanyl (IBS) on the phase transition temperature of aqueous PNIPAM solutions were investigated by high-sensitivity differential scanning calorimetry (HS-DSC),yielding the enthalpy ΔH and the endotherm maximum temperature (T M),and turbidimetry,providing the cloud point (T CP) of each solution.The T CP and T M of the PNIPAM sample of lowest molar mass (M n 7,000 g/mol,0.5 g/L) ranged,respectively,from 38.8 to 22.5 °C and 42.2 to 26.0 °C,depending on the structure of the end-group,whereas H showed no strong end-group dependence.The phase transition of all polymers,except,-di(n-butyl-PNIPAM),exhibited a marked dependence on the polymer molar mass.
