Radiation‐induced grafting of acrylic acid and sodium styrene sulfonate onto high‐density polyethylene membranes. II. Thermal and chemical properties

Strong acid cation‐exchange membranes were obtained by radiation‐induced grafting of acrylic acid and sodium styrene sulfonate onto high‐density polyethylene (HDPE). Thermal and chemical properties of the cation‐exchange membranes were investigated. The effectiveness of ? SO₃Na containing membranes was conformed in inducing high resistance to oxidative degradation. The char residue of the grafted HDPE is greater than that of ungrafted HDPE. It shows that the branch chains, including ? SO₃Na and ? COOH groups, give catalytic impetus to the charring. The crystallinity of the grafted membranes was decreased when increasing the grafting yield. It was assumed that the decreased crystallinity was due to collective effects of the inherent crystallinity dilution by the amorphous grafted chains and the crystal distortion of the HDPE component. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3396–3400, 2006     

Role of additive HCL in the radiation‐induced grafting copolymerization of acrylic acid and sodium styrene sulfonate to high‐density polyethylene

Acrylic acid and sodium styrene sulfonate were grafted onto high‐density polyethylene (HDPE) membrane by preirradiation, and we prepared a cation exchange membrane with strong acid and weak acid groups. The HCl was used as an additive to change the pH of grafting system, and the effect of pH on grafting yield was studied. In simultaneous radiation method, the overall grafting yield (G_t) and grafting yield of SSS onto HDPE (G_s) increased with decreasing of pH. In preirradiation method, G_t and G_s first increased with decreasing of pH, and the highest grafting yield was observed at pH = 2.80, then decreased if we further reduced the pH of the grafting system. Viscosity of grafting system was changed owing to the change of the ionization degree of polyacrylic acid in the presence of HCl, so that diffuse rate of monomers into matrix was affected. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2622–2626, 2007     

Preparation and characterization of a proton‐exchange membrane by the radiation grafting of styrene onto polytetrafluoroethylene films

Radiation‐induced simultaneous grafting of styrene onto polytetrafluoroethylene (PTFE) films and the subsequent sulfonation in the chlorosulfonic acid/dichloroethane were investigated. The effects of the main radiation grafting conditions, such as the type of solvents, irradiation dose, dose rate, the styrene concentrations, etc., on the degree of grafting (DOG) were studied. To elucidate the influence of both the grafting and sulfonation conditions on the properties of the PTFE‐g‐polystyrene‐sulfonic acid (PSSA) membranes, the sulfonation conditions, including the sulfonation temperature and the concentration of the ClSO₃H with respect to the DOG, were systematically evaluated. The grafted and sulfonated membranes were characterized by FTIR–ATR spectra, ion‐exchange capacity (IEC), water uptake, thickness measurement, etc. The as‐prepared PTFE‐g‐PSSA membranes in this work showed a good combination of a high IEC (0.85–2.75 meq g^?1), acceptable water uptake (8.86–56.9 wt %), low thickness, and volume expansion and/or contraction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1415–1428, 2006     

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     

Surface modification of polypropylene sheets by UV‐radiation grafting polymerization

1,6‐Hexanediol diacrylate (HDDA) was grafted onto polypropylene (PP) substrates in the presence of benzophenone (BP) and isopropylthioxanthone (ITX) photoinitiators, and then polyurethane acrylate formulations were coated onto the HDDA‐g‐PP substrates, using UV radiation. The amount grafted and the grafting efficiency of the polymerizations were determined gravimetrically. The effects of the photoinitiator concentration and the UV radiation intensity on the physicochemical surface properties and the grafting efficiency of the UV‐radiation grafting polymerizations were characterized in detail using contact‐angle measurements, Fourier transform infrared spectroscopy with attenuated total internal reflection, and scanning electron microscopy. The results showed that the amount grafted and the surface polarity of the HDDA‐g‐PP substrates both increased linearly with increasing BP photoinitiator concentration and UV radiation intensity, and that the addition of a small amount of ITX markedly enhanced both parameters, probably due to photosensitization. The adhesion of the UV‐cured coating onto the HDDA‐g‐PP substrates was evaluated using the crosshatch adhesion test. The results indicated that the amount of HDDA grafted onto the PP substrates should exceed about 1 mmol/cm² for satisfactory adhesion with the UV‐cured coating. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1446–1461, 2006     

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 glycidyl methacrylate onto high‐density polyethylene (HDPE) and radiation lamination of HDPE

Radiation‐induced grafting of glycidyl meth‐acrylate (GMA) onto high‐density polyethylene (HDPE) and the radiation lamination of HDPE by bulk grafting of GMA were reported. The effects of irradiation dose, monomer concentration, and atmosphere on grafting were investigated. The extent of grafting initially increased with irradiation dose and then remained almost constant. The extent of grafting was higher in 2M GMA than in 1M GMA at the same irradiation dose. The extent of grafting in nitrogen was higher than that in air. The grafted samples were characterized with FTIR spectrometry and thermogravimetric (TG) analysis. A carbonyl group was found on grafted HDPE samples, and the carbonyl index increased with the extent of grafting. TG analyses proved the existence of grafted materials on HDPE and the grafted GMA thermally decomposes at a temperature lower than that of HDPE. Strong adhesion could be obtained with radiation lamination of HDPE by bulk grafting of GMA. Benzophenone facilitates the grafting in a proper concentration range. The adhesion mechanism of the laminated samples was the entanglement of the grafted chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 772–779, 2005     

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     

Studies on grafting of acrylic acid onto polypropylene melt‐blown nonwovens induced by electron‐beam preirradiation

We report the graft copolymerization of acrylic acid onto the polypropylene (PP) melt‐blown nonwovens induced by electron beam (EB) preirradiation in this article. The occurrence of the graft copolymerization was confirmed by means of XPS, FTIR, and SEM. The effects of preirradiation dose, monomer concentration, bath ratio, reaction time, and temperature on the graft ratio were investigated. The water conservation, water absorption rate, and K⁺ exchange capacity were also determined on the grafted PP melt‐blown nonwovens, which showed that EB preirradiation‐induced grafting was an effective way to improve the hydrophicility of PP melt‐blown nonwovens. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4971–4977, 2006     

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 grafting of pentamethyl hindered amine light stabilizer 1,2,2,6,6‐pentamethyl‐4‐piperidinyl methacrylate onto polypropylene

The γ‐radiation‐induced grafting of 1,2,2,6,6‐pentamethyl‐4‐piperidinyl methacrylate (PMPM) onto polypropylene (PP) was investigated with a simultaneous irradiation technique. The effects of the solvent, dose, monomer concentration, and photoinitiator on the grafting were investigated. The grafting was easier in a benzene solution than in chloroform and acetone solutions. The grafting percentage first increased almost linearly with the irradiation dose until 20 kGy and then increased slowly or remained constant. The grafting percentage increased with the monomer concentration until 1.1 mol/L. The grafting percentage was higher when the proper amount of benzophenone was added. The grafted samples were characterized with Fourier transform infrared spectroscopy and thermogravimetric analysis. Carbonyl groups were found on grafted PP samples, and the carbonyl index increased with the grafting percentage. Thermogravimetric analyses proved the existence of grafted materials on PP, and grafted PMPM thermally decomposed at a lower temperature than PP. The radiation resistance of PP with grafted PMPM was better than that of pristine PP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2157–2164, 2005     

Grafting design: a strategy to increase the performance of radiation‐grafted membranes

The polymer design concept of short versus long side chains was successfully adapted to radiation‐grafted membranes, the fabrication of which is an easy and up‐scalable process. This concept was investigated by the generation of two model membranes based on polystyrene sulfonic acid‐grafted ethylene‐alt‐tetrafluoroethylene, prepared using a low versus high irradiation dose. It was shown to be essential to adjust the grafting parameters of both systems to obtain two membranes with similar composition in through‐plane direction. In particular, the high‐dose system showed pronounced grafting fronts. A structure–property correlation was found regarding the influence of the graft lengths on the performance characteristics of electron beam‐grafted ethylene‐alt‐tetrafluoroethylene‐based proton exchange membranes, e.g. the membrane type associated with a higher number density of short grafted chains showed higher water sorption behaviour as well as increased proton conductivity, especially in the lower relative humidity range. © 2015 Society of Chemical Industry     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

A modified model and algorithm for flow‐enhanced crystallization—Application to fiber spinning

The graft copolymerization of acrylamide (AAm) monomer onto polyethylene‐coated polypropylene (PE‐co‐PP) nonwoven fabric was carried out by the mutual irradiation method. The general peculiarities of the grafting have been studied by gravimetric, scanning electron microscope (SEM), mechanical properties, and Fourier transform infrared (FTIR) methods. The influence of absorbed dose, dose rate, as well as the monomer concentration on the degree of grafting has been determined. Metal ions uptake of Cu²⁺, Co²⁺, Ni²⁺ by the grafted fabrics was evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3240–3245, 2006     

Swelling behavior and cell viability of dehydrothermally crosslinked poly(vinyl alcohol) hydrogel grafted with N‐vinyl pyrrolidone or acrylic acid using γ‐radiation

To improve equilibrium water content, dehydrothermally crosslinked poly(vinyl alcohol) (PVA) hydrogel was grafted with N‐vinyl pyrrolidone (NVP) or acrylic acid (AA) monomer using γ‐radiation. Swelling behavior of the grafted hydrogels was studied in phosphate‐buffered saline, and cell viability was evaluated using fibroblast cells from mouse connective tissue. Equilibrium water content of AA‐ and NVP‐grafted PVA hydrogel ranged between 40–60% and 60–80%, respectively, depending on radiation dose and monomer concentration. For maximum degree of swelling, the optimum monomer concentration and radiation dose were 20% by weight and 20 kGy, respectively. Fibroblast cells seeded on NVP‐grafted hydrogel had an extended oval morphology while those seeded on AA‐grafted PVA had a rounded spherical morphology. These results support the use of NVP for grafting PVA to increase swelling and improve cell viability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2862–2868, 2004     

Synthesis and characterization of graft copolymer (guar gum–g–N‐vinyl‐2‐pyrrolidone) and investigation of metal ion sorption and swelling behavior

Graft copolymer of N‐vinyl‐2‐pyrrolidone with guar gum was synthesized and its reaction conditions were optimized for better yield using potassium peroxymonosulfate (PMS) and glycolic acid (GA) as a redox initiator. The effect of PMS, GA, hydrogen ions, guar gum, and N‐vinyl‐2‐pyrrolidone (NVP) along with reaction time and temperature were studied by determining the grafting parameters: grafting ratio, efficiency, conversion, add‐on, homopolymer, and rate of grafting. It was observed that the maximum yield occurred at with a time of 120 min at a temperature of 45°C and a guar gum concentration of 0.4 g/L concentration. The graft copolymer was characterized by infrared spectroscopy and thermal analysis. The activation energy for the grafted and ungrafted gum was calculated. It was observed that the graft copolymer was thermally more stable than the pure gum. The swelling and metal ion sorption behavior of guar gum and guar gum‐g‐N‐vinyl‐2‐pyrrolidone also were studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2480–2489, 2006     

γ‐Radiation‐Induced Graft Copolymerization of Ethyl Acrylate onto Hydroxypropyl Methylcellulose

Summary: Graft copolymerization of EA onto water‐soluble HPMC was carried out using γ‐radiation using both simultaneous and preirradiation in an aqueous medium. The effects of radiation environment, radiation dose, monomer concentration, and reaction temperature on percentage of grafting (G) and grafting efficiency (G_E) were investigated. For preirradiation, the observed values for G and G_E were higher in air than in a nitrogen atmosphere. G and G_E values are obviously higher for preirradiation; their maximum values were obtained for a radiation dose of 1.8 kGy. The grafting parameters increase for increasing monomer concentration up to 0.15 mol · L^?1, where they reach their saturation values. In the case of preirradiation, the largest grafting parameters are obtained at 65 °C. The graft copolymers obtained were characterized by FTIR spectroscopy, TEM, SEM, and XRD methods. The method of irradiation significantly affects the mechanical properties of the grafted HPMC samples. Samples prepared by simultaneous irradiation show superior mechanical properties. In addition, the equilibrium humidity adsorption behaviors of the grafted copolymers were also studied, and the humidity resistance behavior of HPMC was enhanced through the grafting copolymerization.

Transmission electron micrograph of the HPMC‐g‐PEA water dispersion.     

Graft copolymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulphonic acid onto carboxymethylcellulose (sodium salt) using bromate/thiourea redox pair

Unreported graft copolymer of 2‐acrylamido‐2‐methyl‐1‐propanesulphonic acid (AMPS) with sodium carboxymethylcellulose (Na‐CMC) was synthesized and reaction conditions were optimized using a bromate/thiourea redox pair under an inert atmosphere at 40°C. Grafting ratio, add on, and conversion increase as the concentration of thiourea and [H⁺] increases up to 3.6 × 10^?3 and 0.6 × 10^?2 mol dm^?3, respectively, while on increasing the concentration of bromate ion and Na‐CMC, grafting ratio, add on, and conversion decrease. The samples of Na‐CMC and grafted Na‐CMC with AMPS were subjected to thermogravimetric analysis, with the objective of studying the effect of grafting of AMPS on the thermal stability of graft copolymer. The graft copolymer was found to be more thermally stable than pure Na‐CMC. Comparing the IR spectra of pure with grafted Na‐CMC confirm the evidence of grafting. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 100: 26–34, 2006     

Physicochemical investigation of radiation‐grafted poly(acrylic acid)‐graft‐poly(tetrafluoroethylene–ethylene) copolymer membranes and their use in metal recovery from aqueous solution

ET‐g‐PAAc membranes were obtained by radiation grafting of acrylic acid onto poly(tetrafluoroethylene–ethylene) copolymer films using a mutual technique. The ion selectivity of the grafted membranes was determined toward K⁺, Ag⁺, Hg²⁺, Co²⁺, and Cu²⁺ in a mixed aqueous solution. The ion‐exchange capacity of the grafted membranes was measured by back titration and atomic absorption spectroscopy. The Hg²⁺ ion content of the membrane was more than that of either the K⁺ or Ag⁺ ions. The presence of metal ions in the membranes was studied by infrared and energy‐dispersive spectroscopy measurements. Scanning electron microscopy of the grafted and metal‐treated grafted membranes showed modification of the morphology of the surface due to the adsorption of K⁺ and Ag⁺ ions. No change was observed for the surface of the membrane that was treated with Hg²⁺ ions. The thermal stability of different membranes was improved more with Ag⁺ and Hg²⁺ ions than with K⁺ ions. It was found that the modified grafted membranes possessed good hydrophilicity, which may make them promising candidates for practical applications, such as for cation‐exchange membranes in the recovery of metals from an aqueous solution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2692–2698, 2002     

Effect of styrene addition on chemically induced grafting of 4‐vinylbenzyl chloride onto low‐density polyethylene for anion exchange membrane preparation

Anion exchange membranes were prepared from graft polymerization of 4‐vinylbenzyl chloride on low‐density polyethylene matrix and subsequent amination with trimethylamine solution. The graft polymerization was initiated by benzoyl peroxide instead of gamma ray radiation. The resulting membranes had insufficient anion exchange functional groups; however, this could be enhanced by adding 10% styrene to 4‐vinylbenzyl chloride in a graft polymerization reaction. Further addition of styrene resulted in a decrease of the ion exchange capacity of anion exchange membranes due to competition with 4‐vinylbenzyl chloride in graft polymerization onto polyethylene. These were evidenced by analytical titration, elemental analysis, infrared spectroscopy and ¹H NMR. © 2019 Society of Chemical Industry