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     

Thermal and structural characterization of nanofibers of poly(vinyl alcohol) produced by electrospinning

Poly(vinyl alcohol) (PVOH) was obtained from the alkaline hydrolysis of poly(vinyl acetate) (PVAc). Nonwoven membranes (mats) of PVOH nanofibers were produced by electrospinning of solutions of PVOH in water with and without aluminum chloride. The concentration of the PVOH/water solution was 12.4% w/v. The morphology of the mats was analyzed by scanning electron microscopy (SEM). The thermal properties and the degree of crystallinity of the nanofibers were measured by differential scanning calorimetry (DSC); the crystal structure of the mats was evaluated by wide‐angle X‐ray diffraction. The best nanofibers were obtained by electrospinning the PVOH/water solution with aluminum chloride (45% w/v) in which an electrical field of 3.0 kV/cm was applied. It was observed that the addition of the aluminum chloride and the increase in the applied electrical field decreased the number‐average nanofibers diameters. The mats without aluminum chloride had higher melting temperatures and higher degrees of crystallinity than the mats with the salt. The crystal structure of the mats was found to be monoclinic; however, the mats were neither highly oriented nor have a high degree of crystallinity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolymerization of aniline and vinyl acetate by using various surfactants in aqueous media

Polyaniline/poly(vinyl acetate) (PAn/PVAc) copolymer was prepared in aqueous solution by the copolymerization of vinyl acetate and aniline using a mixture of KIO₃ and (NH₄)₂S₂O₈ as an oxidant in the presence of the surfactants sodium dodecylbenzenesulfonate, poly(ethylene glycol), and hydroxypropylcellulose. The PAn/PVAc copolymers were characterized in terms of their conductivity, morphology, and structure. The results indicated that the morphology and conductivity of the products were dependent on the type of surfactant used (anionic or nonionic). Furthermore, it was found that adding vinyl acetate monomer to the stirred aqueous solution containing oxidant, surfactant, and aniline monomer had a great effect on the morphology and increased the amount of the product. The structures of the products were determined by FTIR spectroscopy. J. VINYL ADDIT. TECHNOL., 13:229–233, 2007. © 2007 Society of Plastics Engineers     

Synthesis and characterization of polyvinyl acetate/montmorillonite nanocomposite by in situ emulsion polymerization technique

Exfoliated polyvinyl acetate/montmorillonite nanocomposite (PVAc/MMT) was prepared via in situ emulsion polymerization. The resulting PVAc with various organophilic MMT contents was investigated. In the nanocomposite latex preparation, sodium lauryl sulfate (SLS), ammonium persulfate (APS), and poly (vinyl alcohol) (PVA) are used as anionic emulsifier, conventional anionic initiator, and stabilizer, respectively. The samples were characterized using elemental analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM). The XRD and AFM results demonstrate that the MMT well dispersed at molecular level in the PVAc matrix. Thermal properties of the nanocomposite were studied by using differential scanning calorimetric analysis (DSC). The exfoliated PVAc/MMT nanocomposite showed a higher glass transition temperature and a better thermal stability compared to the pure PVAc.     

Effect of HPC-PANI/SIO2 Emulsion Nanocomposite in Poly(vinyl acetate) for Corrosion-Resistant Coatings

Emulsion nanoparticles of polyaniline were synthesized in an aqueous solution using ammonium persulfate as an oxidant in the presence of nanometer-size SiO₂ and hydroxylpropylcellulose as a stabilizer. Different concentrations of prepared nanocomposites were blended with poly(vinyl acetate) as the major matrix and coated on the carbon steel. The product was characterized and compared by (XRD), (FTIR), (SEM), and (TEM). According to the results 1 wt.% of HPC-PANI/SiO₂ nanocomposite in PVAc has a much lower corrosion current in NaCl solution and 3 wt.% of HPC-PANI/SiO₂ nanocomposite in PVAc has the best corrosion protection in HCl.     

PVAc Microspheres via Semicontinuous Emulsion Polymerization: Synthesis,Characterization, Kinetic,and Surface Morphology Studies

Poly (vinyl acetate) (PVAc) latexes are economically important products with many desirable features. They are used as adhesives for porous materials in various processing stages of industries. Synthesis parameters have an important role on the physico-chemical properties of PVAc latexes such as: viscosity, average molecular weight, degree of polymerization, and surface morphology. In this work, PVAc was prepared via semicontinous emulsion polymerization (delayed monomer and initiator addition process) in the presence of ammonium persulfate (APS) as conventional anionic initiator, poly (vinyl alcohol) (PVA) as stabilizer, and sodium lauryl sulfate (SLS) as anionic emulsifier. The surface morphology of PVAc microspheres was, examined using a scanning electron microscope (SEM) and atomic force microscope (AFM). It is evident from the SEM photographs that all the particles became microspheres and are uniform in shape. The use of AFM for imaging of polyvinyl acetate confirms a typical sphere polymer. The effect of changes in the different parameters such as concentration of emulsifier, initiator concentration, and presence or absence of buffer on the vinyl acetate (VAc) conversion, the steady state polymerization rate, the viscosity-average molecular weight, and the final latex viscosity of synthesized PVAc were investigated. The effects of anionic emulsifier on the synthesized PVAc are also compared with those obtained by the nonionic emulsifier. The comparison indicated that the VAc monomer conversion and the final latex viscosity of the anionic system were higher than for the nonionic system but the viscosity-average polymer molecular weight of the anionic system was lower than that of the nonionic system. The adhesive strength of the synthesized PVAc latex was examined and the load and deflection data were reported.     

Acidic hydrolysis of a poly(vinyl acetate) matrix by the catalytic effect of Ag nanoparticles and the micellization of Ag‐metal‐containing polymer

In this study, we conveniently obtained Ag(0)–polymer nanocomposites by reacting AgNO₃ with commercial poly(vinyl acetate) (PVAc) in the absence of a special reducing agent. The formation of Ag(0) metal was detected after formic acid (HCOOH) was added to a PVAc–AgNO₃ complex system, and some of the acetate groups of the PVAc backbone were hydrolyzed to form hydroxyl groups (OH) under the catalytic effect of the reduced Ag(O) metal. Here, the structure of the partially hydrolyzed PVAc backbone was represented as PVOH‐PVAc. X‐ray diffraction spectra showed that the Ag(0) metal generated in this method was in the form of Ag crystals. The structure of the Ag(0)–polymer was analyzed by ¹H‐NMR and ¹³C‐NMR spectroscopy. The micellization of the Ag(0)–polymer was also investigated by the addition of an inducing solvent to the formic acid solution of Ag(0)–polymer. The image showed that the morphology of the Ag micelles in the H₂O‐induced solvent was a Ag corona with a Ag shell, and that in the p‐xylene induced solvent showed a Ag cluster core structure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1457–1464, 2006     

Gellan/poly(vinyl alcohol) hydrogels: characterization and evaluation as delivery systems

Bioartificial polymeric materials in the form of hydrogels were prepared starting from blends of poly(vinyl alcohol) (PVOH) with gellan, using a procedure based on freeze–thawing cycles. The effect exerted by gellan on the properties of these materials was investigated. The materials were loaded with human growth hormone (GH) and the release of the drug was evaluated. The results obtained indicated that gellan favours the crystallization process of PVOH allowing the formation of a material with a more homogeneous and stable structure than that of pure PVOH hydrogels. Both the PVOH melting enthalpy and the elastic modulus increased with increasing gellan content in the hydrogels; in addition, the higher the gellan content in the samples, the lower was the amount of PVOH released. Gellan/PVOH hydrogels were able to release GH and the release was affected by the content of the biological component. The amount of GH released was within a physiological range. © 2001 Society of Chemical Industry     

NMR imaging of adhesive-bonded structures: the use of the T1 and T2 relaxation time information

—Nuclear magnetic resonance imaging (NMRI) is used to obtain cross-sectional images of three poly(vinyl alcohol) (PVOH) stabilized poly(vinyl acetate) (PVAc) emulsions in glass vials and in glue-lines between a wood block and a ceramic tile. From a series of T, and T₂ weighted images acquired with different repetition and echo times, pure T, and T₂ images of the emulsions are calculated. The T₁ relaxation times are between 0.83 and 1.04 s and the T₂ relaxation times between 15 and 26 ms for the emulsions. The relaxation information is used to compute a proton spin density image. Optimum pulse sequence parameters are determined to detect and to create a maximum intensity contrast for the signals of two different emulsions in a 200-300 μm glue-line.     

Investigation of Adhesion Performance of Aqueous Polymer Latex Modified by Polymeric Methylene Diisocyanate

Aqueous polymer isocyanate (API), which has good adhesive properties at ambient temperature and excellent resistance to warm/boiling water, and is friendly to the environment, is widely used in the timber-processing industry. To prepare high performance API, vinyl acetate homopolymer and copolymer emulsion were respectively cross-linked by three types of polymeric methylene diisocyanate (p-MDI). The potlife, curing time, bonding strength, and water resistance of API adhesives were tested with different cross-linkers and varying loadings (5–20%). Also the effect of polyvinyl alcohol (PVOH) content of aqueous vinyl latex on the performance of API was investigated. It was shown that the potlife and curing time of API were obviously influenced by the types of cross-linker and its loading. Correct loadings of p-MDI as crosslinker can remarkably improve the adhesive performance of aqueous polymer emulsion at ambient temperature. Excess cross-linker cannot maintain such an effect of strengthening and may decrease considerably the bond properties of API. The warm- and boiling-water resistance of API improved markedly with increasing cross-linker loading, where emulsifiable isocyanate gave better cross-linking performance, and p-MDI mixed with organic solvent was the secondbest. With the increase of PVOH content, the curing time of API increased, but no statistically apparent differences in the potlife of API were found. The bonding performance of API was improved as PVOH content increases, but excess PVOH also weakenes the warm- and boiling-water resistance of the joint.     

Influence of the nanofiber dimensions on the properties of nanocellulose/poly(vinyl alcohol) aerogels

The investigation of aerogels made from cellulose nanofibers and poly(vinyl alcohol) (PVOH) as a polymeric binder is reported. Aerogels based on different nanocellulose types were studied to investigate the influence of the nanocellulose dimensions and their rigidity on the morphology and mechanical properties of the resulting aerogels. Thus, cellulose nanocrystals (CNCs) with low (10), medium (25), and high (80) aspect ratios, isolated from cotton, banana plants, and tunicates, respectively, microfibrillated cellulose (MFC) and microcrystalline cellulose (MCC) were dispersed in aqueous PVOH solutions and aerogels were prepared by freeze‐drying. In addition to the cellulose type, the PVOH‐ and the CNC‐concentration as well as the freeze‐drying conditions were varied, and the materials were optionally cross‐linked by an annealing step or the use of a chemical cross‐linker. The data reveal that at low PVOH content, rigid, high‐aspect ratio CNCs isolated from tunicates afford aerogels that show the least amount of shrinking upon freeze‐drying and display the best mechanical properties. However, with increasing concentration of PVOH or upon introduction of a chemical cross‐linker the differences between materials made from different nanocellulose types decrease. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41740.     

Compatibility of nylon 6 with poly(vinyl alcohol), hydroxylated poly(vinyl acetate) and poly(vinyl acetate)

Summary The compatibility of nylon 6 with poly(vinyl acetate)(PVAc) and poly(vinyl alcohol)(PVA) was investigated in terms of the melting-temperature depression. In order to vary the compatibility systematically, a hydroxylated poly(vinyl actate)(m-PVAc) was prepared by hydrolyzing PVAc with KOH in CH₃OH. It was found that the compatibility with nylon 6 is better in the systematic order PVA> m-PVAc> PVAc.     

Ternary nanocomposites: Curing,morphology, and mechanical properties of epoxy/thermoplastic/organoclay systems

The influence of two organically modified montmorillonites on the curing, morphology and mechanical properties of epoxy/poly(vinyl acetate)/organoclay ternary nanocomposites was studied. The organoclays and poly(vinyl acetate) (PVAc) provoked contrary effects on the epoxy curing reaction. Ternary nanocomposites developed different morphologies depending on the PVAc content, that were similar to those observed in the epoxy/PVAc binary blends. The organoclays were only located in the epoxy phase independently of the morphology. All nanocomposites showed intercalated structures with similar clay interlayer distances. Both PVAc and organoclays lowered the T_g of the epoxy phase, the presence of clays did not influence the T_g of the PVAc phase. The addition of the organoclays to the epoxy improved stiffness but lowered ductility while the adition of PVAc improved toughness although reduced stiffness of epoxy thermoset. Ternary nanocomposites exhibited optimal properties that combine the favourable effects of the clay and the thermoplastic. POLYM. COMPOS., 37:2184–2195, 2016. © 2015 Society of Plastics Engineers     

Inherently fluorescent polyaniline nanoparticles in a dynamic landscape

In this paper we report for the first time on the emissive behavior of two polyaniline (PANI) nanoparticle systems produced via oxidative chemical polymerization in the presence of either poly(vinyl alcohol) (PVA) or chitosan as polymeric stabilizers in water. The emission from PANI nanoparticles is irreversibly quenched by an increase of pH of the suspending medium from acid to neutral (chitosan-PANI) or alkaline (PVA-PANI). Conversely, PANI nanorods synthesized in the same conditions of the above, but in presence of poly(N-vinyl pyrrolidone), is not emissive at any pH. The role of the polymeric surfactant as a soft template is key in controlling the morphology and the properties of the obtained PANI dispersions. FTIR, UV-Vis absorption and photoluminescence excitation (PLE) spectra studies suggest that the emissive properties are related to the establishment of strong, non-covalent interactions between nanoscalar PANI particles and the polymeric surfactant at the pH of synthesis. Morphology examination of the three systems, by both dynamic light scattering (DLS) and Transmission Electron Microscopy (TEM), reveal that photoluminescence is associated to the presence of a genuinely 3D nanoscalar morphology, together with an ordered disposition of PANI chains into aligned crystal planes. Concomitant to the irreversible quenching of the emission signal with increasing pH, there is an evolution of the morphology leading to particle coalescence, coarsening and ultimately phase-separation, with consequent modification of PANI-polymeric surfactant interactions, PANI chains supra-molecular organization and optical properties of the PANI nanoparticles dispersion.     

Synthesis of poly(vinyl acetate) containing diblock copolymer by DPE method

Diblock copolymer poly(methyl methacrylate)‐b‐poly(vinyl acetate) (PMMA‐b‐PVAc) was prepared by 1,1‐diphenylethene (DPE) method. First, free‐radical polymerization of methyl methacrylate was carried out with AIBN as initiator in the presence of DPE, giving a DPE containing PMMA precursor with controlled molecular weight. Second, vinyl acetate was polymerized in the presence of the PMMA precursor and AIBN, and PMMA‐b‐PVAc diblock copolymer with controlled molecular weight was obtained. The formation of PMMA‐b‐PVAc was confirmed by ¹H NMR spectrum. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) were used to detect the self‐assembly behavior of the diblock polymer in methanol. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermodynamic studies related to emulsion polymerization

Liquid–liquid and vapor–liquid phase equilibria for the binary, ternary, and quaternary systems of vinyl acetate, surfactant, water, and poly(vinyl acetate) (PVAc) were obtained using liquid–liquid equilibria, inverse gas chromatography, and the headspace methods. The Flory–Huggins interaction parameters for the different species in the emulsion polymerization of PVAc latices are reported. These parameters could not be used to predict the phase equilibria because of their strong dependence on concentration. The UNIFAC‐vdW‐FV model was applied to predict the vapor–liquid equilibria in the binary and ternary systems containing vinyl acetate, 4‐nonylphenol polyethoxilate surfactant, and PVAc. The predicted results compare favorably with the experimental data for all systems. Diffusion coefficients were also measured for the solvents in the PVAc. Analysis confirmed that the diffusion in the latex particles was so fast compared to the reaction that the assumption of uniform monomer composition through the particles was valid. On the other hand, the results indicate that the complex thermodynamic interactions will lead to changes with time in the monomer concentration in the reacting polymer phase. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Investigation of Adhesion Performance of Aqueous Polymer Latex Modified by Polymeric Methylene Diisocyanate

Aqueous polymer isocyanate (API), which has good adhesive properties at ambient temperature and excellent resistance to warm/boiling water, and is friendly to the environment, is widely used in the timber-processing industry. To prepare high performance API, vinyl acetate homopolymer and copolymer emulsion were respectively cross-linked by three types of polymeric methylene diisocyanate (p-MDI). The potlife, curing time, bonding strength, and water resistance of API adhesives were tested with different cross-linkers and varying loadings (5-20%). Also the effect of polyvinyl alcohol (PVOH) content of aqueous vinyl latex on the performance of API was investigated. It was shown that the potlife and curing time of API were obviously influenced by the types of cross-linker and its loading. Correct loadings of p-MDI as crosslinker can remarkably improve the adhesive performance of aqueous polymer emulsion at ambient temperature. Excess cross-linker cannot maintain such an effect of strengthening and may decrease considerably the bond properties of API. The warm- and boiling-water resistance of API improved markedly with increasing cross-linker loading, where emulsifiable isocyanate gave better cross-linking performance, and p-MDI mixed with organic solvent was the secondbest. With the increase of PVOH content, the curing time of API increased, but no statistically apparent differences in the potlife of API were found. The bonding performance of API was improved as PVOH content increases, but excess PVOH also weakenes the warm- and boiling-water resistance of the joint.     

Measurement and simple equation models of the specific heats of neat and glycerol‐plasticized poly(vinyl alcohol)

The specific heats (C_sp) of neat and glycerol‐plasticized poly(vinyl alcohol) (PVOH) were studied by differential scanning calorimetry at 330–530 K. Glycerol‐plasticized poly(vinyl alcohol) was prepared by a melt‐blending method. The outcomes were modeled into mathematical functions. Incorporation of glycerol increased the specific heat of PVOH. Glycerol provided internal lubrication to the PVOH system, giving a smoother and lower‐amplitude melting curve. As a result, glycerol‐plasticized PVOH had a lower melting‐temperature range than neat PVOH. However, higher energy was required to increase the temperature of glycerol‐plasticized PVOH. The modeling functions showed a best fits regression range of 0.967–0.999. Neat PVOH and glycerol‐plasticized PVOH required 1166.05 J/g and 2113.09 J/g, respectively, to increase the temperature from 330 to 530 K. J. VINYL ADDIT. TECHNOL., 18:198–203, 2012. © 2012 Society of Plastics Engineers     

聚乙烯醇/微纤化纤维素复合微发泡材料的制备

通过溶液浇铸法制备了聚乙烯醇(PVOH)/微纤化纤维素(MFC)复合薄膜材料,以超临界二氧化碳(scCO₂)为物理发泡剂,采用间歇式降压法制备了一系列PVOH/MFC复合微发泡材料,主要讨论了在没有水分的影响下,不同发泡温度和时间以及MFC含量对PVOH/MFC复合微发泡材料的泡孔形貌、泡孔尺寸和泡孔密度的影响;同时,也对MFC的分散性和PVOH/MFC复合材料的流变性能和热性能对发泡行为的影响进行了研究。实验结果表明,均匀分散在PVOH基体中的MFC作为异相成核剂提高了气孔成核能力,且随着MFC含量的增加,泡孔尺寸降低,泡孔密度增大;并研究了发泡温度对PVOH/MFC复合材料的发泡形貌的影响,获得最优发泡温度。     

Study on preparation of monodispersed poly(styrene‐co‐N‐dimethylaminoethyl methacrylate) composite microspheres by SPG (Shirasu Porous Glass) emulsification technique

Monodispersed poly(styrene‐co‐N‐dimethylaminoethyl methacrylate) [P(St‐DMAEMA)] composite microspheres were prepared by employing a Shirasu Porous Glass (SPG) emulsification technique. A mixture of monomer, hexadecane (HD), and initiator N,N′‐azobis(2,4‐dimethylvaleronitrile) (ADVN) was used as a dispersed phase and an aqueous phase containing stabilizer [poly(vinyl pyrrolidone) (PVP) or poly(vinyl alcohol) (PVA)], sodium lauryl sulfate (SLS), and water‐soluble inhibitor [hydroquinone (HQ), diaminophenylene (DAP), or sodium nitrite (NaNO₂)], was used as a continuous phase. The dispersed phase was permeated through the uniform pores of SPG membrane into the continuous phase by a gas pressure to form the uniform droplets. Then, the droplets were polymerized at 70°C. The effects of inhibitor, stabilizer, ADVN, and DMAEMA on the secondary nucleation, DMAEMA fraction in the polymer, conversion, and morphologies of the particles were investigated. It was found that the secondary nucleation was prevented effectively in the presence of HQ or DAP when PVP was used as the stabilizer. The secondary particle was observed when ADVN amount was raised to 0.3 g (/18 g monomer); however, no secondary nucleation occurred even by increasing DMAEMA fraction to 10 wt %. This result implied that the diffusion of ADVN into the aqueous phase was a main factor responsible to the secondary nucleation more than that of DMAEMA. The hollow particles were obtained when NaNO₂ was used, while one‐hole particles formed in the other cases. By adding crosslinking agent, the hole disappeared and the monomer conversion was improved. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2408–2424, 2001