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     

Preparation of syndiotacticity‐rich high molecular weight poly(vinyl alcohol)/iodine polarizing film with high water resistance

To enhance durability of poly(vinyl alcohol) (PVA)/iodine polarizing film under humid and warm atmospheres and to identify the effects of syndiotacticity on the polarizing efficiency (PE) and durability of PVA/iodine complex film, we prepared three high molecular weight (PVA)s with similar number‐average degree of polymerization (P_n) of 4000 and with different syndiotactic diad (s‐diad) contents of 53, 56, and 59%, respectively. It was found that syndiotacticity of PVA had a significant influence on the durability of PVA/iodine complex film in warm and humidity conditions (relative humidity of 80% and temperature of 50°C). That is, both desorption of iodine in PVA/iodine film and transmittance of film decreased with increasing syndiotacticity of PVA. In the case of PE, the values of over 99% were obtained at each optimum conditions. The change of PE (durability) of PVA/iodine complex films having P_n of 4000 and s‐diad contents of 56 and 59%, respectively, in warm and humidity conditions was almost zero, whereas those of PVA/iodine film with s‐diad content of 53% and with (P_n)s of 1700 and 4000 were about 60% and 50%, respectively, under same conditions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Role of molecular weight of atactic poly(vinyl alcohol) (PVA) in the polarizing efficiency of PVA/azo dye complex film with high durability

To precisely identify the effect of molecular weight of atactic poly(vinyl alcohol) (a‐PVA) on the durability and polarizing efficiency (PE) of a‐PVA/dye polarizing film, we prepared two (a‐PVA)s with similar syndiotactic diad contents of 54.0%, degrees of saponification of 99.9%, and with different number‐average degrees of polymerization [(P_n)s] of 1700 and 4000, respectively. Through a series of experiments, it was found that molecular weight of a‐PVA had a significant influence on the durability of a‐PVA/dye film in heat and humidity conditions (relative humidity of 80% and temperature of 90°C). That is, both desorption of dye in a‐PVA/dye film and transmittance of film decreased with increasing molecular weight of PVA. The change of PE (durability) of a‐PVA/dye film in heat and humidity conditions was limited to about below 5%. The change of PE of PVA/dye film having P_n of 4000 especially was limited to 1%, whereas that of a‐PVA/iodine film with P_n of 4000, was almost 80% under the same condition. Also, transmittance of the drawn a‐PVA/dye film was far higher than that of the undrawn one. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 967–974, 2005     

Syndiotacticity‐rich ultrahigh molecular‐weight poly(vinyl alcohol) film. I. Determination of optimum polymer concentration by zone‐drawing method in film preparation

A new method using a simple zone‐drawing technique has been suggested for determining the optimum initial concentration of a polymer solution that has suitable macromolecular entanglements. This method was developed to replace the incorrect inherent viscosity‐measuring method for syndiotacticity‐rich (syndiotactic diad content of 63.4%) ultrahigh molecular‐weight (number‐average degree of polymerization of 12,300) (UHMW) poly(vinyl alcohol) (PVA) solution. Syndiotacticity‐rich UHMW PVA films were prepared from dimethyl sulfoxide (DMSO) solutions with different initial concentrations: of 0.1, 0.2, 0.3, 0.4, and 0.5 g/dL. In order to investigate the drawing behavior of the syndiotacticity‐rich UHMW PVA films with different solution concentrations, the films were drawn under various zone‐drawing conditions. Through a series of experiments, it was discovered that the initial concentration of PVA solution in DMSO caused significant changes in the draw ratio of the syndiotacticity‐rich UHMW PVA film. That is, the one‐step and maximum zone draw ratios of the film at an initial concentration of 0.3 g/dL exhibited its maximum values and gradually decreased at higher or lower concentrations. Thus, it was disclosed that the initial concentration of 0.3 g/dL is the optimum polymer concentration to produce a maximum draw ratio in this work. Based on the above results, it may be concluded that the optimum concentration of the initial PVA solution can be determined directly by measuring the zone draw ratio. The draw ratio, birefringence, crystallinity, degree of crystal orientation, tensile strength, and tensile modulus of the maximum drawn PVA film were 32.9, 0.0449, 0.61, 0.991, 1.91, and 46.2 GPa, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 123–134, 2000     

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     

Gas permeation through water‐swollen polysaccharide/poly(vinyl alcohol) membranes

The effect of Na‐alginate content on the gas permeation properties of water‐swollen membranes prepared by varying Na‐alginate and poly(vinyl alcohol) (PVA) content in membranes was investigated. The influences of water content and crystallinity of the membranes on the gas permeation performance of the water‐swollen membranes were studied. The gas permeation rate and selectivity of Na‐alginate/PVA water‐swollen membranes were compared with those of the dry membranes. The permeation rates of nitrogen and carbon dioxide through water‐swollen membranes were in the range of 0.4–7.6 × 10^?7 to 3.7–8.5 × 10^?6 cm³ (STP)/cm² s^?1 cmHg^?1, which were 10,000 times higher than those of dry‐state membranes. The permeation rates of mixture gases through water‐swollen Na‐alginate/PVA membranes were found to increase exponentially with the increase of Na‐alginate content, whereas carbon dioxide concentration in permeates was decreased linearly. It was found that the gas permeance of the water‐swollen membranes increased with increasing the Na‐alginate content in the membrane. Gas permeation rates of the water‐swollen Na‐alginate/PVA membranes increased with increasing the water content in the membrane and decreasing the crystallinity of the membrane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3225–3232, 2004     

Preparation and characterization of LDPE/PVA blend films filled with glycerin‐plasticized polyvinyl alcohol

A series of LDPE/PVA blend films were prepared via a twin‐screw extruder, and their morphology, thermal property, oxygen and water vapor permeation, surface properties, and mechanical properties were investigated as a function of the PVA content. During the extrusion process of the blend films, glycerin improved the compatibility and processing conditions between LDPE and PVA. The melting temperature (T_m), melting enthalpy (ΔH_m), crystallinity (%), and thermal stability of the thermal decomposition temperature (T_5%) of the LDPE/PVA blend films decreased with increasing PVA content. The oxygen permeabilities of the blend films decreased from 24.0 to 11.4 cm³·cm (m²·day·atm)^?1 at 23°C. The WVTR increased from 7.8 to 15.0 g(m² day)^?1 and the water uptake increased from 0.13 to 9.31%, respectively. The mechanical properties of blend films were slightly enhanced up to 2% PVA and then decreased. The physical properties of the blend films strongly varied with the chemical structure and morphology depending on the PVA and glycerin. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41985.     

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     

Effects of additives with different functional groups on the physical properties of starch/PVA blend film

The effects of additives with different functional groups, that is, hydroxyl and carboxyl groups, on the physical properties of starch/PVA blend films were examined. Starch/PVA blend films were prepared by the mixing process. Glycerol (GL) with 3 hydroxyl groups, succinic acid (SA) with 2 carboxyl groups, malic acid (MA) with 1 hydroxyl and 2 carboxyl groups, and tartaric acid (TA) with 2 hydroxyl and 2 carboxyl groups were used as additives. The results of measured tensile strength and elongation verified that hydroxyl and carboxyl groups as functional groups increased the flexibility and strength of the film. The degree of swelling (DS) and solubility (S) of the GL/SA‐added films were low. However, the DS and S of the films with added MA or TA with both hydroxyl and carboxyl groups were comparatively high. When the film was dried at low temperature, the properties of the films evidently improved, probably because hydrogen bonding was activated at low temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3733–3740, 2006     

Preparation of novel gold‐coated syndiotactic poly(vinyl alcohol) microfibrils by sputtering

To prepare a syndiotactic poly(vinyl alcohol) (PVA)/gold complex for various biomedical applications, ultrahigh‐molecular‐weight syndiotactic PVA microfibrils were directly prepared by the saponification of poly(vinyl pivalate) that was obtained through bulk polymerization of vinyl pivalate at 30°C. PVA microfibrils with a number‐average degree of polymerization, syndiotactic diad content, and degree of saponification of 14,300, 61.7%, and 99.9%, respectively, were gold‐coated by sputtering at 140 and 150 W (Watt) for 1, 2, and 3 min, respectively. A weight gain of up to 7% by the gold atoms for the PVA microfibrils treated at 150 W for 3 min was found. Morphological changes at the surface were observed by a microscopic method. A mechanism of gold coating on PVA microfibrils is suggested. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2369–2372, 2003     

Synthesis of ion‐imprinting chitosan/PVA crosslinked membrane for selective removal of Ag(I)

A novel ion‐imprinted membranes were synthesized for selective removal and preconentration for Ag(I) ions from aqueous solutions. The membranes were obtained via crosslinking of chitosan (CS), PVA, and blend chitosan/PVA using glutaraldehyde (GA) as crosslinker. The FTIR spectra were used to confirm the membrane formation. Comparing with the nonimprinted membranes, Ag(I)‐imprinted CS and CS/PVA has higher removal capacity and selectivity for Ag⁺ ions. An enhancement in the Ag⁺ removal capacity by ～ 20% (from 77.8 to 94.4 mg g^–1) and ～ 50% (from 83.9 to 125 mg g^–1) was found in the Ag(I)‐imprinted CS and Ag(I)‐imprinted CS/PVA membranes, respectively, when compared with the nonimprinted membranes. Removal equilibra was achieved in about 40 min for the non‐ and ion‐imprinted CS/PVA. The pH and temperature significantly affected the removal capacity of ion‐imprinted membrane. The relative selectivity coefficient values of Ag⁺/Cu²⁺ and Ag⁺/Ni²⁺ are 9 and 10.7 for ion‐imprinted CS membrane and 11.1 and 15 for ion‐imprinted CS/PVA membrane when compared with nonimprinted membranes. The imprinted membranes can be easily regenerated by 0.01M EDTA and therefore can be reused at least five times with only 15% loss of removal capacity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties of starch‐based blend films using citric acid as additive. II

Starch/polyvinyl alcohol (PVA) blend films were prepared by using corn starch, polyvinyl alcohol (PVA), glycerol (GL), and citric acid (CA) as additives and glutaraldehyde (GLU) as crosslinking agent for the mixing process. The additives, drying temperature, and the influence of crosslinker of films on the properties of the films were investigated. The mechanical properties, tensile strength (TS), elongation at break (% E), degree of swelling (DS), and solubility (S) of starch/PVA blend film were examined adding GL and CA as additives. At all measurement results, except for DS, the film adding CA was better than GL because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA, and additives. CA improves the properties of starch/PVA blend film compared with GL. TS, % E, DS, and S of film adding GLU as crosslinking agent were examined. With increasing GLU contents, TS increases but % E, DS, and S value of GL‐added and CA‐added films decrease. When the film was dried at low temperature, the physical properties of the films were clearly improved because the hydrogen bonding was activated at low temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2554–2560, 2006     

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     

Preparation and characterization of CMCS/PVA blend membranes and its sorption and pervaporation performance (I)

Novel pervaporation (PV) membranes for ethanol dehydration were prepared by blend poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMCS), followed by the crosslinking reaction with glutaraldehyde; the structure and miscibility of the blend membranes were characterized by Fourier transform infrared, X‐ray diffraction, and differential scanning calorimetry; the results indicated that the blends were miscible. The effect of feed concentration, operation temperature, crosslinking agent content, etc. on sorption performance and PV performance of the blend membrane is investigated. The membrane of CMCS/PVA blend ratio of 8 : 2 exhibited a high separation factor of 2959 with a reasonably high water flux value of 0.14 kg m^?2h^?1 at the azeotropic feed composition (95 wt % of ethanol) at a temperature of 45°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improvement of the water resistance of atactic poly(vinyl alcohol) nanowebs by a heat treatment

Nanoscale materials can be rationally designed to exhibit significantly changed physical, chemical, and biological properties because of the extremely small dimensions. Therefore, atactic poly(vinyl alcohol) (a‐PVA) nanowebs by an electrospinning technique have very high water solubility because of their nanoscale in comparison with microscale materials such as fibers and films. In this study, a‐PVA nanowebs were prepared via electrospinning under suitable conditions to form PVA webs with uniform nanofibers (fiber average diameter = 200 ± 50 nm), not a bead or bead‐and‐string morphology. Furthermore, to improve the water resistance of the water‐soluble a‐PVA nanowebs, the PVA nanowebs were heat‐treated at various heat‐treatment temperatures. The melting temperature of the heat‐treated PVA nanowebs shifted toward a lower temperature with an increase in the heat‐treatment temperature, and this indicated that micronetwork domains formed. Moreover, with the exception of a PVA nanoweb treated at an excessive heat‐treatment temperature, the heat‐treated PVA nanowebs showed higher crystalline and mechanical properties than a pure PVA nanoweb. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Formation of poly(vinyl alcohol)–iodine complex in aqueous solution: a SEM study of the freeze-dried substances

The freeze-dried samples prepared from dilute PVA aqueous solutions and PVA–iodine complex aqueous solutions have been examined using a scanning electron microscope. The samples prepared from syndiotacticity-rich PVA (S-PVA) solutions were found to have a network structure due to the formation of intermolecular hydrogen bonds, whereas in the case of atactic PVA (A-PVA) a network structure was not found. The network structure became more finely structured with increasing syndiotacticity. The structure of the freeze-dried sample of the complex solution prepared from S-PVA having a syndiotactic diad content of 63·8%, and iodine, was coarse in comparison with that of the freezedried sample of the S-PVA solution. In addition, the formation of spherical bulges, which are considered to correspond to microgels in the aqueous solution, were observed in several places. In the S-PVA having a syndiotactic diad content of 57·8%, the spherical bulges were not observed, whereas the absorbance of the aqueous solution was the highest. Although A-PVA did not form a PVA– iodine complex at 30°C in solution, the frozen solution turned blue due to the formation of aggregates. These phenomena were confirmed by the degree of crystallinity estimated from IR spectra, and the amount of iodine estimated from X-ray microanalysis of the freeze-dried samples. The PVA–iodine complexes are formed by the interaction of the aggregates of PVA molecules with iodine molecules. However, the PVA microgels do not interact with iodine. © 1998 Society of Chemical Industry     

Characterization of konjac glucomannan–quaternized poly(4‐vinyl‐N‐butyl) pyridine blend films and their preservation effect

Novel polymer blends were prepared from a mixture of 2 wt % konjac glucomannan and 4 wt % quaternized poly(4‐vinyl‐N‐butyl) pyridine (QPVP) in aqueous solution and dried at room temperature for 72 h. Their structure and properties were studied by infrared, wide‐angle X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry. Thermal stability in the dry state was reduced with increasing content of QPVP. Compared with QPVP film, the tensile strength of the films was improved in the dry state. The maximum value of 12.74% tensile break elongation was reached when the content of QPVP was 30%. Structural analysis indicated that clear phase separation was observed when the content of QPVP was only 50%. Results from the filmcoating preservation experiments with lychee showed that this blend film had water‐holding ability. The fruit weight loss rate and rot rate both decreased in various degrees. The potential uses of these novel polymer films could be as preservative films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1868–1875, 2004     

Pervaporation behavior of PVA membrane containing β‐cyclodextrin for separating xylene isomeric mixtures

To evaluate molecular recognition function of β‐cyclodextrin to xylene isomers, β‐CD polymer of branching chain extension (β‐CD‐EGDE) was synthesized by crosslinking β‐CD with ethylene glycol diglycidyl ether (EGDE). The pervaporation blend membranes of β‐CD‐EGDE/PVA were prepared by casting an aqueous solution of PVA and β‐CD polymer mixture, and the membranes were used for separation of p‐/m‐ and p‐/o‐xylene mixtures. It was observed that the pristine PVA membrane almost had no selectivity for xylene isomer mixtures. The PVA membrane incorporating β‐CD polymer had molecular recognition function, which selectively facilitated the transport of the xylene isomers. To ascertain pervaporation behavior, the sorption and desorption processes of the membrane in xylenes were investigated. The sorption result showed that the complex formation constant between β‐CDs and xylenes played a key role in swelling behavior. There was a significant difference between diffusion coefficients D and D⁰, calculated from the sorption and desorption measurements, respectively, indicating that the diffusivity selectivity in desorption stage may have remarkable effect on the total selectivity during pervaporation process. © 2012 American Institute of Chemical Engineers AIChE J, 59: 604–612, 2013     

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     

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