Synthesis,characterization, and swelling behaviors of chitosan‐g‐poly(acrylic acid)/poly(vinyl alcohol) semi‐IPN superabsorbent hydrogels

A series of granulated semi‐interpenetrating polymer network (semi‐IPN) superabsorbent hydrogels composed of chitosan‐g‐poly(acrylic acid) (CTS‐g‐PAA) and poly(vinyl alcohol) (PVA) were prepared by solution polymerization using ammonium persulfate (APS) as an initiator and N,N′‐methylenebisacrylamide (MBA) as a crosslinker. The effects of reaction conditions such as the concentration of MBA, the weight ratio of AA to CTS, and the content of PVA on water absorbency were investigated. Infrared (IR) spectra and differential scanning calorimetry (DSC) analyses confirmed that AA had been grafted onto CTS backbone, and PVA semi‐interpenetrating into CTS‐g‐PAA networks. SEM analyses indicated that CTS‐g‐PAA/PVA has improved porous surface and PVA was uniformly dispersed in CTS‐g‐PAA network. The semi‐IPN hydrogel containing 10 wt% PVA shows the highest water absorbency of 353 and 53 g g^?1 in distilled water and 0.9 wt% NaCl solution, respectively. Swelling behaviors revealed that the introduction of PVA could improve the swelling rate and enhance the pH stability of the superabsorbent hydrogel. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation and characterization of a nanoscale poly(vinyl alcohol) fiber aggregate produced by an electrospinning method

Nanoscale poly(vinyl alcohol) (PVA) fiber (100–500 nm) aggregates were prepared with an electrospinning technique. Additionally, a chemical crosslinking method was used to crosslink the nanoscale PVA fiber aggregates. Differential scanning calorimetry, wide‐angle X‐ray diffraction, and scanning electron microscopy techniques were employed to characterize the PVA fiber aggregates. The different crosslinking densities of the PVA fiber aggregates were obtained through the control of the weight percentage of glyoxal to PVA. The crosslinking densities due to heat treatment and chemical crosslinking were studied. The influence of heat treatment could be neglected in contrast to chemical crosslinking when the curing temperature was 120 °C. The primary factor that affected the crosslinking density was the volume of the chemical crosslinking agent. The results showed that the properly crosslinked PVA fiber aggregates had better antiwater solubility and mechanical properties than the noncrosslinked PVA fiber aggregates. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1261–1268, 2002     

Factors influencing the swelling and elution properties of poly(vinyl alcohol) cast gels

Swelling and elution properties of physically crosslinked poly(vinyl alcohol) (PVA) cast gels depend on the network structure of the PVA and crosslink, which is characterized by the size, number, and distribution of microcrystallites. Therefore, the swelling and elution ratios can be manipulated by adept control of the conditions adopted for the preparation of gels. Among the various factors that influence the formation of microcrystallites, the temperature and relative humidity at gelation play an important role. In addition, the size of gel is also a key factor that determines the network structure of gels. To this end, this study quantitatively evaluates the macroscopic properties of swelling and elution, and the microscopic properties of the network structures in disk‐shaped PVA cast gels of the same diameter prepared by casting different weights of PVA solution in the same dish. Although the drying speed can be controlled by adjusting the three processing parameters, namely, drying temperature, humidity, and cast weight, the changes in swelling and elution ratios, microcrystallite size, and crystallinity independently depended on each parameter. Regardless of the three factors, the swelling ratio was found to correlate strongly with the elution ratio. Optimum factors to minimize the elution ratio are discussed on the basis of the change in the network structures obtained by varying the preparatory conditions. Based on the results of the systematic analyses, this study proposes a method to control the elution ratio while retaining high water‐absorbance ability. Copyright © 2015 John Wiley & Sons, Ltd.     

Study on superabsorbent of maleic anhydride/acrylamide semi‐interpenetrated with poly(vinyl alcohol)

A series of superabsorbents of maleic anhydride (MAH)/acrylamide (AM) interpenetrated with poly(vinyl alcohol) (PVA) were prepared by aqueous polymerization, using N,N‐methylenebiacrylamide (NNMBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The samples were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and scanning electron microscope (SEM). The effects of reaction variables on the water absorbency of the superabsorbents in distilled water and in 0.9 wt% NaCl solution were investigated. In addition, the effect of the PVA content on the swelling rate and sensitivity to saline of the superabsorbents were also investigated. The results showed that the absorbency, both in 0.9 wt% NaCl solution and in distilled water, first decreased and then increased with increasing PVA content. Moreover, the resultant superabsorbent had a higher absorption rate and it became less sensitive to saline by incorporating certain amount of PVA into the network of the hydrogel. Copyright © 2009 John Wiley & Sons, Ltd.     

Solid‐state 13C and 129Xe NMR study of poly(vinyl alcohol) and poly(vinyl alcohol)/lactosilated chitosan gels

Dry and hydrated poly(vinyl alcohol) (PVA) gels with 55% (a‐PVA) and 61% (s‐PVA) syndiotacticity and related PVA/lactyl chitosan (LC) blends have been investigated with ¹²⁹Xe and cross‐polarization/magic‐angle‐spinning ¹³C NMR techniques. Although the dry gels exhibit two broad ¹²⁹Xe resonances in the slow‐to‐intermediate exchange limit, both hydrated gels show three resonances. The corresponding dry blends exhibit two signals, the chemical shifts and line widths of which change with respect to those of pure PVA, whereas one (a‐PVA/LC) or two (s‐PVA/LC) signals appear in the spectra of the hydrated blends. A comparative analysis of the data demonstrates that LC rearranges the domains of the polymeric matrix in both the dry and hydrated blends according to the syndiotacticity of the PVA chains. Information on the molecular motions of the amorphous and swollen polymeric domains in the kilohertz range has been obtained from an analysis of the spin‐lattice relaxation times. These data indicate that the dynamics and arrangement of the PVA chains in the gels are strongly affected by their tacticity and the addition of the copolymer LC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3123–3131, 2003     

Radiation effects on the thermal degradation of poly(vinyl chloride) and poly(vinyl alcohol)

Radiation effects on the formation of conjugated double bonds in the thermal degradation of poly(vinyl chloride) (PVC) and poly(vinyl alcohol) (PVA) were investigated. Thin films of PVC and PVA were either irradiated with γ-rays at ambient temperature (pre-irradiation) and then subjected to thermal treatment, or irradiated at elevated temperatures (in situ irradiation). An extensive enhancement of the thermal degradation was observed for the pre-irradiation of the PVC films, which was more effective than the effect of the in situ irradiation at the same absorption dose. For the PVA degradation, however, the effect of the in situ irradiation was larger than that of the pre-irradiation. The results were explained and related mechanisms were discussed based on radiation-induced chemical reactions and their individual contributions to the thermal degradation behaviors of the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3089–3095, 1998     

Grafting reactions of vinyl acetate onto poly[(vinyl alcohol)-co-(vinyl acetate)]

The grafting preference of vinyl acetate onto the methine carbon of poly(vinyl alcohol) (PVOH) versus the acetate group of poly(vinyl acetate) (PVAc) was determined as part of an attempt to prepare novel branched PVOH from partially hydrolyzed PVAc. The results showed long chain grafting on the acetate groups of the PVAc units rather than the methine carbons of the PVOH or PVAc units. Decreasing the monomer or initiator concentration decreased the molecular weight of the graft copolymer formed. Of the initiators studied, ammonium persulfate gave the largest increase in copolymer molecular weight. Both hydrolysis and reacetylation combined with gel permeation chromatography (GPC) and ¹³C-NMR of the fully hydrolyzed material were used to estimate the number and location of grafts. © 1996 John Wiley & Sons, Inc.     

Alignment effect of attapulgite on the mechanical properties of poly(vinyl alcohol)/attapulgite nanocomposite fibers

Poly(vinyl alcohol) (PVA)/attapulgite (AT) nanocomposite fibers have been prepared by wet spinning. The morphology and mechanical properties of the modified PVA fibers have been characterized with transmission electron microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), birefringence measurements, and mechanical testing. The PVA/AT nanocomposite fibers show much higher tensile strength, initial modulus, and work to break than pure PVA fibers with the same draw ratio. SEM observations demonstrate that the AT nanorods can align orderly along the fiber axis by stretching and have good adhesion to the fiber matrix. The results of birefringence measurements prove that the modified fibers have higher orientation than pure PVA fibers after stretching. The results of DSC analysis indicate that the crystallinity of the PVA fibers can be increased by the addition of AT. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1995–2000, 2006     

Liquid-state transitions (T>T g) of poly(vinyl alcohol)

The two liquid state transitions,T _ll andT _ll, of non-crystalline, uncrosslinked poly(vinyl alcohol) were determined by differential scanning calorimetry.T _ll increased as the molecular weightM _n increased, whileT _ll remained almost constant. Crosslinking and crystallinity lead to disappearance of the transitionT _ll. The transitionT _ll was linked to mobility of whole chains, whereasT _ll was characteristic of segmental mobility.     

Properties of a novel thermal sensitive polymer based on poly(vinyl alcohol) and its layer‐by‐layer assembly

Structurally modified poly(vinyl alcohol) (PVA) was prepared as novel thermally sensitive polymers by partially acetalyzing and/or ionizing the commercially available PVA. Their aqueous solutions experience completely reversible polymer aggregation and dissolution above and below the lower critical solution temperature (LCST), respectively. The LCST of a partially acetalyzed PVA (APVA) can be readily controlled by the degree of acetalysis or the molecular weight of the starting PVA. Introduction of a small amount of cationic group onto the APVA backbone increases the LCST obviously, while the LCST is highly sensitive to NaCl concentration. Then APVA and cationic APVA multilayers are assembled on rayon to make a thermal responsive fiber. The atomic force microscopy (AFM) images of the surface reveal the increment of roughness stimulated by temperature. Copyright © 2007 John Wiley & Sons, Ltd.     

Photo‐Induced Solid‐State Crosslinking of Electrospun Poly(vinyl alcohol) Fibers

Summary: Poly(vinyl alcohol) (PVA) was derivatized by polymer analogous reaction with thienyl acryloyl chloride and processed to submicrometer fibers by electrospinning from aqueous solution. Water solubility of otherwise water‐soluble PVA fibers was reduced considerably by UV crosslinking of thienyl acrylate modified PVA fibers in the solid state. Water stability of these crosslinked fibers was proven by water steam test at 95 °C.

UV/Vis spectrum of PVA‐Thio fibers irradiated for different periods at 300 nm.     

Effects of microcrystallites on swelling behavior in chemically crosslinked poly(vinyl alcohol) gels

We report the swelling ratio and network structure of a poly(vinyl alcohol) (PVA) gel chemically crosslinked by glutaraldehyde with different degrees of crosslinks. Microcrystallites were formed in a chemical PVA gel during a drying process and were confirmed by X‐Ray diffraction (XRD) measurements and Fourier transform infrared (FTIR) spectroscopy. The formation of microcrystallites in the dried gels was suppressed by increasing the degrees of chemical crosslinks. When the dried samples were immersed in pure water at 25 °C, the swelling ratio depended on the degree of chemical crosslinks resulting from the destruction of physical crosslinks by microcrystallites. On the other hand, when the dried samples were immersed in a poor solvent of a mixture of dimethyl sulfoxide and water at 8 °C, the gels did not swell and stayed in the collapsed state. Starting from the collapsed state, the equilibrium swelling ratios were measured while the temperature was increased to 90 °C and then decreased to 8 °C. As a result, irreversible swelling behaviors were observed for all gels with different degrees of crosslinks, which were attributed to the destruction of microcrystallites. The swelling behavior is discussed in terms of the formation and destruction of additional physical crosslinks in the chemical PVA gels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Characterization of poly(vinyl alcohol) during the emulsion polymerization of vinyl acetate using poly(vinyl alcohol) as emulsifier

During the emulsion polymerization of vinyl acetate (VAc) using poly(vinyl alcohol) (PVA) as stabilizer and potassium persulfate as initiator, the VAc reacts with PVA forming PVA-graft-PVAc. When the grafted polymer reaches a critical size it becomes water-insoluble and precipitates from the aqueous phase contributing to the formation of polymer particles. Since particle formation and therefore the properties of the final latex will depend on the degree of grafting, it is important to quantify and to characterize the grafted PVA. In this work, the quantitative separation and characterization of the grafted water-insoluble PVA was carried out by a two-step selective solubilization of the PVAc latex, first with acetonitrile to separate PVAc homopolymer, followed by water to separate the water-soluble PVA from the remaining acetonitrile-insoluble material. After the separation, the water-soluble and water-insoluble PVA were characterized by Fourier Transform Infrared (FTIR) spectroscopy and ¹H and ¹³C nuclear magnetic resonance (NMR) analyses, from which the details of the PVA-graft-PVAc structure were obtained. © 1996 John Wiley & Sons, Inc.     

Carbendazim‐loaded electrospun poly(vinyl alcohol) fiber mats and release characteristics of carbendazim therefrom

Ultra‐fine poly(vinyl alcohol) (PVA) electrospun fiber mats containing carbendazim were successfully fabricated by electrospinning from the neat PVA solution containing carbendazim in various amounts based on the weight of PVA. The morphological appearance of both the neat and the carbendazim‐loaded electrospun PVA fibers were smooth and the incorporation of carbendazim in the neat PVA solution did not affect the morphology of the resulting fibers. The average diameters of the neat and the carbendazim‐loaded electrospun PVA fibers ranged between 155 and 160 nm. The chemical integrity of the as‐loaded carbendazim in the carbendazim‐loaded electrospun PVA fiber mats was intact as verified by the ¹H‐nuclear magnetic resonance spectroscopy. Thermal properties of the carbendazim‐loaded electrospun PVA fiber mats were analyzed by differential scanning calorimetry and thermogravimetric analysis. The release characteristics of the carbendazim‐loaded electrospun PVA mats were investigated by the total immersion method in distilled water at 30°C. The carbendazim‐loaded electrospun PVA mats exhibited greater amount of carbendazim released than the carbendazim‐loaded as‐cast films. Copyright © 2010 John Wiley & Sons, Ltd.     

Study of the self‐diffusion of poly(ethylene glycol)s in poly(vinyl alcohol) aqueous systems

We have measured the self‐diffusion coefficients of a series of oligo‐ and poly(ethylene glycol)s with molecular weights ranging from 150 to 10,000, in aqueous solutions and gels of poly(vinyl alcohol) (PVA), using the pulsed‐gradient spin‐echo NMR techniques. The PVA concentrations varied from 0 to 0.38 g/mL which ranged from dilute solutions to polymer gels. Effects of the diffusant size and polymer concentration on the self‐diffusion coefficients have been investigated. The temperature dependence of the self‐diffusion coefficients has also been studied for poly(ethylene glycol)s with molecular weights of 600 and 2,000. Several theoretical models based on different physical concepts are used to fit the experimental data. The suitability of these models in the interpretation of the self‐diffusion data is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2396–2403, 1999     

Effect of poly(vinyl alcohol) fine particles as a novel biodegradable nucleating agent on the crystallization of poly(3‐hydroxybutyrate)

The effect of poly(vinyl alcohol)(PVA) fine particles as the nucleating agent on the crystallization behavior of bacterial poly(3‐hydroxybutyrate)(PHB) was studied using differential scanning calorimetry measurements and polarized light microscope observation. The results were compared with the effect of PVA conventionally blended with PHB. The PVA fine particles were found to be able to greatly enhance the crystallization of PHB, while the conventionally blended PVA extremely retarded the crystallization of PHB. The nucleating effect of PVA fine particles is almost comparable to that of the talc powder. Considering the biodegradability and biocompatibility of PVA, the usage of PVA particle as a nucleating agent provides marked benefits over the currently employed nonbiodegradable nucleating agents, such as talc and boron nitride. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44:1813–1820, 2006     

Silylation of poly(vinyl alcohol) with hexamethyldisilazane in liquid ammonia

Silylation of poly(vinyl alcohol) has been performed with hexamethyldisilazane in liquid ammonia in an autoclave. This novel procedure has the advantage that the educt, the reagent, and the product are soluble in ammonia, which works under homogeneous conditions. No salt like by-products are formed and no tedious purification of the product is necessary. The degree of silylation has been adjusted through the ratio of silylating agent to hydroxy groups. Random incorporation of trimethylsilyl groups was proven by the linear dependence of the glass transition temperature from the degree of silylation and the solubility of the partially silylated material. Quantitative investigation of the silylation reaction showed first-order kinetics for the initial and final stages of the reaction indicative of a reaction where k₁ > k₂ > k₃. © 1995 John Wiley & Sons, Inc.     

Effect of poly(ethylene oxide) on the structure and properties of poly(vinyl alcohol)

To improve the drawability of poly(vinyl alcohol) (PVA) thermal products, poly(ethylene oxide) (PEO), a special resin with good flexibility, excellent lubricity, and compatibility with many resins, was applied, and the Fourier transform infrared spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WXRD) were adopted to study the hydrogen bonds, water states, thermal properties, crystal structure, and nonisothermal crystallization of modified PVA. It was found that PEO formed strong hydrogen bonds with water and PVA, thus weakened the intra‐ and inter‐hydrogen bonds of PVA, changed the aggregation states of PVA chains, and decreased its melting point and crystallinity. Moreover, the interactions among PVA, water, and PEO retarded the water evaporation and made more water remain in the system to plasticize PVA. The existence of PEO also slowed down the melt crystallization process of PVA, however, increased the nucleation points of system, thus made more and smaller spherulites formed. The weakened crystallization capability of PVA and the lubrication of PEO made PVA chains to have more mobility under the outside force and obtain high mechanical properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1946–1954, 2010     

Ion-specific swelling behavior of poly(vinyl alcohol) gel prepared by γ-ray irradiation

Poly(vinyl alcohol) gel was prepared by γ-ray irradiation of an aqueous solution of the polymer and its swelling behavior in solutions of the alkali-metal and alkaline-earth-metal salts was investigated. The gel deswelled in solutions containing strongly hydrated anions and swelled in solutions containing strongly hydrated cations. The degree of swelling of the gel was in the following order: SO₄ ²⁻<Cl⁻<Br⁻ ≅ NO₃ ⁻<I⁻ for the anions and K⁺<Na⁺<Li⁺ and Sr²⁺<Ca²⁺<Mg²⁺ for the cations. These results were interpreted in terms of interactions between the polymer and the ions through the hydration layers. Received: 6 November 2000 Accepted: 24 May 2001     

Correlation of macromolecular permeability to network characteristics of multivinyl poly(vinyl alcohol) hydrogels

Modulation of the structural parameters of multivinyl hydrogels allows optimization of their permeability, which is a prerequisite for different biomedical applications. However, only a few studies to date have been reported regarding macromolecular diffusion within divinyl and multivinyl systems, and even less provide information about the correlation of diffusion to the network characteristics. Therefore, this study aimed to understand the permeability performance of tailored poly(vinyl alcohol) (PVA) multivinyl hydrogels and correlating it to the network characteristics using two common theories: rubber elasticity and equilibrium swelling. A systematic increase in the number of functional groups per PVA backbone successfully modulated the PVA physicomechanical properties. These modifications resulted in varying the hydrogel permeability performance to solutes of different sizes and shapes. Correlating the network characteristics to macromolecular permeability of hydrogels proved the reliability of applying the equilibrium swelling theory for hydrogel mesh size estimation over the rubber elasticity theory. © 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 63–72