Behavior of Water during Temperature-Induced Phase Separation in Poly(vinyl methyl ether) Aqueous Solutions. NMR and Optical Microscopy Study

The behavior of water during the temperature-induced phase separation in PVME/D2O solutions was investigated by 1H NMR methods and optical microscopy. A fast exchange between water (HDO) bound in mesoglobules and free water was found from 1H NMR spin−spin relaxation measurements at temperature above the LCST transition for semidilute PVME/D2O solutions where the exchange time is 1.2 ms for c = 6 wt %. In contrast, there is a slow exchange between bound and free water in highly concentrated PVME solutions and the residence time of the bound water 2 s was found for concentrations c = 20−50 wt % using one-dimensional NOE 1H NMR experiment. A 3 order of magnitude slower exchange in highly concentrated PVME/D2O solutions is in accord with our optical microscopy findings that globular-like structures are here approximately 20 times larger than in PVME solution with c = 6 wt %.

[1]  K. Ariga,et al.  Probing the micro-phase separation of thermo-responsive amphiphilic polymer in water/ethanol solution. , 2010, Journal of nanoscience and nanotechnology.

[2]  Ding-hai Huang,et al.  Investigation of the heat capacity of poly (vinyl methyl ether)/water mixtures using the stepscan method , 2010 .

[3]  J. Spĕvác̆ek NMR investigations of phase transition in aqueous polymer solutions and gels , 2009 .

[4]  Ruixue Liu,et al.  Thermoresponsive copolymers: from fundamental studies to applications , 2009 .

[5]  M. Zhang,et al.  Study of Phase Separation of Poly(vinyl methyl ether) Aqueous Solutions with Rayleigh Scattering Technique , 2009 .

[6]  T. Tahara,et al.  Picosecond time-resolved fluorescence study of poly vinyl methyl ether aqueous solution , 2009 .

[7]  Hana Kouřilová,et al.  Polymer‐Solvent Interactions in Solutions of Thermoresponsive Polymers Studied by NMR and IR Spectroscopy , 2008 .

[8]  Peiyi Wu,et al.  Phase separation of poly(vinyl methyl ether) aqueous solution: a near-infrared spectroscopic study. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[9]  Peiyi Wu,et al.  FT-IR and 2D-IR Spectroscopic Studies on the Effect of Ions on the Phase Separation Behavior of PVME Aqueous Solution , 2007, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[10]  J. Spĕvác̆ek,et al.  NMR Study on Polymer-Solvent Interactions during Temperature-Induced Phase Separation in Aqueous Polymer Solutions , 2007 .

[11]  J. Spĕvác̆ek,et al.  Effect of time on the hydration and temperature-induced phase separation in aqueous polymer solutions. 1H NMR study , 2006 .

[12]  Haitao Hu,et al.  Revisiting the initial rate approximation in kinetic NOE measurements. , 2006, Journal of magnetic resonance.

[13]  J. Spĕvác̆ek,et al.  NMR study of temperature-induced phase separation and polymer–solvent interactions in poly(vinyl methyl ether)/D2O/ethanol solutions , 2006 .

[14]  S. King,et al.  Upper critical solution temperature phase behavior, composition fluctuations, and complex formation in poly (vinyl methyl ether)/D2O solutions: small-angle neutron-scattering experiments and wertheim lattice thermodynamic perturbation theory predictions. , 2006, The journal of physical chemistry. B.

[15]  Françoise M. Winnik,et al.  Temperature dependence of the colloidal stability of neutral amphiphilic polymers in water , 2006 .

[16]  B. Mele,et al.  Phase Behavior of Poly(vinyl methyl ether) in Deuterium Oxide , 2005 .

[17]  J. Spĕvác̆ek,et al.  1H NMR Study on the Hydration during Temperature-Induced Phase Separation in Concentrated Poly(vinyl methyl ether)/D2O Solutions , 2005 .

[18]  J. Spĕvác̆ek,et al.  1H NMR Relaxation Study of Thermotropic Phase Transition in Poly(vinyl methyl ether)/D2O Solutions , 2004 .

[19]  Hiroki Yamamoto,et al.  Effects of Ions on Two-Step Phase Separation of Poly(vinyl methyl ether) in Water As Studied by IR and Raman Spectroscopy , 2003 .

[20]  J. Spĕvác̆ek,et al.  1H NMR relaxation study of polymer-solvent interactions during thermotropic phase transition in aqueous solutions , 2003 .

[21]  B. Mele,et al.  Modulated‐temperature differential scanning calorimetry study of temperature‐induced mixing and demixing in poly(vinylmethylether)/water , 2003 .

[22]  J. Spĕvác̆ek,et al.  1H NMR study of thermotropic phase transition of linear and crosslinked poly(vinyl methyl ether) in D2O , 2001 .

[23]  M. Billeter,et al.  NMR studies of Brownian tumbling and internal motions in proteins , 2001 .

[24]  J. Spĕvác̆ek,et al.  Polymer‐solvent interactions during phase transition in poly(vinyl methyl eiher)/D2O solutions as studied by NMR methods , 2001 .

[25]  Y. Maeda IR Spectroscopic Study on the Hydration and the Phase Transition of Poly(vinyl methyl ether) in Water , 2001 .

[26]  K. Dušek,et al.  Zero and Off-Zero Critical Concentrations in Systems Containing Polydisperse Polymers † with Very High Molar Masses. 2. The System Water-Poly(vinyl methyl ether) , 1997 .

[27]  H. G. Schild Poly(N-isopropylacrylamide): experiment, theory and application , 1992 .

[28]  Howard G. Schild,et al.  Microcalorimetric detection of lower critical solution temperatures in aqueous polymer solutions , 1990 .

[29]  N. Yu,et al.  Macromolecule hydration and the effect of solutes on the cloud point of aqueous solutions of polyvinyl methyl ether: a possible model for protein denaturation and temperature control in homeothermic animals. , 1971, Journal of colloid and interface science.

[30]  S. Meiboom,et al.  Nuclear Magnetic Resonance Study of the Protolysis of Trimethylammonium Ion in Aqueous Solution—Order of the Reaction with Respect to Solvent , 1963 .