Hydrogels from glycidyl derivatives of poly(vinyl alcohol)

Poly(vinyl alcohol) (PVA) was modified with phthalic anhydride to obtain half esters with carboxylic acid groups, which made the reaction with epichlorohydrin easier. The oxirane ring underwent a further crosslinking that led to crosslinked polymers with polar groups capable of interacting strongly with water and therefore with properties of hydrogels. The curing kinetics of the crosslinking were studied by differential scanning calorimetry, and the dependence of the activation energy on conversion degree was studied by isoconversional kinetic analysis. Water absorption was determined gravimetrically as a function of time at room temperature. The swelling behavior of these hydrogels was related to the degree of crosslinking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 693–698, 2003     

Synthesis of poly(vinyl benzal) from poly(vinyl alcohol) in nonaqueous medium

Poly(vinyl alcohol) (PVA) is soluble only in water and so some important derivatives like esters cannot be prepared from PVA. The 100% conversion of PVA to acetal is also elusive as there is strong intermolecular and intramolecular hydrogen bonding. However, PVA can be dissolved in a nonaqueous medium in the presence of a small amount of C₂H₅NO₃ · DMSO(EN · DMSO) and so a maximum extent of conversion may be possible. Here, we report the preparation of poly(vinyl benzal) (PVB) by acid-catalyzed homogeneous acetalization of PVA with benzaldehyde in a nonaqueous medium. The formation of PVB was confirmed by IR and ¹H-NMR spectra. The molecular mass of the polymer was determined by the GPC method. The PVB prepared had a degree of acetalization of 95 mol%. The glass transition temperature, T_g was measured from differential scanning calorimetric (DSC) thermograms. Thermal stabilities were checked by thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). A possible mechanism of three-step thermal decomposition of PVB is proposed. © 1996 John Wiley & Sons, Inc.     

含氯化钠的聚乙烯醇静电纺丝研究

研究了不同聚合度聚乙烯醇与少量氯化钠盐混合物水溶液的静电纺丝,并与单纯聚乙烯醇水溶液的静电纺丝进行了对比。利用扫描电镜观察纤维的形态、直径变化。结果表明:聚乙烯醇水溶液中加入少量氯化钠,由于离子的作用可以使喷射流表面电荷密度增大,静电纺丝可得到比单纯聚乙烯醇更细的纳米纤维。     

Builder performance in detergent formulations and biodegradability of poly(sodium carboxylate) containing vinyl alcohol groups

Two series of poly[(disodium fumarate)co-(vinyl alcohol)] and poly[(disodium maleate)-co-(vinyl alcohol)], containing vinyl alcohol moieties as biodegradable segments in the polymer chain, were prepared and evaluated for builder performance in detergent formulations as well as for their biodegradability. From the biological oxygen demand test and gel permeation chromatography of the polymer in the biodegradation test media, it was found that biodegradability of the copolymers was dependent on the content of vinyl alcohol moieties in the polymer chain. Significant degradation was observed for fumarate copolymers containing more than 75% vinyl alcohol units and for maleate copolymers containing more than 88≈99% vinyl alcohol units in the copolymer chain. The decisive factor for rapid degradation of the polymer by polyvinyl alcohol (PVA)-degrading microbes seems to be the chainlength of the successive vinyl alcohol groups in the polymer chain. A definite chainlength is needed to become a substrate for the PVA-degrading enzyme. For rapid biodegradation to occur, a copolymer containing more than about five to seven successive vinyl alcohol blocks is needed. Builder performance in the detergent formulation is dependent on the content of carboxylate groups in the polymer. Polymers with high carboxylate content showed better detergency, and the fumarate copolymer was more effective than the maleate copolymer. Detergency performance improved greatly with increasing amounts of polymeric builder used in the detergent formulation.     

Synthesis and characterization of poly(vinyl alcohol) carbonate

Poly(vinyl alcohol) (PVA) was reacted with dimethyl carbonate (DMC) to prepare PVA carbonate (PVAC), which is considered to have three structures, cyclic carbonate (I), monocarbonate (II) and crosslinking carbonate (III). Though the reaction proceeded easily in dimethyl sulfoxide at 120 °C without any catalyst, the yield of the ethanol‐insoluble part of the products was less than that with the reaction containing a catalyst such as tetrabutylammonium bromide (TBAB). TBAB concentration did not affect the rate of carbonic esterification but affected the yield of the ethanol‐insoluble part. The rate of carbonic esterification increased with an increase in reaction temperature, and the activation energy of this reaction was 114 kJ mol⁻¹. Carbonic esterification under reduced pressure showed a larger degree of esterification than that of the reaction under atmospheric pressure. PVAC was soluble in water at a low degree of carbonic esterification (DC) but became insoluble as DC increased. The thermal property of PVA reduced by the carbonic esterification was improved as DC increased. © 2000 Society of Chemical Industry     

Synthesis of poly(vinyl alcohol-co-vinyl gallate) by the chemical modification of poly(vinyl alcohol)

Summary Poly(vinyl alcohol-co-vinyl gallate) was successfully synthesized utilizing an esterification reaction in which poly(vinyl alcohol) was transesterified with methyl gallate under alkaline conditions. Aqueous solutions of this copolymer exhibited a sharp critical micelle concentration value, indicating that surface activity is exhibited by the copolymer. Most aqueous solutions of this copolymer possess a black coloring, which indicates that the gallate group is complexing with metal ions present in solution.     

Polarization characteristics of poly(vinyl alcohol) films containing metal iodide

The polarization properties of iodine complex layer deposited by oxidation of poly(vinyl alcohol) (PVA) containing metal iodide were investigated. Heat-resistant polarizing films with high polarization efficiency were produced by oxidizing and stretching the PVA containing metal iodide. The results indicate that i) the polarization efficiency of a polarizing film prepared by oxidation of a PVA film containing 1 mmol or more of potassium iodide (KI)/g PVA at 0°C for 120 s in a 10 wt.-% aqueous solution of H₂O₂ and a degree of stretching of 400% is high, ii) the heat resistance of the polarizing film in this experiment is higher than that of a filter prepared from a commercial PVA film.     

Multifunctionality of poly(vinyl alcohol) nanofiber webs containing titanium dioxide

We prepared titanium dioxide/PVA nanocomposite fiber webs for application in multifunctional textiles by electrospinning. The morphological properties of the TiO₂/PVA nanocomposite fibers were characterized using scanning electron microscopy and transmission electron microscopy. Layered fabric systems with electrospun TiO₂ nanocomposite fiber webs were developed using various concentrations of TiO₂ and a range of web area densities, and then the UV‐protective properties, antibacterial functions, formaldehyde decomposition ability, and ammonia deodorization efficiency of the fabric systems were assessed. Layered fabric systems with TiO₂ nanocomposite fiber webs containing 2 wt% TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited an ultraviolet protection factor of greater than 50, indicating excellent UV protection. The same system showed a 99.3% reduction in Staphylococcus aureus. Layered fabric systems with TiO₂ nanocomposite fiber webs containing 3 wt % TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited a 85.3% reduction in Klebsiella pneumoniae. Titanium dioxide nanocomposite fiber webs containing 3 wt % TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited a formaldehyde decomposition efficiency of 40% after 2 h, 60% after 4 h, and 80% after 15 h under UV irradiation. The same system showed an ammonia deodorization efficiency of 32.2% under UV irradiation for 2 h. These results demonstrate that TiO₂ nanocomposite fibers can be used to produce advanced textile materials with multifunctional properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of chemically bonded poly(vinyl alcohol)-starch composite

Poly(vinyl alcohol) (PVA) was grafted on hydrolysed starch through introduction of the chemically reactive bifunctional compound N-methylolacrylamid (N-MAm). The grafting reaction was carried out in two separate reaction steps. The first step was the reaction of PVA with N-MAm in alkaline medium. The reaction mechanism and reaction conditions such as alkali concentration, temperature, reaction time as well as N-MAm concentration were studied. According to the results obtained, the most appropriate conditions for the preparation of this reactive PVA are: treating PVA with N-MAm (1.25 mol/mol PVA) in the presence of NaOH (6% based on solution volume) at 20°C for 8 h. Second step was the reaction of this reactive PVA (N-MAm-PVA) with hydrolysed starch in the presence of NH₄Cl. The latter was carried out under different conditions including temperature, reaction time, catalyst concentration as well as N-MAm-PVA/hydrolysed starch ratio. The results obtained show that the extent of the grafting reaction is governed by each of these factors. Furthermore, GPC data showed that the molecular weight distribution and the apparent viscosity of PVA-N-MAm-starch composite depend on the initial molecular weight of both PVA and hydrolysed starch used.     

Synthesis and characterization of hydrophobically modified poly(vinyl alcohol)

Summary Two different routes for the preparation of hydrophobically modified poly(vinyl alcohol), PVA are reported. The first method involves the formation of the polymeric alcoholate. An alkylhalide and propanesultone are coupled with the polymer in two subsequent steps of the Williamson ether synthesis. The product is a hydrophobically modified polymer with anionic functionality. The other method proceeds via a 1,4 addition of acrylamide and the Hoffman degradation of the amide to an amine. In the next step, the amine is alkylated with an alkylhalide. The polymers are characterised by quantitative ¹HNMR spectroscopy and titration. Received: 14 January 1999/Revised version: 19 April 1999/Accepted: 19 April 1999     

Synthesis of poly(vinyl alcohol) core-polystyrene shell-type flower microgels

Four types of poly(vinyl alcohol-b-styrene-b-vinyl alcohol) (P(VA-b-S-b-VA)) triblock copolymers were synthesized by hydrolysis of poly(vinyl acetate-b-styrene-b-vinyl acetate) triblock copolymers prepared by radical living polymerization. The polyvinyl alcohol (PVA) core-polystyrene corona-type flower micelles were formed with ASA-4 in benzene at 25°C. The PVA core part of the micelle was crosslinked with hexamethylene diisocyanate in solution. The monodispersed spherical products (microspheres) were synthesized by crosslinking. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 849–854, 1997     

Biodegradability of poly(vinyl alcohol)

Plastic waste increases at a rate of several tons per year and the time required for their biodegradation is often unknown. The Phanerochaete chysosporium fungus oxidizes a wide variety of toxic organic compounds to nontoxic compounds or CO₂ and H₂O. The biodegradability of the poly(vinyl alcohol) (PVOH) caused by this fungus was analyzed by gel permeation chromatography (GPC) with differential refractive index (Δn) and ultraviolet (UV) detectors. During the GPC analyses, the PVOH is in contact with the components of the culture medium. These components can interact with the stationary phase and also with the polymer producing erroneous results in the molecular weight determination. Therefore, we compare results using differnt mobile phases. A phosphate-acetate buffer of pH 7.4 was found to be appropriate mobile phase to follow the degree of degradation of the PVOH by the change in the average molecular weight determined by GPC in this culture medium. UV detection enabled us to identify structural changes associated with transformations of the carbonyl groups, mainly to enolized β-diketones groups. Infrared absorption (FTIR) confirmed these changes and also showed important modifications in the C-O stretching region probably due-to apertures of cyclic ether groups or transformations of the OH groups by oxidation reactions.     

Characterization of poly(vinyl alcohol)

Molecular weight distributions, long chain branching frequency, and solution viscosities of samples of commercial poly(vinyl alcohol) (PVA) are reported. The PVA was fully reacetylated to poly(vinyl acetate) (PVAc) for characterizations by size exclusion chromatography using a low angle light scattering detector. The Mark–Houwink constants for PVAc in toluene were determined to be K = 0.106 cm³ g^?1 and α = 0.59, at 25°C. Long chain branching frequency in the commercial PVAs studied was small and was little affected by polymer molecular weight. Some 95% or more of the branches in these species were short. Aqueous solutions at 10% (w/v) of PVA were Newtonian. The polymers examined differed in chemical composition, molecular weight distributions, and mean block lengths of vinyl acetate residues. Variations in a single characteristic, like a solution or intrinsic viscosity, cannot be used to deduce structural differences between PVAs.     

On the viscoelastic properties of poly(vinyl alcohol) and chemically crosslinked poly(vinyl alcohol)

Poly(vinyl alcohol)(PVA) films chemically crosslinked with glutaraldehyde(GA) in the presence of HCl were prepared by casting from aqueous solutions. The PVA and PVA gels were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA); their swelling characteristics and tensile strength were also determined. The DSC results for the gels displayed depressions of the melting and crystallization temperatures, as well as a decrease of the heat of fusion, when compared to those of PVA free of crosslinker. The DMA analysis revealed that: (1) The glass transition temperature of the wet PVA was lower than that of the dry one, indicating that the water had a plasticizing effect. (2) The gels had a lower glass transition temperature than PVA. (3) The glass transition temperature of the wet gels increased with increasing crosslink density. Possible explanations are provided for these observations. Whereas the thermogravimetric curves of PVA exhibited a single degradation peak, two degradation peaks were detected for the crosslinked PVA. The wet PVA and PVA gels displayed lower tensile strengths and higher elongations than the dried ones. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1816–1823, 2001     

Sticky poly(vinyl alcohol) hydrogels

Low-temperature gelation of poly(vinyl alcohol) (PVA) solution was performed in the presence of CaCl₂. The resulting PVA hydrogels showed high stickiness and excellent water-holding ability. These properties became more remarkable with increasing CaCl₂ concentration in solvent. Furthermore, both the peel strength on stainless steel and the degree of swelling of the PVA hydrogel drastically increased as CaCl₂ concentration was increased from 20 to 30 wt %. It is concluded that the sticky and water-holding properties of PVA hydrogels are intimately related to the state of hydration of Ca ions in aqueous environment. © 1993 John Wiley & Sons, Inc.     

Synthesis and rheological properties of hydrophobically modified poly(vinyl alcohol)

A novel series of water-soluble hydrophobically modified poly(vinyl alcohol) (HMPVA) with various hydrophobe contents was prepared by grafting poly(vinyl alcohol) (PVA) using 1-dodecanol and toluene-2,4-diisocyanate as hydrophobic monomer and coupling agent, respectively. The chemical structure of HMPVA was analyzed by Fourier Transform Infrared Spectrometer (FTIR) and ¹H NMR. Rheological properties of the aqueous solutions also confirmed the incorporation of hydrophobic groups into PVA. In dilute concentration regime, HMPVAs exhibited lower intrinsic viscosity than PVA, suggesting that HMPVA molecules were more shrunken. While the aqueous solution viscosity was enhanced due to hydrophobic modification at a high concentration, and HMPVAs with higher hydrophobe contents exhibited lager values of apparent viscosities. Over a frequency range of 1 to10² rad/s, the dynamic storage modulus of PVA solution was smaller than the dynamic loss modulus whereas the dynamic storage modulus of HMPVAs solutions was greater than the dynamic loss modulus, indicating the evolution of viscoelastic solid properties in HMPVAs solutions. The yield stress of PVA was nearly zero whereas that of HMPVAs represented positive values, implying that networks were present in HMPVAs solutions.     

Synthesis of poly(vinyl alcohol)s with narrow molecular weight distribution from poly(benzyl vinyl ether) precursors

Summary A series of poly(benzyl vinyl ether)s of low molecular weight (5000 to 15000 g mol^-1) and narrow molecular distribution ( ) have been synthesisedvia the cationic polymerisation of benzyl vinyl ether. Acetylation with acetic anhydride/tin (IV) chloride leads to poly(vinyl acetate), which can be hydrolysed to near-monodisperse water-soluble poly(vinyl alcohol) with an isotacticity of approximately 47%. This polymer was re-acetylated and its molecular weight distribution assessed to confirm that hydrolysis gives minimal chain scission.     

Characterization of brominated poly(4-hydroxystyrene) derivatives containing unsaturated groups

Brominated poly(4-hydroxystyrene) (HS) derivatives containing unsaturated groups such as alkenyl or alkenoyl were investigated with infrared and ¹H nuclear magnetic resonance spectroscopy. HS derivatives have good thermal properties and their decomposition temperatures were higher than 300°C. Their thermal degradation behaviour is interpreted by the strength of electron withdrawal of substituent groups. The dielectric constants of HS derivatives can be predicted by the Clausius-Mosotti equation. The calculated values are found to agree with the observed values. The dielectric constants of the polymer can be reduced by replacing hydroxy groups with alkenoyl groups, especially methacryloyl units.     

Characterization of associating hydrogels of poly(vinyl alcohol) and poly(vinyl pyrrolidone)

In this study, hydrogels were prepared from blends of poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP). The miscibility of the polymers was confirmed with differential scanning calorimetry with the appearance of a single glass‐transition temperature. Additionally, a negative Flory–Huggins interaction parameter further verified the interaction between PVA and PVP. We evaluated the stability of the hydrogels by swelling the gels in phosphate‐buffered saline solutions at pH 7.4. With attenuated total reflectance‐Fourier transform infrared spectroscopy, it was determined that, during swelling, PVP dissolved out of the gel over time and the equilibrium gel content of PVP was nearly identical in all of the samples investigated. After the dissolution of PVP, the equilibrium water content of the gels ranged from 64 to 76 wt %. Additionally, rubber elasticity studies were performed to elucidate information about the physically crosslinked network structure. As determined from rubber elasticity experiments, the mesh size of the physically crosslinked hydrogels ranged from 90 to 230 Å. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(dimethyl siloxane) containing poly(vinyl pyrrolidinone) block copolymers

ABA‐type block copolymers containing segments of poly(dimethyl siloxane) and poly(vinyl pyrrolidinone) were synthesized. Dihydroxyl‐terminated poly(dimethyl siloxane) was reacted with isophorone diisocyanate and then with t‐butyl hydroperoxide to obtain macroinitiators having siloxane units. The peroxidic diradical macroinitiators were used to polymerize vinyl pyrrolidinone monomer to synthesize ABA‐type block copolymers. By use of physicochemical methods, the structure was confirmed, and its characterization was accomplished. Mechanical and thermal characterizations of copolymers were made by stress–strain tests and differential scanning calorimetric measurements. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1915–1922, 1999