Immobilization of bacteriocin nisin into a poly(vinyl alcohol) polymer matrix crosslinked with nontoxic dicarboxylic acid

This work is focused on novel methodology of poly(vinyl alcohol) crosslinking by non‐toxic dicarboxylic acid, glutaric acid. The cross‐linked system was used as a matrix for immobilization of bacteriocin nisin. Effect of the crosslinking degree on physico‐chemical, morphology, mechanical, and thermal properties of poly(vinyl alcohol) films were investigated by using swelling test, Fourier transform infrared spectroscopy, scanning electron microscopy, stress–strain analysis, differential scanning calorimetry, and thermogravimetry. Release profile of the nisin from the cross‐linked poly(vinyl alcohol) was studied by high performance liquid chromatography. Antibacterial activity of the prepared systems was tested by agar diffusion test and dilution and spread plate technique. Results showed suitability of glutaric acid as effective crosslinking agent of poly(vinyl alcohol) that acts synergistically with bacteriocin nisin against the tested Gram‐positive and Gram‐negative bacterial strains. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43674.     

Thermal and rheological properties of poly(vinyl alcohol) gel with boric acid as a crosslinking agent

The gel of poly(vinyl alcohol) polymer with boric acid, added as a crosslinking agent, was made with a mixture of dimethyl sulfoxide and water. The thermal and dynamic modulus properties of poly(vinyl alcohol) gel were measured by a differential scanning calorimeter and a dynamic mechanical thermoanalyst. Results show that an increase of poly(vinyl alcohol) polymer or boric acid content to the gel makes an increasing of gel to sol transition temperature, endothermic enthalpy, and dynamic modulus. The maximum value of gel to sol transition temperature, endothermic enthalpy, and dynamic modulus happened at the volume ratio of 6 : 4 of dimethyl sulfoxide to water, which is independent on the poly(vinyl alcohol) and the boric acid content. According to the modified Eldridge–Ferry theory for thermoreversible gel, it is found that both the gel to sol transition temperature and the endothermic enthalpy versus poly(vinyl alcohol) content could be superimposed with respect to the boric acid content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2219–2226, 1999     

An NMR study of the dissociation of N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate) and its crosslinking of polymers containing labile hydrogens. II

Nuclear magnetic resonance spectroscopy has been used to study the dissociation and reaction of N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate), as a crosslinking agent for polymers containing labile hydrogens. The crosslinking of poly(acrylic acid), polyacrylamide, and poly(vinyl alcohol) was found to result upon heating each to 150°C for 10 min with this component at 2–10 wt %.     

New Types of Ecologically Safe Flame Retardant Polymer Systems

Abstract

New types of ecologically safe flame retardant composition based on poly(vinyl)alcohol and poly(vinyl)alcohol oxidized by KMnO₄ (polymer-organic char formers) were proposed for nylon 6,6. These systems can promote the formation of char by intermolecular crosslinking (“synergetic carbonization”). The Cone Calorimeter tests indicated the improvement of fire retardant properties for the compositions of nylon 6,6 with poly(vinyl)alcohol and poly(vinyl)alcohol oxidized by KMnO₄ in comparison with pure nylon 6,6.     

Exploitation of acetalization process of poly(vinyl alcohol) for the formation of crosslinked poly(vinyl formal) foams

In the present work, poly(vinyl formal) (PVF) foams were prepared using water as the pore-forming agent and formaldehyde as the crosslinking agent. The acetalization process of poly(vinyl alcohol) was exploited in depth in order to obtain a precise guidance on the preparation of PVF foams with adjustable properties. With the increasing of formaldehyde, the crosslinking degree was gradually increased and the prepared PVF foams changed to be amorphous. Morphology observation showed that the porous structure of PVF foams was successfully created using water as the blowing agent and it was strongly affected by the crosslinking agent and polymer concentration, leading to an easily tuned pore size from hundreds of microns to few microns. The prepared foams were proved to have small apparent density below 0.27 g/cm⁻³ and excellent mechanical strength, with the largest specific compressive strength of 11.54 MPa·cm³·g⁻¹. Based on the results, it is believed that this study can provide a scientific basis for the design and optimization of PVF foams with controllable structure and properties.     

Coating of cotton yarn with poly(vinyl alcohol) and poly(N‐vinyl‐2‐pyrrolidone) crosslinked via ultraviolet radiation

The coating of cotton fiber is used in the textile industry to increase the mechanical resistance of the yarn and their resistance to vibration, friction, impact, and elongation, which are some of the forces to which the yarn is subjected during the weaving process. The main objective of this study was to investigate the use of synthetic hydrophilic polymers, poly(vinyl alcohol) (PVA), and poly(N‐vinyl‐2‐pyrrolidone) (PVP) to coat 100% cotton textile fiber, with the aim of giving the fiber temporary mechanical resistance. For the fixation of the polymer on the fiber, UV‐C radiation was used as the crosslinking process. The influence of the crosslinking process was determined through tensile testing of the coated fibers. The results indicated that UV‐C radiation increased the mechanical resistance of the yarn coated with PVP by up to 44% and the yarn coated with PVA by up to 67% compared with the pure cotton yarn, that is, without polymeric coating and crosslinking. This study is of great relevance, and it is important to consider that UV‐C radiation dispenses with the use of chemical substances and prevents the generation of toxic waste at the end of the process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Pervaporation separation of aqueous organic mixtures through sulfated zirconia‐poly(vinyl alcohol) membrane

Sulfated zirconia‐poly(vinyl alcohol) membranes were prepared, and pervaporation performances for aqueous organic mixtures were investigated. These hydrophilic membranes were formed by crosslinking poly(vinyl alcohol) (PVA) with the solid acid of sulfated zirconia by an acid‐catalyzed reaction. The pervaporation performances were measured as a function of the content ratio of sulfated zirconia to PVA, which affected the degree of swelling for water and the crosslinking density of the membrane. The membrane selectivity in pervaporation of aqueous organic mixtures increased in order of acetic acid < ethanol < 2‐ethoxyethanol without sacrificing the permeation rate, depending on their feed compositions. The effects of feed temperature and concentration on the membrane performance were also significant. It was found that sulfated zirconia in the membrane preparation played an important role as a filler material as well as an effective crosslinking or insolubilization agent in improving and controlling the membrane performance, i.e., permeation rate and selectivity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1450–1455, 2001     

Separation of MTBE-Methanol Mixtures by Pervaporation

Abstract

Membranes made of a polymer blend of poly(acrylic acid) and poly(vinyl alcohol) were evaluated for the separation of methanol from methyl tert-butyl ether (MTBE) by pervaporation. The influence of the blend composition and the feed composition on the pervaporation performance were investigated. Methanol permeates preferentially through all tested blend membranes, and the selectivity increases with increasing poly(vinyl alcohol) content in the blends. However, a flux decrease is observed with increasing poly(vinyl alcohol) content. With increasing feed temperature the flux increases, and the selectivity remains constant. In addition, the influence of crosslinking on the permselectivity was investigated. The pervaporation flux decreases with increasing crosslinking density, but the selectivity is enhanced. This is due to a more rapid decrease in the component flux of MTBE compared to that of methanol.     

丙烯酸-丙烯酰胺共聚物/聚乙烯醇高吸水纤维研制

采用潜交联剂丙烯酸羟丙酯与丙烯酸、丙烯酰胺等单体共聚后与聚乙烯醇共混配制成纺丝原液, 湿法纺丝成形后经后交联处理赋予纤维三维网状结构,制得具有较好吸水性能的丙烯酸-丙烯酰胺共聚物/ 聚乙烯醇共混纤维,研究了后交联处理条件对纤维结构及性能的影响。结果表明,随着交联温度的升高,交联时间的延长,纤维的饱和吸水率降低。纤维经130℃交联处理12 min后,其饱和吸水率可达405 g/g。     

Facile fabrication of poly(vinyl alcohol) gels and derivative aerogels

A facile preparation of poly(vinyl alcohol) (PVOH) hydrogels and their derivative PVOH/montmorillonite clay aerogels is reported, using water as solvent and divinylsulfone as crosslinking agent, making use of an environmentally friendly freeze drying process. The materials exhibit significantly increased mechanical properties after crosslinking. The compressive modulus of an aerogel prepared from an aqueous suspension containing 2 wt% PVOH/8 wt% clay increased 29-fold upon crosslinking, for example. Crosslinking of the polymer/clay aerogels decreased the onset decomposition temperature as measured by thermogravimetric analysis, and generated a more continuous structure at higher clay contents. Such polymer/clay aerogels are promising materials for low flammability applications.     

Synthesis of copolymeric acrylamide/potassium acrylate hydrogels blended with poly(vinyl alcohol): Effect of crosslinking and the amount of poly(vinyl alcohol) on swelling behavior

A novel series of copolymeric acrylamide/potassium acrylate superabsorbents, blended with poly(vinyl alcohol), have been synthesized by using N, N′‐methylenebisacrylamide as a crosslinker and potassium persulphate (K₂S₂O₈) as an initiator. Swelling behavior of these hydrogels in water was investigated; and on the basis of swelling properties, the diffusional behavior of water into these hydrogel systems was analyzed. It was observed that with the increase of amount of poly(vinyl alcohol) or crosslinking, the swelling of the hydrogels decreased. The hydrogel synthesized by addition of 5% poly(vinyl alcohol) and 0.25% crosslinking showed maximum swelling of 54445%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1927–1931, 2005     

Thickening of poly(vinyl alcohol) by borate

Viscosity and pH of aqueous borate–poly(vinyl alcohol) mixtures were determined under different conditions toward a clarification of the thickening mechanism. Boric acid has little effect on dilute poly(vinyl alcohol) (PVOH), but sodium borate causes sharp viscosity increases which are temperature sensitive and apparently stem from labile exothermic crosslinking of PVOH by borate ions. The pH data indicate that the complexing of borate with simple polyols such as mannitol and glycerol is a different process from borate crosslinking of PVOH. The PVOH thickening and gelling effect probably arises from the replacement of labile waters of hydration on borate ion by OH groups of PVOH rather than from borospirane formation.     

Radiation-convertible polymers from norbornenyl derivatives. Crosslinking with ionizing radiation

Vinyl polymers with pendant norbornenyl (bicyclo[2.2.1]heptenyl) groups crosslink rapidly on exposure to ionizing radiation. Analysis (according to Charlesby-Pinner theory) of extraction data from an ethylene–vinyl acetate copolymer and the corresponding ethylene–vinyl norbornenecarboxylate copolymer shows that the unsaturated polymer crosslinks by a chain reaction. At low doses, the kinetic chain length is about 4. Pendant norbornenyl groups accelerate crosslinking of a vinyl alcohol–vinyl acetate–vinyl chloride copolymer and convert poly(vinyl alcohols) and cellulose acetate from degrading to crosslinking polymers. A novel application of the Charlesby-Pinner plot strongly suggests linear dependence of the extent of crosslinking on the norbornenyl group concentration in a series of modified poly(vinyl alcohols). The greater effectiveness of pendant norbornenyl groups, compared to cyclohexenyl groups, demonstrates the importance of the reactivity of the double bond.     

氯乙烯悬浮法聚合分散体系综述

简单介绍了国内外氯乙烯悬浮聚合分散体系应用情况及常用的聚乙烯醇及纤维素类分散剂的品种和规格。具体分析了影响聚乙烯醇及羟丙基甲基纤维素分散剂分散能力及保胶能力的因素。指出了PVC生产中应用分散剂时的一般规律,并探讨了不同搅拌强度、转化率和充N2压力下分散剂的不同应用对聚合体系的作用情况。     

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

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

Effect of Operating Conditions on PV Performance of PVA Membranes: Experimental and Neural Network Modeling

Poly (vinyl alcohol) membranes were prepared by in-situ crosslinking of poly(vinyl alcohol) with glutaraldehyde as crosslinking agent and hydrochloric acid as catalyst and used for dehydration of IPA mixtures. Effects of feed composition, operating temperature, vacuum pressure, and Reynolds number on the permeation performance of the membranes were evaluated. Eighty-nine experimental data was applied to investigate ANN modeling. A multi layered feedforward neural network was applied to model the PV membranes. Two major training algorithms and optimum number of neurons and layers were investigated. As a result, Bayesian regularization successfully predicted experimental data. Different network structures were optimized, using multi object genetic optimization algorithm. The results concluded that the network with structure composing two hidden layers performs better than the other with one hidden layer, and also there is an excellent compatibility between the experimental data and the predicted values of optimum network structure (4:3:2:2). Furthermore, the optimum network was applied to predict extrapolation data and the results showed that this network can extrapolate data as well as interpolating.     

原位交联聚乙烯醇/二氧化硅杂化功能膜的制备与性能

以正硅酸乙酯（TEOS）为前驱体,戊二醛（GA）为交联剂,利用溶胶凝胶法和原位化学交联法相结合的方法,制备了交联的聚乙烯醇/二氧化硅（PVA/SiO2）杂化功能膜。通过FTIR、SEM、溶胀和拉伸实验研究了二氧化硅和原位化学交联对杂化膜结构和性能的影响。结果表明,制备的膜是具有梯度交联结构的有机/无机杂化体系,原位化学交联对膜断面形貌影响不大。二氧化硅的引入和戊二醛原位交联都能有效地降低杂化膜的平衡溶胀度,两种因素在提高杂化膜耐水性方面具有互补作用。     

Preparation,characterization, and water‐sorption study of polyvinyl alcohol based hydrogels with grafted hydrophilic and hydrophobic segments

The interpenetrating polymer network hydrogels based on poly(vinyl alcohol) were obtained by graft copolymerization of acrylamide and styrene onto polyvinyl alcohol in the presence of N,N′‐methylene bisacrylamide as a crosslinking agent. The hydrogels were characterized by optical microscopy, scanning electron microscopy, infrared spectral analysis, differential scanning calorimeter, and thermogravimetric analysis. The hydrogels showed enormous swelling in aqueous medium and displayed swelling characteristics, which were highly dependent on the chemical composition of the hydrogels and pH of the swelling medium. The kinetics of water uptake and the mechanisms of water transport were studied as a function of composition of the hydrogel and pH of the swelling medium. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1129–1142, 2005     

Synthesis and Characterization Superabsorbent Polymers Made of Starch,Acrylic Acid,Acrylamide, Poly(Vinyl Alcohol), 2-Hydroxyethyl Methacrylate, 2-Acrylamido-2-methylpropane Sulfonic Acid

Three polymers with excellent absorption properties were synthesized by graft polymerization: soluble starch-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate), poly(vinyl alcohol)/potato starch-g-poly(acrylic acid-co-acrylamide), poly(vinyl alcohol)/potato starch-g-poly(acrylic acid-co-acrylamide-co-2-acrylamido-2-methylpropane sulfonic acid). Ammonium persulfate and potassium persulfate were used as initiators, while N,N′-methylenebisacrylamide was used as the crosslinking agent. The molecular structure of potato and soluble starch grafted by synthetic polymers was characterized by means of Fourier Transform Infrared Spectroscopy (FTIR). The morphology of the resulting materials was studied using a scanning electron microscope (SEM). Thermal stability was tested by thermogravimetric measurements. The absorption properties of the obtained biopolymers were tested in deionized water, sodium chroma solutions of various concentrations and in buffer solutions of various pH.     

The heterogeneous formalization of poly(vinyl alcohol) accompanying crosslinking reaction – I

The effect of the solvents of poly(vinyl alcohol) (PVA) species on the crosslinking reaction accompanying in the heterogeneous formalization of PVA was studied. The crosslinking reaction was prevented when PVA film was allowed to react with formaldehyde in the solution containing methanol, ethanol or propanol, whereas it occurred in the solution containing acetone. The crosslinking reaction occurred more easily in syndiotacticity-rich PVA than in atactic PVA (commercial PVA).