Proton exchange membranes prepared by simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films. I. Effect of grafting conditions

The simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films was studied at room temperature. The effects of grafting conditions (type of solvent, irradiation dose, dose rate, and monomer concentration) were investigated. The degree of grafting was found to be dependent on the investigated grafting conditions. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be of 0.5 and 1.3 orders, respectively. The results suggest that grafting proceeds by the so‐called front mechanism in which the grafting front starts at the surface of the film and moves internally toward the middle of the film by successive diffusion of styrene through the grafted layers. Some selected properties of the grafted films were evaluated in correlation with the degree of grafting. We found that the grafted FEP films possess good mechanical stability, which encourages their use for the preparation of proton exchange membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 220–227, 2000     

Radiation‐induced grafting of styrene onto poly(tetrafluoroethylene) (PTFE) films. I. Effect of grafting conditions and properties of the grafted films

Radiation‐induced grafting of styrene onto poly(tetrafluoroethylene) (PTFE) films was studied by a simultaneous irradiation technique. Grafting was carried out using γ‐radiation from a ⁶⁰Co source at dose rates of 1.32–15.0 kGy h⁻¹ at room temperature. The effects of type of diluent, dose rate, irradiation dose, and the initial monomer concentration in the grafting solution on the degree of grafting were investigated. The degree of grafting was found to be strongly dependent upon the grafting conditions. The dependence of the initial rate of grafting on the dose rate and the initial monomer concentration in the grafting solution was found to be in the order of 0.6 and 1.7, respectively. The chemical structure and the crystallinity of the grafted PTFE films were studied by means of Fourier‐transform infrared, (FTIR), electron spectroscopy for chemical analysis (ESCA) and X‐ray diffractometry (XRD). © 2000 Society of Chemical Industry     

Preparation of crosslinked polystyrene-grafted PFA films by a simultaneous irradiation method

A series of polystyrene (PS)/divinylbenzene (DVB)-grafted poly(tetrafluoroethylene-co-perfluorovinyl vinyl ether) (PFA) films with various DVB contents were prepared by a simultaneous radiation grafting method. The degree of grafting was found to be strongly dependent on the grafting conditions, such as the monomer concentration, irradiation dose, dose rate, and crosslinker concentration. The results show that the highest degree of grafting was achieved at a 10% DVB content at the same irradiation conditions. The prepared PFA-g-PS/DVB films were characterized using FTIR, TGA, and a mechanical strength test.     

Effect of solvents on radiation‐induced grafting of styrene onto fluorinated polymer films

The effect of solvents on radiation‐induced grafting of styrene onto commercial fluorinated polymer films such as poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) and poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA) was investigated by a simultaneous irradiation technique. Three solvents, ie methanol, benzene and dichloromethane, were used to dilute styrene under various irradiation doses, dose rates and monomer concentrations. The effect of addition of mineral and organic acids on the degree of grafting in the presence of the three solvents was also studied. The degree of grafting was found to be strongly dependent upon the type of solvent and composition of the monomer/solvent mixture. Dilution of styrene with dichloromethane in various grafting conditions was found to enhance dramatically the degree of grafting compared with other solvents, and the maximum degree of grafting was achieved at a monomer/solvent mixture having a composition of 60:40 (v/v). The formation of polystyrene grafts in the three fluorinated films was verified using FTIR spectrometry. © 2001 Society of Chemical Industry     

Electron‐beam‐radiation‐induced grafting of acrylonitrile onto polypropylene fibers: Influence of the synthesis conditions

Electron‐beam‐radiation‐induced grafting of acrylonitrile onto polypropylene fibers was investigated with a pre‐irradiation method. Grafting conditions such as the solvents, additives, monomer concentration, radiation dose, and temperature were varied, and the effects on the degree of grafting were studied. The nature of the reaction medium and additives had a considerable influence on the degree of grafting. The dilution of acrylonitrile with N,N‐dimethylformamide significantly enhanced the degree of grafting in comparison with other solvents. The addition of sulfuric acid to the reaction mixture led to an increase in the degree of grafting and an acceleration of the rate of grafting. The order of dependence of the rate of grafting on the pre‐irradiation dose and monomer concentration was found to be 1.31 and 1.21, respectively, in the presence of sulfuric acid. The activation energy for grafting was calculated to be 21.9 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Cation exchange membranes by radiation-induced graft copolymerization of styrene onto PFA copolymer films. I. Preparation and characterization of the graft copolymer

PFA-g-polystyrene graft copolymers were prepared by simultaneous radiation-induced graft copolymerization of styrene onto poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA) films. The effects of grafting conditions such as monomer concentration, dose, and dose rate were investigated. Three solvents, i.e., methanol, benzene, and dichloromethane, were used as diluents in this grafting system. Of the three solvents employed, dichloromethane was found to greatly enhance the grafting process, and the degree of grafting increased with the increase of monomer concentration until it reached its highest value at a styrene concentration of 60 (vol %). The dependence of the initial rate of grafting on the monomer concentration was found to be of the order of 1.2. The degree of grafting was found to increase with the increase in irradiation dose, while it considerably decreased with the increase in dose rate. The formation of graft copolymers was confirmed by FTIR analysis. The structural investigation by X-ray diffraction (XRD) shows that the degree of crystallinity content of such graft copolymers decreases with the increase in grafting, and consequently, the mechanical properties of the graft copolymers were influenced to some extent. Both tensile strength and elongation percent decreased with the increase in the degree of grafting. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2095–2102, 1999     

Comparative study of the radiation‐induced grafting of styrene onto poly(tetrafluoroethylene‐co‐perfluoropropylvinyl ether) and polypropylene substrates. I: Kinetics and structural investigation

A comparative study has been made of the radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐perfluoropropyl vinyl ether) (PFA) and polypropylene (PP) substrates, using the simultaneous irradiation method. Effects of grafting conditions such as monomer concentrations, type of solvent, dose rate and irradiation dose on the grafting yield were investigated. Under the same grafting conditions it was found that a higher degree of grafting of styrene was obtained using a mixture of dichloromethane/methanol solvents for PFA and methanol for PP and the degree of grafting was higher in PP than in PFA at all doses. However, the micro‐Raman spectroscopy analysis of the graft revealed that, for the same degree of grafting, the penetration depth of the grafted polystyrene into the substrate was higher in PFA than in PP substrates. In both polymers the crystallinity was hardly affected by the grafting process and the degree of crystallinity decreased slightly with grafting dose. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be 0.6 and 1.4 order for PFA and 0.15 and 2.2 for PP, respectively. The degree of grafting increased with increasing radiation dose in both polymers. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield for PFA and PP was accompanied by a proportional increase in the penetration depth of the graft into the substrates. Copyright © 2003 Society of Chemical Industry     

Radiation-induced graft polymerization of acrylonitrile onto isotactic polypropylene and poly(tetrafluoroethylene–ethylene) copolymer films

Direct radiation-induced grafting of acrylonitrile (AN) onto both isotactic polypropylene (IPP) and (tetrafluoroethylene–ethylene) copolymer (ET) films has been studied. The effect of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield was investigated. Homopolymerization of acrylonitrile was reduced to a minimum using ferric chloride (FeCl₃), and the suitable optimum concentration of the inhibitor was found to be 0.1 wt%. The higher the monomer concentration, the higher the degree of grafting obtained. It was observed that the degree of grafting onto IPP was higher than onto ET, at given grafting conditions. The effect of aging on IPP was also examined. IR spectroscopy showed that IPP was susceptible to photooxidation by aging. The swelling behaviour and electrical conductivity of the graft and hydrolysed graft films were investigated. The electrical conductivity was improved by hydrolysis of polyacrylonitrile in the graft chains.     

Development of membranes by radiation grafting of acrylamide into polyethylene films: Influence of synthesis conditions

SYNOPSIS: The graft copolymerization of acrylamide monomer into polyethylene films was carried out by the preirradiation method. The influence of synthesis conditions, such as monomer concentration, preirradiation dose, reaction temperature, Mohr's salt, and pregrafting storage was investigated. The order of dependence of the rate of grafting on preirradiation dose and monomer concentration was found to be 0.87 and 1.86, respectively. An activation energy of 22.9 kJ/mol for the grafting reaction was obtained. The storage of preirradiated polyethylene film at −4°C prior to the reaction showed a decrease in the degree of grafting up to 10 days, beyond which the degree of grafting remained constant. The addition of FeSO₄ in the grafting medium not only inhibits the homopolymerization of the monomer but also decreases the degree of grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1331–1337, 2000     

Radiation-induced grafting of N,N′-dimethylaminoethylmethacrylate onto chitosan films

Chitosan films were grafted with N,N ′-dimethylaminoethylmethacrylate using the ⁶⁰Co gamma irradiation method. The effect of solvent composition, monomer concentration, dose rate, and total dose on grafting was studied. The solvent composition has a marked effect on the degree of grafting. Maximum yield was obtained in the water-methanol (1 : 1) system. The percent grafting increased with monomer concentration and was found to be higher at a lower dose rate for a constant total dose of 0.216 Mrad. The tensile strength, crystallinity, and degree of swelling of grafted films decreased on increasing graft level. However, the graft copolymers showed improved thermal stability. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 869–877, 1997     

Simultaneous radiation grafting of vinylbenzyl chloride onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films

In this study, we demonstrated that vinylbenzyl chloride (VBC), a versatile monomer with reactive a chloromethyl group could be grafted onto a poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) film without a degradation of the chloromethyl group during a simultaneous irradiation process. The effects of various irradiation conditions such as the total dose, dose rate, solvent, and VBC concentration on the degree of grafting of VBC onto a FEP film were also investigated. The prepared PVBC‐grafted films were characterized using FTIR, TGA, and SEM EDX. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The study on radiation grafting of acrylic acid onto fluorine-containing polymers. IV. Properties of membrane obtained by preirradiation grafting onto poly(tetrafluoroethylene–hexafluoropropylene)

Some properties of the membranes obtained by preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene–hexafluoropropylene) (FEP) film have been investigated. Swelling behavior, dimensional change by grafting, electric conductivity, and mechanical properties of the grafted films were found to depend largely on the degree of grafting and to increase as the grafting proceeds. These properties were also found to be independent of the preparation conditions such as irradiation dose, grafting temperature, film thickness, and monomer concentration lower than 60 wt %. The electric conductivity of the membranes prepared at lower monomer concentration (lower than 60 wt %) is higher than that prepared at 80 wt % acrylic acid concentration. X-ray microscopy of the grafted film revealed that the grafting proceeds from both surfaces of the film to the direction of center to give finally homogeneous grafting through the whole bulk of film. At lower monomer concentration the homogeneous grafting was achieved at a degree of grafting around 18%, while at 80 wt % acrylic acid it was achieved at a degree of grafting higher than 70%. The homogeneously grafted membranes show good electrochemical and mechanical properties which make them acceptable for practical uses as cation-exchange membranes.     

Influence of the radiation grafting conditions on the cross‐sectional distribution of poly(vinylbenzyl chloride) grafted polymer onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films

Poly(vinylbenzyl chloride) (PVBC)‐grafted poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films were prepared as precursors for ion‐exchange membranes with a radiation grafting technique. A scanning electron microscopy–energy dispersive X‐ray spectroscopy (SEM‐EDX) instrument was used to investigate the effects of the radiation grafting conditions on the distribution profiles of the grafts in the FEP‐g‐PVBC films because the properties of the ion‐exchange membranes were largely affected not only by the degree of grafting (DOG) but also by the distribution of the graft chain. These results indicate that the distribution profile of the grafts largely depended on the grafting parameters, such as the solvent, monomer concentration, film thickness, and irradiation dose. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on antithrombosis dialytic membrane prepared by preirradiation grafting

A new antithrombosis dialytic membrane with a hydrophilic–hydrophobic microphase structure was prepared by preirradiation grafting of β‐hydroxyethyl methacrylate (HEMA) and styrene (St) onto ethylene–vinyl acetate (EVA). The influence of some effects, such as preirradiation dose, dose rate, grafting reaction temperature, reaction time, and monomer component, on the degree of grafting was determined, and the properties of the grafted films were investigated. Compared with the conventional EVA‐grafted hydrophilic monomer, the EVA films grafted with HEMA and St have superior antithrombogenicity; the antithrombogenicity and permeability of EVA‐g‐(HEMA‐co‐St) were 30 and 20 times higher than those of the ungrafted films, respectively, when the volume ratio (HEMA versus St) was about 7:3. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1321–1327, 2000     

Effect of mineral and organic acids on radiation grafting of styrene onto polyethylene

A study has been made on the effect of mineral and organic acids on the radiation-induced graft polymerization of styrene onto low-density polyethylene films. Effects of different solvents and dose rate of irradiation on the grafting yield were also investigated. The influence of irradiation time and monomer concentration in the presence and absence of acid on the initial rate and grafting yield was studied. The dependence of the grafting rate on monomer concentration was found to be of the order 1.34 (in absence of acid), 0.61 (in presence of HCl), and 1.25 (in presence of oxalic acid). Such acid enhancement of the radiation grafting process is of practical importance from an economical point of view.     

Kinetics study of radiation‐grafting of acrylic acid,acrylonitrile, and their mixture onto wool fabric

The effect of monomer concentration, exposure time, irradiation temperature, and weaving direction on the kinetics of grafting acrylic acid (AA), acrylonitrile (AN), and their mixture onto wool fabric has been studied at the dose rate of 1.38 Gy/s. The degree of grafting is found to depend on the methanol‐to‐water solvent ratio and fabric‐to‐liquor ratio. The grafting rate and rate constant are dependent on irradiation temperature, type of grafted monomer, and weaving direction. The grafting rates increase with the increase in irradiation temperature (276–308 K). The calculated activation energy is nearly the same (16.4–17.2 kJ mol^?1) and the preexponential rate constant is dependent on the type of grafted monomer. The grafting of AA, AN, and their mixture are confirmed from the dyeing affinity of grafted fabrics towards Sandocryl Blue (SB), a basic dye. The formation of wool grafts and structural changes resulting from grafting were verified by using FTIR spectrometry and X‐ray diffraction analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4328–4340, 2006     

Radiation grafting of acrylic acid/N‐vinyl pyrrolidone binary mixture onto poly(ethylene terephthalate) fabric and growth of human mesenchymal stem cell

Radiation grafting of acrylic acid (AA)/N‐vinyl pyrrolidone (NVP) binary mixture onto poly(ethylene terephthalate) (PET) knittings was investigated by preirradiation technique. The influence of the grafting conditions, such as monomer composition, reaction temperature, and the effect of storage time with temperature after irradiation on the degree of grafting was determined. ATR‐FTIR spectroscopy analysis of the grafted knittings confirmed the existence of amide group of NVP in the knittings. The concentration of peroxides and effect of storage time on peroxide concentration were also determined by 2,2‐Diphenyl‐1‐picrylhydrazyl at different temperatures. There was an increase in surface roughness of grafted PET in comparison to virgin PET as determined by atomic force microscopy and scanning electron microscopy. The grafted knittings were subsequently immobilized with collagen Type I which was further apt for the study of growth and morphology of human mesenchymal stem cell (hMSC). The immobilization of collagen on PET knittings has provided an excellent surface for the growth of hMSCs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Radiation-induced grafting of functional acrylic monomers onto polyethylene and polypropylene films using acryloyl chloride

Summary Radiation-induced graft polymerization of acryloyl chloride onto films of polyolefins (polyethylene and polypropylene) using gamma radiation was investigated in order to establish a convenient method to obtain polymer films grafted with polyacrylic esters. Grafting was carried out by three different methods; (i) direct irradiation of film in monomer solution (ii) vapor phase irradiation method, and (iii) pre-irradiation in air. The effects of monomer concentration, radiation dose and methods of grafting, on the formation of grafted polyolefins are reported in this paper. Received: 5 April 2000/Revised version: 17 November 2000/Accepted: 20 November 2000     

Preparation of hydrophilic membranes by grafting acrylic acid onto pre-irradiated teflon-FEP films

Grafting of acrylic acid onto pre-irradiated poly(tetrafluoroethylene-hexafluoropropylene) (Teflon-FEP) films was investigated, and the reaction parameters dose, dose rate, monomer concentration and grafting temperature were examined. The results show that the degree of grafting depends on the dose (5-60 kGy), the weight of grafted specimen increased up to 37%. The degree of grafting was found to be independent of the dose rate. The overall activation energies were calculated to be 28.8 and 81.6 kJ mol^-1 for treatments at above and below 50°C, respectively. The swelling of grafted films was measured in water, aqueous potassium hydroxide and methanol. The degree of swelling was found to increase with the length of grafted chains.     

Radiation‐induced graft copolymerization of α‐methyl styrene and butyl acrylate mixture into polyetheretherketone films

Radiation‐induced graft copolymerization of α‐methyl styrene (AMS), butyl acrylate (BA) monomers, and their mixture was investigated on poly(etheretherketone) films. The graft polymerization was carried out using ethyl methyl ketone as the medium for the copolymerization and the maximum degree of grafting of 27% was achieved. It was observed that the grafting is significantly influenced by the reaction conditions, such as reaction time, preirrradiation dose, monomer concentration, monomer ratio, and the reaction temperature. The degree of grafting increases as the monomer concentration increases up to 30%, beyond which a decrease in the grafting was observed. The degree of grafting showed a maximum at 40% BA content in the monomer mixture. The temperature dependence of the grafting process shows decreasing grafting with the increase in the reaction temperature. The presence of AMS and BA grafts in the film was confirmed by FTIR spectra. The relative change in the PBA/PAMS fraction with respect to the reaction temperature has been found in this study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013