Radiation‐induced GMA/DMAA graft copolymerization onto porous PE hollow‐fiber membrane

Radiation‐induced graft copolymerization is a powerful technique to prepare a grafted chain with the desired properties pending onto the trunk material. In this work, a polyethylene hollow‐fiber membrane was modified by this technique. The monomers glycidyl methacrylate (GMA) and N,N‐dimethylacrylamide (DMAA) were cografted onto macroporous polyethylene hollow fiber with a grafting degree in the order of 200%. DMAA/GMA cografted membranes were compared to GMA grafted ones for the introduction of an amino acid as a specific ligand. Grafted membranes with a copolymer composition between 0 and 2 DMAA/GMA were prepared by soaking them in solutions of different mixtures of monomers. Copolymers were characterized by FTIR and their composition was estimated by the analysis of the ratio of carbonyl signals. Copolymers with a higher proportion of DMAA showed improved hydrophilic properties and higher conversion rates of epoxy groups on phenyalanine ligands than those of the GMA grafted ones. However, copolymers with a DMAA/GMA ratio higher than 1 showed a detrimental effect on the pure water flux. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1646–1653, 2003     

Chemically induced graft copolymerization of acrylonitrile onto lignocellulosic fibers

The grafting of vinyl monomers is an important method for replacing hydrophilic hydroxyl groups present on the surface of natural fibers by hydrophobic polymer chains. It improves the compatibility of natural fibers with polymer matrixes during the fabrication of natural‐fiber‐reinforced polymer composites. This article deals with the graft copolymerization of acrylonitrile onto Agave americana fibers in air in the presence of ceric ammonium nitrate as a redox initiator. A maximum percentage grafting of 24% was obtained after the optimization of various reaction parameters, including the reaction time, temperature, and concentrations of nitric acid, initiator, and monomer. The graft copolymers obtained under the optimum conditions were then subjected to the evaluation of different physicochemical properties, including swelling behavior in different solvents, moisture absorption behavior under different humidity levels, and chemical resistance. The graft copolymers were further characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermal analysis (thermogravimetric analysis/differential thermal analysis), and X‐ray diffraction techniques. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

UV‐radiation‐induced preirradiation graft copolymerization of methacrylic acid and acrylic acid onto jute fibre

UV‐radiation‐induced graft copolymerization of methacrylic acid and acrylic acid onto jute fibre was carried out using a preirradiation method with 1‐hydroxycyclohexyl‐phenylketone as a photoinitiator. 2‐methyl‐2‐propene 1‐sulfonic acid, sodium salt was incorporated into the grafting solution in suppressing the homopolymer/gel formation and facilitating graft copolymerization. In comparison, results showed that the type of monomer significantly influence on grafting. The results of the characterisation showed that the graft weight and the type of monomer have significant influence on the mechanical and water absorption properties in the case of grafted samples. Copyright © 2004 Society of Chemical Industry     

Chemically induced graft copolymerization of acrylic acid onto cellophane films

Grafting of acrylic acid (AA) onto cellophane films was studied using ferrous ion- hydrogen peroxide a redox initiator system. Different variables affecting the graftingyield, graft efficiency and total weight conversion were studied. The swelling properties as well as I.R. spectroscopy analysis of the grafted films were also examined in the hope of developing improved membranes.     

Radiation‐induced graft polymerization of glycidyl methacrylate onto PE/PP nonwoven fabric and its modification toward enhanced amidoximation

A nonwoven fabric made of polypropylene coated by polyethylene was used as the trunk polymer in the preparation of a highly efficient new adsorbent. Metal ion uptake capacity has been aimed to be increased by introducing double amidoxime groups per repeating unit of the chains grafted to trunk polymer. The base polymer was irradiated by electron beams with a dose of 200 kGy under N₂ atmosphere and glycidyl methacrylate (GMA) was grafted onto irradiated nonwoven fabric. Grafting conditions were optimized, and GMA‐grafted polymer was modified with 3,3′‐iminodipropionitrile in ethanol at 80°C. GMA grafting (150%) was determined to be the optimum degree given that higher extent of grafting rendered the materials brittle. Pendant nitrile groups were then amidoximated by using 6% hydroxylamine in methanol–water mixture (1 : 1). The all‐polymeric structures were characterized by using FTIR, SEM, and thermal analysis methods, confirming the grafting, modification, and amidoximation stages gravimetrically, spectroscopically, and visually. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Graft copolymerization of acrylic acid onto methylcellulose by potassium permanganate‐p‐xylene redox pair

Poly(acrylic acid) was grafted onto methylcellulose in aqueous media by a potassium permanganate‐p‐xylene redox pair. Within the concentration range from 0.93 × 10^?3 to 9.33 × 10^?3M, p‐xylene, the graft copolymerization reaction exhibited minimum and maximum graft yields and was associated with two precursor‐initiating species, a p‐xylyl radical and its diradical derivative. The efficiency of the graft was low, not higher than 12.9% at a p‐xylene concentration of 0.93 × 10^?3M and suggested the dominance of a competitive homopolymerization reaction under homogeneous conditions. The effect of permanganate on the graft yield was normal and optimal at 135% graft yield, corresponding to a concentration of the latter of 33.3 × 10^?3M over the range from 8.3 × 10^?3 to 66.7 × 10^?3M. The conversion in graft yield showed a negative dependence on temperature in the range 30–60°C and suggested a preponderance of high activation energy transfer reaction processes. The calculated composite activation energy for the graft copolymerization was 7.6 kcal/mol. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 278–281, 2004     

Radiation‐induced graft copolymerization of 2‐vinylpyridine and styrene onto isotactic polypropylene fiber

Isotactic polypropylene fiber (IPP) was graft‐copolymerized using 2‐vinyl pyridine (2‐VP) and styrene (sty) as the monomers by the mutual irradiation method in air. The percentage of grafting was determined as a function of various reaction parameters and it was found that the maximum grafting of 2‐VP (114%) and sty (76%) was obtained at an optimum dose of 1.08 × 10⁴ and 0.64 × 10⁴ Gy using 1.8 × 10⁻² mol of 2‐VP and 4.3 × 10⁻² mol of sty, respectively. The graft copolymers were characterized by differential scanning calorimetric analysis and isolation of the grafted chains from the grafted iPP samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2959–2969, 1999     

Chemically induced graft copolymerization of vinyl monomers onto cotton fibers

We investigated the chemically induced graft copolymerizations of acrylic acid (AA), acrylamide, crotonic acid, and itaconic acid (IA) onto cotton fibers. Benzoyl peroxide was used as an initiator. The effects of grafting temperature, grafting time, and monomer and initiator concentrations on the grafting yields were studied, and optimum grafting conditions were determined for the sample material. The maximum grafting yield value obtained was 23.8% for AA. Swelling tests, Fourier transform infrared spectroscopy, and scanning electron microscopy analyses of grafted and ungrafted fibers were also performed to characterize fiber properties. IA‐grafted fibers were measured as the most swollen fibers, with a swelling value of 510%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2343–2347, 2006     

Plasma‐induced graft polymerization of acrylic acid onto poly(ethylene terephthalate) films

The graft polymerization of acrylic acid was carried out onto poly(ethylene terephthalate) films that had been pretreated with argon plasma and subsequently exposed to oxygen to create peroxides. The influence of synthesis conditions, such as plasma treatment time, plasma power, monomer concentration, temperature, and the presence of Mohr's salt, on the degree of grafting was investigated. The observed initial increase in grafting with monomer concentration accelerated at about 20% monomer. The grafting reached a maximum at 40% monomer and subsequently decreased with further increases in monomer concentration. The reaction temperature had a pronounced effect on the degree of grafting. The initial rate of grafting increased with increasing temperature, but the degree of grafting showed a maximum at 50°C. The activation energy of the grafting obtained from an Arrhenius plot was 29.1 kJ/mol. The addition of Mohr's salt to the reaction medium not only led to a homopolymer‐free grafting reaction but also diminished the degree of grafting. The degree of grafting increased with increasing plasma power and plasma treatment time. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2993–3001, 2001     

Free‐radical graft copolymerization of phosphonated methacrylates onto low‐density polyethylene

Dimethyl 2‐methacryloxyethylphosphonate, its monosodium salt, and methyl 2‐methacryloyloxyethylphosphonic acid were synthesized, characterized, and grafted onto low‐density polyethylene (LDPE) powder under melt‐processing conditions in a Rheocord batch mixer (Karlsruhe, Germany). We studied the graft copolymerization onto LDPE in the presence of free‐radical initiators, benzoyl peroxide, and dicumyl peroxide, and we performed grafting onto ozone‐pretreated LDPE without any free‐radical initiator. Effects of reaction time, initiator concentration, and reaction temperature were studied. The possibility of modifying LDPE in the molten state with phosphonated methacrylates was clearly demonstrated. Graft copolymers were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, scanning electron microscopy, and water contact angles. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2011–2020, 2002     

Radiation‐induced graft copolymerization of methylmethacrylate onto poly(tetrafluoroethylene‐co‐ethylene) film

Modification of poly(tetrafluoroethylene‐co‐ethylene), Tefzel (ETFE), film has been carried out by grafting methylmethacrylate (MMA) by radiation method including preirradiation and double‐irradiation methods. Percentage of grafting has been determined as a function of the (i) total dose, (ii) monomer concentration, (iii) amount of liquor ratio, (iv) reaction time, and (v) temperature.The effect of different alcohols such as methanol, ethanol, 2‐propanol, n‐butanol, n‐pentanol, and 2‐ethoxy ethanol on percentage of grafting of MMA was also studied. The graft copolymers were characterized by IR spectroscopy and thermogravimetric analysis (TGA). Methylmethacrylate produces higher percentage of grafting by preirradiaton method than double‐irradiation method. MMA‐grafted ETFE films (S_irr), i.e., prepared by preirradiation involving single irradiation show better thermal stability than MMA‐grafted ETFE films (D_irr), i.e., prepared by double irradiation and unmodified ETFE film. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. IV. Morphological investigations using X‐ray photoelectron spectroscopy

Morphological investigations of poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA)‐g‐polystyrene sulfonic acid membranes prepared by radiation‐induced graft copolymerization of styrene onto PFA films followed by sulfonation were performed by X‐ray photoelectron spectroscopy. The analyzed materials included grafted film and sulfonated membrane samples having various degrees of grafting. Original PFA film was used as a reference material. The results of the X‐ray photoelectron spectral analysis show that PFA film undergoes changes in terms of chemical compositions and binding energies of its basic elemental components under the influence of membrane preparation procedure, i.e., grafting and sulfonation. The chemical compositions of the surfaces of the membranes were found to be dependent on the degree of grafting unlike the binding energies of their elemental components (C, F, O, and S), which were found to be independent of the degree of grafting. The atomic ratio of F/C was found to decrease drastically with the increase in the degree of grafting and the membranes were found to have almost pure hydrocarbon structure at the layers close to their surfaces where degradation is suggested to be concentrated. The results of these investigations suggest that the morphology of the membranes plays an important role in the chemical degradation of the membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2455–2463, 2000     

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     

Ceric‐initiated free radical graft copolymerization of acrylonitrile onto kappa carrageenan

The polysaccharide, kappa carrageenan (kC), was modified using ceric‐initiated graft copolymerization of acrylonitrile (AN) under inert atmosphere in a homogeneous aqueous medium. Grafting was confirmed using FTIR spectroscopy, solubility test, elemental analysis, acid hydrolysis, and thermogravimetric analysis (TGA). kC‐graft‐poly(AN) products had a higher thermal stability than kC as revealed by TGA analysis. The polyacrylonitrile branches were isolated by acidic degradation of the carrageenan main chains and characterized by size exclusion chromatography (SEC). Residual monomers were not found by HPLC in graft copolymers stored even for longer periods. The effect of various factors affecting on grafting, i.e., concentration of the initiator, monomer, and polysaccharide as well as the reaction time and temperature were studied by conventional methods to achieve the optimum grafting parameters. The graft copolymerization reactions were kinetically investigated using semi‐empirical expressions and a suitable rate expression has been derived. According to the empirical rates of the polymerization and the graft copolymerization of AN onto kC backbone, the overall activation energy of the graft copolymerization reaction was estimated to be 20.96 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Gamma ray induced graft copolymerization of N-vinylpyrrolidone,acrylamide and their mixtures onto polypropylene films

The radiation initiated grafting of N-vinylpyrrolidone (NVP) acryl-amide (AAm) and their mixtures onto polypropylene (PP) films using a direct radiation technique has been investigated. Different solvents were used for diluting the monomers and it was found that dioxane was suitable for this grafting system. The influence of other grafting parameters such as inhibitor, monomer concentration and dose rate on the rate of grafting and grafting yield was studied. The values of the coefficients relating the grafting rate to monomer concentration and dose rate were found to be 1·4 and 1·5 for (NVP), and 1·6 and 1·47 for (AAm), respectively. Also, the coefficients relating grafting rate to co-monomer concentration for 20/80 and 50/50 AAm/NVP mixtures were found to be 1·6 and 1·7. Some physicochemical properties such as swelling, thermal behaviour, mechanical and electrical conductivity were also investigated, and the possibility of some practical uses, e.g. the removal of heavy metals from solution, for the grafted membranes is discussed. © 1998 SCI.     

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     

Radiation‐induced graft copolymerization of MMA monomer onto UHMWPE: Adhesion improvement

Graft copolymerization of methyl methacrylate monomer onto ultra high molecular weight polyethylene (UHMWPE) and acid‐etched UHMWPE was conducted using preirradiation method in air in the presence of a Mohr salt and sulfuric acid to improve adhesion to the bone cement. The grafted samples were characterized by Fourier transform infrared (FTIR) spectroscopy, gravimetric method, goniometry, and interfacial bonding strength measurements. The FTIR results showed the presence of ether, carbonyl, and hydroxyl groups for grafted films. The gravimetric results showed that the chromic acid etching and graft copolymerization had a synergetic effect so, the irradiated, then chromic acid etched at room temperature and grafted sample (Rad etch25) had the highest grafting degree. The interfacial bonding strength between UHMWPE and poly methyl methacrylate bone cement was considerably improved by graft copolymerization and chromic acid etching. The surface morphology was studied by scanning electron microscopy. The substitution of polar groups into the backbone of UHMWPE by chromic acid etching and graft copolymerization changed its contact angles with water and methylene iodide and increased its surface energy, as evidenced by contact angle measurements. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Graft copolymerization of styrene and acrylonitrile onto EPDM

Acrylonitrile–EPDM–styrene (AES) graft copolymers were synthesized by solution graft polymerization of styrene (St) and acrylonitrile (AN) onto EPDM in an n‐hexane/benzene solvent with benzoyl peroxide (BPO) as an initiator. The structure changes were studied by an FTIR spectrophotometer. The grafting parameters were calculated gravimetrically. The influence of the polymerization conditions, such as the reaction time, concentration of the initiator, EPDM content, and weight ratio of St/AN, on the structure of the products was investigated. It was found that a proper initiator concentration and EPDM content will give a high grafting ratio of the AES resin. The thermal property of the copolymer was studied using programmed thermogravimetric analysis (TGA). The results showed that the copolymer has a better heat‐resistant property than that of ABS, especially for the initial decomposition temperature (T_in) and the maximum weight loss rate temperature (T_max). Also, the mechanism of the graft reaction was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 428–432, 2002     

Synthesis and characterization of polyethylene modified through phase‐transfer‐catalyzed graft copolymerization

In an effort to impart biodegradability, polyethylene (PE) was modified through the graft copolymerization of vinyl monomers such as acrylamide (AAm) and acrylic acid (AAc) by a phase‐transfer‐catalyst method. The grafting percentage of AAm and AAc for PE was found to be dependent on the dibenzoyl peroxide concentration, monomer concentration, time, temperature, and concentration of the phase‐transfer catalyst. Some AAm‐ and AAc‐grafted PE samples were prepared by chemical, UV, and γ‐radiation methods. The biodegradation of samples of PE, polyethylene‐g‐polyacrylamide, and polyethylene‐g‐poly(acrylic acid) prepared by all these methods was studied. The weight loss of the samples over a period of time was observed with soil‐burial tests. The grafted samples prepared by the phase‐transfer‐catalyst method showed better biodegradation results than those prepared by other methods of grafting. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

UV‐radiation induced graft copolymerization of methyl methacrylate onto sodium salt of partially carboxymethylated psyllium

UV‐radiation induced grafting of methyl methacrylate onto sodium salt of partially carboxymethylated psyllium has been carried out using ceric ammonium nitrate as a photoinitiator in an aqueous medium. The reaction variables including concentrations of initiator, nitric acid, monomer, and amount of the backbone as well as time and temperature have been varied for establishing the optimized reaction conditions for grafting. The influence of these reaction conditions on the grafting yields has been discussed. The overall activation energy of grafting has been calculated. The infrared spectroscopic, thermogravimetric analysis, and scanning electron microscopic techniques have been used for the characterization of graft copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011