Molecular understanding of the UCST-type phase separation behavior of a stereocontrolled poly(N-isopropylacrylamide) in bis(2-methoxyethyl) ether.
The upper critical solution temperature (UCST)-type phase separation of an isotactic-rich poly( N-isopropylacrylamide) (PNiPA) in bis(2-methoxyethyl) ether (diglyme) has been investigated by turbidity measurement and infrared (IR) spectroscopy. The IR spectra of stereocontrolled PNiPAs in various solvents have clearly indicated that the amide I bands do not directly reflect the tacticity of the polymer. The relative intensity of the amide I bands changes depending upon the molecular environment around the amide groups of PNiPA, which is influenced by the tacticity. During the UCST-type phase separation of the isotactic-rich PNiPA in diglyme, the amide I band at around 1625 cm (-1) changes. To link the IR spectral change with the molecular information, quantum chemical calculations have been carried out for NiPA n-mers ( n = 1-4) with an isotactic stereosequence. The result has suggested that the amide I band at around 1625 cm (-1) arises from a helical structure formed by the isotactic stereosequences in the PNiPA main chain with the aid of intramolecular CO...H-N hydrogen bonding. The experimental IR spectra have revealed that the helical structures are unfolded as the temperature rises. The folding and unfolding of the isotactic sequences in the main chain may induce the thermal change in the solubility of the isotactic rich PNiPA in diglyme, resulting in the UCST-type phase separation of the solution.
Koyama
Misao
M
Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-Hiroshima 739-8526, Japan.
Hirano
Tomohiro
T
Ohno
Keiichi
K
Katsumoto
Yukiteru
Y