Phase behavior and properties of polyvinyl alcohol/gelatin blends with novel pH‐dependence

A novel change of phase behavior and properties of polyvinyl alcohol (PVA)/gelatin blends as a function of pH was reported. The PVA/gelatin blends were found to be completely miscible in acidic condition (pH 8), and immiscible in neutral condition (pH was ca. 6). As a result, the membranes cast from acidic condition showed the highest tensile strength and the lowest alcohol vapor permeation (AVP) rate; those obtained from neutral condition showed the lowest tensile strength and highest AVP rate; the properties of membranes cast from basic condition lay in between. The interaction between PVA and gelatin was investigated via Fourier transform infrared spectrum (FTIR), differential scanning calorimetry (DSC), and Zetasizer measurement. The novel pH-dependence of the blends was ascribed to the protonation of amino groups of gelatin in acidic condition, which resulted in a strong electrostatic attraction between NH of gelatin and OH of PVA. The partial miscibility in basic condition was due to the ionization of carboxyl groups of gelatin, which caused a stretching of gelatin via electrostatic repulsive force and a breakage of the H-bonding among the molecular chains, leading to a limited interaction between PVA and gelatin and forming a partially miscible blend. In neutral conditions, there were almost no charges (very limited protonation and ionization) at the weak polyampholyte gelatin, and the strong H-bonding among gelatin molecules themselves or PVA molecules themselves caused the phase separation between gelatin and PVA. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 239–247, 2009

[1]  Z. Su,et al.  Temperature Dependence of Surface Composition and Morphology in Polymer Blend Film , 2008 .

[2]  E. Chiellini,et al.  Gelatin-based blends and composites. Morphological and thermal mechanical characterization. , 2001, Biomacromolecules.

[3]  Andrij Pich,et al.  Temperature-, pH-, and magnetic-field-sensitive hybrid microgels. , 2007, Small.

[4]  M. Scandola,et al.  Viscoelastic and thermal properties of collagen/poly(vinyl alcohol) blends. , 1995, Biomaterials.

[5]  H. Bohidar,et al.  Effect of gelatin molecular charge heterogeneity on formation of intermolecular complexes and coacervation transition , 2007 .

[6]  A. Pradhan,et al.  Laser Raman spectroscopic study of water in gelatin–surfactant solutions and gels , 1999 .

[7]  Y. Nishio,et al.  Thermal and viscoelastic properties of alginate/poly(vinyl alcohol) blends cross-linked with calcium tetraborate , 1999 .

[8]  Sun I. Kim,et al.  Electrical/pH-sensitive swelling behavior of polyelectrolyte hydrogels prepared with hyaluronic acid–poly(vinyl alcohol) interpenetrating polymer networks , 2003 .

[9]  F. Mi,et al.  Antibacterial activity of chitosan–alginate sponges incorporating silver sulfadiazine: Effect of ladder-loop transition of interpolyelectrolyte complex and ionic crosslinking on the antibiotic release , 2005 .

[10]  N. Peppas,et al.  Complexation Phenomena in pH-Responsive Copolymer Networks with Pendent Saccharides , 2002 .

[11]  Nicholas A. Peppas,et al.  Dynamic swelling behavior of pH-sensitive anionic hydrogels used for protein delivery , 2003 .

[12]  Yansong Wang,et al.  Studies on preparation and properties of PAA/gelatin core-shell nanoparticles via template polymerization , 2007 .

[13]  A. R. Kulkarni,et al.  Chemically modified polyacrylamide-g-guar gum-based crosslinked anionic microgels as pH-sensitive drug delivery systems: preparation and characterization. , 2001, Journal of controlled release : official journal of the Controlled Release Society.

[14]  P. Sobral,et al.  Thermomechanical properties of biodegradable films based on blends of gelatin and poly (vinyl alcohol) , 2008 .

[15]  A. Bajpai,et al.  Preparation and characterization of novel pH-sensitive binary grafted polymeric blends of gelatin and poly(vinyl alcohol): Water sorption and blood compatibility study , 2006 .

[16]  Jeff Blyth,et al.  Holographic sensors for the determination of ionic strength , 2004 .

[17]  L. Huynh,et al.  In situ particle film ATR FTIR spectroscopy of carboxymethyl cellulose adsorption on talc: binding mechanism, pH effects, and adsorption kinetics. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[18]  J. W. Barlow,et al.  Transition behavior of poly(vinylidene fluoride)/poly(ethyl methacrylate) blends , 1976 .

[19]  T. Zemb,et al.  Osmotic Equilibrium and Depletion Induced by Polyelectrolytes in Clay Dispersions , 1994 .

[20]  Dursun Saraydın,et al.  Water uptake in chemically crosslinked poly(acrylamide-co-crotonic acid) hydrogels , 2005, Materials & Design.

[21]  Toshio Nishi,et al.  Melting Point Depression and Kinetic Effects of Cooling on Crystallization in Poly(vinylidene fluoride)-Poly(methyl methacrylate) Mixtures , 1975 .

[22]  P. Linse,et al.  Electrostatic attraction and phase separation in solutions of like-charged colloidal particles , 1999 .

[23]  K. Knudsen,et al.  Temperature-induced intermicellization and contraction in aqueous mixtures of sodium dodecyl sulfate and an amphiphilic diblock copolymer. , 2008, Journal of colloid and interface science.

[24]  D. Hjelme,et al.  Determination of swelling of responsive gels with nanometer resolution. Fiber-optic based platform for hydrogels as signal transducers. , 2008, Analytical chemistry.

[25]  D. Billaud,et al.  FTIR and Raman spectroscopic investigations on the redox behaviour of poly(5-cyanoindole) in acidic aqueous solutions , 1998 .

[26]  P. Barbara,et al.  Field-Induced Photoluminescence Modulation of MEH−PPV under Near-Field Optical Excitation , 2001 .