聚氨酯的氮取代.pdf

Synthesis and Thermal Behavior of Poly(ethylene oxide) Poly(N-substituted urethane) JUNG-OHK KWEON, YONG-KUEN LEE, SI-TAE NOH Department of Chemical Engineering, College of Engineering Sciences, Hanyang University, Ansan, Kyunggi-do 425-791, Korea Received 2 March 2001; accepted 5 September 2001 ABSTRACT: Poly(N-substituted urethane)s with an alkyl or ligo(ethylene oxide) mono- methyl ether side chain were synthesized by the reaction operating in the following two-step process: first, by metalation of the starting polymer with potassium tertiary butoxide (t-BuOK) and then by treatment of the obtained urethane polyanion with tosylate in dimethyl sulfoxide. The thermal properties of poly(ethylene oxide) poly(N- substituted urethane) (N-sub PEOPU) were investigated in view of the N-substitution degree and properties of the substituent. The chemical structures were characterized by Fourier transform infrared, 1H NMR, and 13C NMR spectroscopies. DSC and thermo- gravimetric analysis (TGA) were used to investigate the thermal properties of N-sub PEOPUs. As the degree of N-methylation increased, the glass-transition temperature (T ) of the N-sub PEOPUs linearly decreased from 6 to 29 °C, and the weight-loss g temperature of 5% (T5%) from TGA in air increased from 278 to 360 °C. In the fully d N-substituted PEOPUs, the behavior of the thermal decomposition of the PEOPU that was processed in two stages was changed to one-step decomposition in the temperature range of 360– 440 °C. The Tg was shifted to a lower temperature with an increasing length of the substituent in N-sub PEOPU. Improvement of the thermal stability