Rheological properties of high molecular weight (HMW) syndiotactic poly(vinyl alcohol) (PVA)/HMW atactic PVA blend solutions

To identify the effect of blend ratios of syndiotacticity‐rich poly(vinyl alcohol) (s‐PVA)/atactic PVA (a‐PVA) having similar number‐average degrees of polymerization (P_n)s of 4000 and degrees of saponification (DS)s of 99.9% on the rheological properties of s‐PVA/a‐PVA/water solutions, water‐soluble s‐PVA and a‐PVA with different syndiotactic diad contents of 58.5 and 54.0%, respectively, were prepared by bulk copolymerization of vinyl pivalate and vinyl acetate (VAc) and solution polymerization of VAc, followed by saponifying the corresponding copoly(vinyl pivalate/vinyl acetate) and poly(vinyl acetate). The blend ratios played a significant role in rheological behavior. Over the frequency range of 10^?1–10² rad/s, s‐PVA/a‐PVA blend solutions with larger s‐PVA content show more shear thinning at similar (P_n)s and (DS)s of polymer, suggesting that PVA molecules are more readily oriented as s‐PVA content increases. Yield stress is higher for s‐PVA/a‐PVA blend solutions with larger s‐PVA content at similar (P_n)s and (DS)s of polymer. This indicates that more domains with internal order are produced at larger s‐PVA content in s‐PVA/a‐PVA blend solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3934–3939, 2006     

Water stability of high‐molecular‐weight (HMW) syndiotacticity‐rich poly(vinyl alcohol) (PVA)/HMW atactic PVA/iodine complex blend films

To precisely identify the effect of blend ratios of syndiotacticity‐rich poly(vinyl alcohol) (s‐PVA)/atactic PVA (a‐PVA) on the water stability of s‐PVA/a‐PVA/iodine complex blend films, we prepared two PVAs with similar number‐averaged degrees of polymerization of 4000 and degrees of saponification of 99.9% and with different syndiotactic diad contents of 58.5 and 53.5%, respectively. The desorption behavior of iodine in s‐PVA/a‐PVA/iodine complex films in water was investigated in terms of the solubility of s‐PVA/a‐PVA blend films in water. The degree of solubility of s‐PVA/a‐PVA blend films with s‐PVA content over 50% in water at 70°C was limited to about 10–20%, whereas that of s‐PVA/a‐PVA blend films with s‐PVA content of 10% was 85% under the same conditions. The degree of iodine desorption of complex blend films decreased with increasing s‐PVA content. The degree of iodine desorption of s‐PVA/a‐PVA drawn film with s‐PVA content of 90% was limited to 7%, regardless of the soaking temperature from 30 to 70°C. The desorption of iodine in water was strongly affected by the dissolution of blends. Moreover, the stability of iodine in the drawn s‐PVA/a‐PVA/iodine blend films in hot water was far superior to that of the undrawn film. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1435–1439, 2004     

Enhanced oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) blended with poly(acrylic acid) for packaging applications

To enhance the oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) (PVA) and expand its food packaging applicability, five crosslinked poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blend films were prepared via esterification reactions between hydroxyl groups in PVA and carboxylic acid groups in PAA. The physical characteristics of the blends, including the thermal, barrier, mechanical and optical properties, were investigated as a function of PAA ratio. With increasing PAA content, the crosslinking density was significantly increased, resulting in changes in the chemical structure, morphology and crystallinity of the films. The oxygen transmission rate of pure PVA decreased from 5.91 to 1.59 cc m^?1 day^?1 with increasing PAA ratio. The water resistance, too, increased remarkably. All the blend films showed good optical transparency. The physical properties of the blend films were strongly correlated with the chemical structure and morphology changes, which varied with the PAA content. © 2016 Society of Chemical Industry     

Blends of poly(vinyl butyral‐co‐vinyl alcohol) and poly(ethylene terephthalate‐co‐ethylene naphthalate): thermal,mechanical, and morphological properties

The miscibility behavior and morphology of a series of poly(vinyl butyral‐co‐vinyl alcohol) (PVBA) copolymers containing 29, 52, 76, and 88 mol % of vinyl alcohol units with poly(ethylene terephthalate‐co‐ethylene naphthalate) (PETN) was investigated by DSC and SEM. Blends of the PETN with PVBA were prepared by coprecipitation from a chloroform/o‐chlorophenol (20/80 wt %) mixture solvent. It was found that PVBAs with different vinyl alcohol content will form an immiscible phase with the amorphous PETN in the solution‐cast films. Also, PETN and PVBA with 29 mol % vinyl alcohol (PVBA‐29) are not miscible within the whole composition range. The glass‐transition temperatures of the blends were higher than those of the two‐component polymers. The values of the tensile properties of the blend films were also better than those of the original copolymer films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2746–2751, 2001     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001     

Electrical conductivity of LTA‐zeolite in the presence of poly(vinyl alcohol) and poly(vinyl pyrrolidone) polymers

In this work we studied the electrical behavior of Linde type A zeolite (K⁺) in the presence of two polymers, poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP), with excellent film forming properties. Homogeneous composite thin films of PVA/LTA‐zeolite and PVP/LTA‐zeolite were prepared with different zeolite concentrations. The current?voltage (I?V) characteristics of the composites were measured at different applied voltages. The results show that the conductivity properties are composition‐ratio‐dependent and are also related to the type of polymers. Moreover, a well‐defined step‐like change was detected in the I?V curve of PVP/LTA‐zeolite at very high applied voltage. © 2013 Society of Chemical Industry     

Structure and properties of poly(vinyl alcohol)/κ‐carrageenan blends

Blends of a commercial atactic poly(vinyl alcohol) (a‐PVA) derived from vinyl acetate and κ‐carrageenan were prepared by mixing the aqueous solutions of both samples. Blend films prepared by casting were transparent. In the DSC curves of the blend films, the endothermic peaks shifted to lower temperature with an increase of the content of κ‐carrageenan. The Young's modulus and the strength at break increased with an increase of the content of a‐PVA. As the standing temperature of the blend solutions decreased, the gelation region increased also at high content of carrageenan. In the amorphous regions of blend films, a‐PVA and κ‐carrageenan were miscible. © 2001 Society of Chemical Industry     

Production of polymeric membranes made of polypropylene,poly(ethylene‐co‐vinyl acetate), and poly(vinyl alcohol)

In this study, we prepared and characterized membranes containing polypropylene, poly(ethylene‐co‐vinyl acetate) (EVA), and poly(vinyl alcohol) (PVA). The production process involved blend extrusion and calendering followed by solvent extraction by toluene and water of the EVA and PVA phases. Morphology studies involving scanning electron microscopy determined the pore size distribution at the surface and in the internal regions of the membrane. The resulting membrane properties were related to the processing variables (extension rate, process temperature, and solvent extraction methods) and blend composition. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3275–3286, 2004     

Solution and solid‐state NMR investigation of poly(methyl methacrylate)/poly(vinyl pyrrolidone) blends

The development of polymer blends has become very important for the polymer industry because these blends have shown to be a successful and versatile alternative way to obtain a new polymer. In this study, binary blends formed by poly(methyl methacrylate) (PMMA) and poly(vinyl pyrrolidone) were prepared by solution casting and evaluated by solution and solid‐state NMR. Variations in the microstructure of PMMA were analyzed by ¹³C solution NMR. Solid‐state NMR promotes responses on physical interaction, homogeneity, and compatibility to use these blends to understand the behavior of the ternary blends. The NMR results led‐us to acquire information on the polymer blend microstructure and molecular dynamic behavior. From the NMR solution, it was possible to evaluate the microstructure of both polymer blend components; they were atactic. From the solid state, good compatibility between both polymer components was characterized. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 372–377, 2004     

High‐resolution solid‐state NMR and SEM study of the interaction behavior of poly(ethylene‐co‐vinyl acetate)/poly(vinyl acetate) blends

Binary blends formed by two types of ethylene‐co‐vinyl acetate (EVA), which have different vinyl acetate contents, and poly(vinyl acetate) (PVAc) were prepared in a Haake Rheocord 9000 plastograph. A series of samples were obtained varying the PVAc amount up to 50%. The studies were carried out employing solid‐state nuclear magnetic resonance spectroscopy (NMR) and scanning electronic microscopy (SEM). The xenon‐129 (¹²⁹Xe) and carbon‐13 (¹³C) NMR response together with the microscopy results showed that the systems are heterogeneous. Therefore, EVA with a higher vinyl acetate content presented some interaction between the polymer blend components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 116–124, 2002     

Water‐absorptive blend fibers of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol)

Through the addition of N‐hydroxymethyl acrylamide as a potential crosslinker, water‐absorptive blend fibers of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol) with three‐dimensional network structures were prepared with heat‐crosslinking technology after fiber formation. Fourier transform infrared, scanning electron microscopy, dynamic mechanical analysis, and thermogravimetry were used to analyze the structures and properties of the fibers. The tensile behavior and absorbent capacities of the fibers were also studied. The results showed that there were lots of chemical crosslinking points in the fibers, the compatibility of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol) was perfect, and the tensile properties of the fibers could be improved effectively through stretching in a vapor bath. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3353–3357, 2006     

Swelling behavior of semi‐interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(acrylamide‐co‐sodium methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐sodium methacrylate) poly(AAm‐co‐SMA) were prepared by the semi IPN method. These IPN hydrogels were prepared by polymerizing aqueous solution of acrylamide and sodium methacrylate, using ammonium persulphate/N,N,N¹,N¹‐tetramethylethylenediamine (APS/TMEDA) initiating system and N,N¹‐methylene‐bisacrylamide (MBA) as a crosslinker in the presence of a host polymer, poly(vinyl alcohol). The influence of reaction conditions, such as the concentration of PVA, sodium methacrylate, crosslinker, initiator, and reaction temperature, on the swelling behavior of these IPNs was investigated in detail. The results showed that the IPN hydrogels exhibited different swelling behavior as the reaction conditions varied. To verify the structural difference in the IPN hydrogels, scanning electron microscopy (SEM) was used to identify the morphological changes in the IPN as the concentration of crosslinker varied. In addition to MBA, two other crosslinkers were also employed in the preparation of IPNs to illustrate the difference in their swelling phenomena. The swelling kinetics, equilibrium water content, and water transport mechanism of all the IPN hydrogels were investigated. IPN hydrogels being ionic in nature, the swelling behavior was significantly affected by environmental conditions, such as temperature, ionic strength, and pH of the swelling medium. Further, their swelling behavior was also examined in different physiological bio‐fluids. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 302–314, 2005     

Solution and solid‐state blend compatibility of poly(vinyl alcohol) and poly(methyl methacrylate)

The blend miscibility of poly(vinyl alcohol) and poly(methyl methacrylate) in N,N′‐dimethylformamide solution was investigated by viscosity, density, ultrasonic velocity, refractive index, and UV and fluorescence spectra studies. Differential scanning calorimetry and scanning electron microscopy were used to confirm the blend miscibility in the solid state. Blends were compatible when the concentration of poly(vinyl alcohol) was greater than 60 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2415–2421, 2006     

Preparation of ketoprofen‐loaded high‐molecular‐weight poly(vinyl alcohol) gels

High‐molecular‐weight atactic poly(vinyl alcohol) (a‐PVA) gels loaded with (R,S)‐2‐(3‐benzoylphenyl)propionic acid (ketoprofen) were prepared from 5, 6, 7, and 8 g/dL solutions of a‐PVA with a number‐average degree of polymerization of 4000 in an ethylene glycol/water mixture with an aging method to identify the effect of the initial polymer concentration on the swelling behavior, morphology, and thermal properties of a‐PVA gels. Then, the release behavior of ketoprofen from a‐PVA gels was investigated. As the polymer concentration decreased, the ability for network formation decreased, and the degree of swelling of the a‐PVA gels increased. In addition, the enthalpy increased with an increase in the a‐PVA concentration, but the melting temperatures of the gels prepared at different initial polymer concentrations were the same; this indicated that tighter gel networks would be formed by a higher polymer chain density. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) and poly(vinyl alcohol)‐graft‐poly(lactide) in melt with magnesium hydride as catalyst

Grafting of poly(ε‐caprolactone) (PCL) and poly(lactide) (PLA) chains on poly(vinyl alcohol) backbone (PVA degree of hydrolysis 99%) was investigated using MgH₂ environmental catalyst and melt‐grown ring‐opening polymerization (ROP) of ε‐caprolactone (CL) and L ‐lactide (LA), that avoiding undesirable toxic catalyst and solvent. The ability of MgH₂ as catalyst as well as yield of reaction were discussed according to various PVA/CL/MgH₂ and PVA/LA/MgH₂ ratio. PVA‐g‐PCL and PVA‐g‐PLA were characterized by ¹H‐ and ¹³C‐NMR, DSC, SEC, IR. For graft copolymers easily soluble in tetrahydrofuran (THF) or chloroform, wettability and surface energy of cast film varied in relation with the length and number of hydrophobic chains. Aqueous solution of micelle‐like particles was realized by dissolution in THF then addition of water. Critical micelle concentration (CMC) decreased with hydrophobic chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization, and properties of poly(vinyl acetate)‐ and poly(vinyl alcohol)‐grafted chitosan

Graft copolymers of chitosan and vinyl acetate were synthesized by free radical technique using cerium (IV) as the initiator. Under controlled conditions, as much as 92% grafting with a grafting yield of 30–40% could be achieved. Chitosan‐g‐poly(vinyl alcohol) copolymers were derived by the alkaline hydrolysis of the chitosan‐g‐poly(vinyl acetate) precursor. Thermogravimetric, FTIR, and X‐ray diffraction analyses of chitosan and the copolymers confirmed the grafting reaction between chitosan and vinyl acetate and also the subsequent hydrolysis. Both the copolymers possessed very good film‐forming properties. Grafting resulted in a significant increase in mechanical strength of both the copolymers in the dry condition. Chitosan‐g‐poly(vinyl acetate) (CH‐PVAc) proved more hydrophobic than did pure chitosan, whereas chitosan‐g‐poly(vinyl alcohol) (CH‐PVOH) exhibited enhanced hydrophilicity as evident from their swelling characteristics and contact angle measurements. The enhanced swelling of CH‐PVOH was ascribed to the presence of the pendant poly(vinyl alcohol) group. At pH 1.98, the CH‐PVAc copolymer films showed greater stability than do pure chitosan films, which is highly beneficial for specific biomedical applications. Both the copolymers showed lower glass transition temperature than do pure chitosan. Grafting did not affect the overall thermal stability, and the differential thermogram substantiated the grafting. The investigations indicate that the synthetic–natural hybrid copolymers having desirable mechanical properties and tailored hydrophilic/hydrophobic characteristics are realizable. These polymers could be exploited for varied biomedical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1852–1859, 2007     

Poly(vinyl alcohol) and poly(vinyl amine) blend membranes for isopropanol dehydration

Blended membranes of hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) were prepared and crosslinked with glutaraldehyde. The prepared membranes were characterized using infrared (attenuated total reflection mode) spectroscopy, differential scanning calorimetry, X‐ray diffractometry, and scanning electron microscopy measurements. Pervaporation performances of the membranes were evaluated for the separation of water‐isopropanol (IPA) mixtures. As the PVAm content increased from PVAm0 to PVAm1.5, the flux through a 70 μm film increased from 0.023 to 0.10 kg/m² h at an IPA/water feed ratio of 85/15 at 30 °C. The driving force for permeation of water increased due to the temperature but it has no effect on IPA permeation. Activation energies for the permeation of IPA and water were calculated to be 17.11 and 12.46 kJ/mol, respectively. Controlling the thickness of the blend membrane could improve the permeation flux with only a marginal reduction in the separation factor. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45572.     

Properties of blends of syndiotactic-rich and atactic poly(vinyl alcohols)

The crystallinity, solubility, degree of swelling, and hygroscopicity of the blends of syndiotactic-rich (st-PVA) and atactic poly(vinyl alcohols) (at-PVA) were studied. The crystallinity of the blends increased with increasing annealing temperature and that of the blends annealed at 200°C was larger than that of at-PVA. In the 200°C annealed blends containing st-PVA about 50%, the insoluble fraction in boiling water was larger than the fraction of st-PVA in each blend. The soluble fraction for the blend containing 75% st-PVA was 1.7%. The moisture regain of the blends was less than that of at-PVA.     

Dynamic–mechanical properties of modified poly(ethylene‐co‐vinyl acetate)

To study the relationship among relaxation peaks observed in dynamic mechanical experiments and the structure of poly(ethylene‐co‐vinyl acetate) (EVA), EVA copolymers with different substitution in the carbonyl group were synthesized. EVA was hydrolyzed to obtain poly (ethylene‐co‐vinyl alcohol) and was subsequently reacted with formic, hexanoic, and octanoic acids. The copolymers synthesized were characterized by infrared spectroscopy. Analysis of the DMA spectra of the copolymers showed that their relaxation behavior depends on the vinyl acetate concentration. The α‐ and β‐transitions were observed in EVA copolymers with 8 and 18 wt % of functional groups, and the relationship among relaxation process with the structure of polymer was investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1371–1376, 2005     

Water stability of syndiotactic poly(vinyl alcohol)/iodine complex film

The desorption behavior of iodine in syndiotactic poly(vinyl alcohol) (s-PVA) with a syndiotactic diad content of 63.1% iodine film in water was investigated in relation to the solubility of s-PVA in water. Despite a low number-average degree of polymerization of 900, the degree of solubility of s-PVA film in water at 80°C was limited to about 10%, whereas atactic poly(vinyl alcohol) (a-PVA) film was completely soluble at a lower temperature, 50°C. The degree of iodine desorption of s-PVA/iodine film at a high temperature decreased remarkably compared with that of a-PVA/iodine film. The fastness of iodine of the drawn s-PVA/iodine film was far superior to that of the undrawn film. Over a draw ratio of 5, the iodine desorption was suppressed significantly with increasing drawing temperature rather than the draw ratio. In addition, the iodine desorption of postdrawn s-PVA/iodine film was lower than that of predrawn s-PVA/iodine film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 108–113, 2001