Citation: Fumihiko Tanaka, Tsuyoshi Koga, Hiroyuki Kojima, Francoise M. Winnik. HYDRATION AND PHASE SEPARATION OF TEMPERATURE-SENSITIVE WATER-SOLUBLE POLYMERS[J]. Chinese Journal of Polymer Science, ;2011, 29(1): 13-21. doi: 10.1007/s10118-010-1018-2 shu

HYDRATION AND PHASE SEPARATION OF TEMPERATURE-SENSITIVE WATER-SOLUBLE POLYMERS

Corresponding author: Fumihiko Tanaka,
Received Date: 13 July 2010
Revised Date: 23 August 2010

Collapse of a poly(N-isopropylacrylamide) (PNIPAM) chain upon heating and phase diagrams of aqueous PNIPAM solutions with very ?at LCST phase separation line are theoretically studied on the basis of cooperative dehydration (simultaneous dissociation of bound water molecules in a group of correlated sequence), and compared with the experimental observation of temperature-induced coil-globule transition by light scattering methods. The transition becomes sharper with the cooperativity parameter ? of hydration. Reentrant coil-globule-coil transition in mixed solvent of water and methanol is also studied from the viewpoint of competitive hydrogen bonds between polymer-water and polymer-methanol. The downward shift of the cloud-point curves (LCST cononsolvency) with the mole fraction of methanol due to the competition is calculated and compared with the experimental data. Aqueous solutions of hydophobically-modi?ed PNIPAM carrying short alkyl chains at both chain ends (telechelic PNIPAM) are theoretically and experimentally studied. The LCST of these solutions is found to shift downward along the sol-gel transition curve as a result of end-chain association (association-induced phase separation), and separate from the coil-globule transition line. Associated structures in the solution, such as ?ower micelles, mesoglobules and higher fractal assembly, are studied by USANS with theoretical modeling of the scattering function.
- Cooperative dehydration,
- LCST phase separation,
- Poly(N-isopropylacrylamide),
- Cononsolvency,
- Coil-globule transition,
- Flower micelle
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