Gamma radiation induced graft copolymerization of acrylamide onto poly(vinyl chloride) films

Grafting of acrylamide (AAm) onto poly(vinyl chloride) (PVC) films using gamma radiation has been carried out. The effects of different parameters on the graft yield have been investigated. These parameters include radiation dose, monomer concentration, solvent composition, types of inhibitors and acidity of the medium. In addition, the effects of the multifunctional monomers N,N′-methylene allyl amide (MAAm) and 2,4,6-triallyloxy-1,3,5 triazine (TARA) on the graft yield have been investigated. It has been found that methanol/water mixture in the ratio (1:1) is the proper diluent mixture for enhancing the graft copolymerization process. The presence of sulphuric acid in the reaction medium adversely affects the graft yield more than acetic acid. The presence of MAAm in the reaction medium markedly increases the graft yield, while TARA has practically no effect on the grafting process. Grafted films have been characterized and evidence of grafting has been obtained using thermal and spectroscopic analysis together with swelling measurements in water. © 1998 SCI.     

Gamma‐radiation‐induced graft copolymerization of acrylamide onto crosslinked poly(N‐vinylpyrrolidone)

Crosslinked poly(N‐vinylpyrrolidone) (PVPy) beads were irradiated with γ‐rays in air from a ⁶⁰Co source. Preirradiated beads were grafted with polyacrylamide by refluxing with acrylamide in water or dioxane. Conditions for optimum grafting were determined under a variety of reaction parameters, such as the total dose, duration, and temperature of heating, and the molar concentration of acrylamide used. The effect of the addition of methanol to the aqueous medium during grafting was also studied. The pendant carboxamide groups of PVPy‐g‐polyacrylamide were transformed into amino, aminoethylamido, and hydrazide functionalities terminating in primary amino or hydrazido groups. These provide sites for immobilizing proteins through their amino or carboxyl groups and, also, handles for attaching reagent molecules. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2163–2168, 1999     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. II. Characterization of sulfonated graft copolymer membranes

PFA‐g‐polystyrene sulfonic acid membranes were prepared by simultaneous radiation‐induced graft copolymerization of styrene onto poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA) film followed by sulfonation. The membrane physico‐chemical properties such as swelling behavior, ion exchange capacity, hydration number, and ionic conductivity were studied as a function of the degree of grafting. Thermal as well as chemical stability of the membranes was also investigated. The membrane properties were found to be mainly dependent upon the degree of grafting. The water uptake, ion exchange capacity, hydration number, and ionic conductivity of the membranes were increased, whereas the chemical stability decreased as the degree of grafting increased. The membranes showed reasonable physico‐chemical properties compared to Nafion 117 membranes. However, their chemical stability has to be further improved to make them acceptable for practical use in electrochemical applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1–11, 2000     

Functionalization of poly(tetrafluoroethylene‐co‐ethylene) film by radiation‐induced graft copolymerization

To introduce functional moieties to Tefzel film, a copolymer of tetrafluoroethylene and ethylene, graft copolymerization of vinyl monomers such as acrylonitrile (AN) and methacrylonitrile (MAN) was attempted by a preirradiation method in aqueous medium. Optimum conditions for obtaining the maximum percentage of grafting have been evaluated for both monomers. Maximum grafting of AN (52.2%) and MAN (77.7%) is obtained at a total dose of 3.14 and 2.69 × 10⁴ Gy, respectively, using [AN] = 3.018 mol/L and [MAN] = 1.177 mol/L in 10 mL of water. The effect of aliphatic alcohols of varying chain length, such as methanol, ethanol, isopropanol, n‐butanol, and cyclohexanol, on percentage add‐on of AN and MAN has also been studied. It has been found that all the alcohols decreased the percentage of grafting. Characterization of Tefzel and grafted Tefzel films has been carried out by IR spectroscopy and thermogravimetric analysis. Grafted Tefzel film has been found to have improved thermal resistance. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1171–1178, 2000     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. III. Thermal stability of the membranes

Thermal stability of cation exchange, PFA‐g‐polystyrene sulfonic acid membranes prepared by radiation‐induced graft copolymerization of styrene onto PFA films followed by sulfonation was studied by thermal gravimetric analysis (TGA) and oven heat treatment. The tested samples included original and grafted PFA films as reference materials. All the membranes showed multistep decomposition patterns due to dehydration, desulfonation, dearomatization, and decomposition of the PFA matrix. Investigations of the individual decomposition behaviors showed that the weight loss strongly depends upon the degree of grafting. However, the decomposition temperatures were found to be independent of the degree of grafting. The loss in some selected membrane properties such as ion exchange capacity and water uptake was found to be function of the degree of grafting, temperature, and the time of heat treatment. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1877–1885, 2000     

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 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     

Gamma‐radiation‐induced graft copolymerization of N‐[4‐(N′‐substituted amino carbonyl)phenyl] maleimide onto poly(vinlyl chloride) films

Three types of N[4‐(N‐substituted amino carbonyl)phenyl] maleimide (RPhMI:N‐substituent (R) = phenyl, cyclohexyl, p‐chlorophenyl) were grafted onto poly(vinyl chloride) (PVC) films by using gamma irradiation. The effects of different parameters on the graft yield were investigated. These parameters included radiation dose and monomer concentration. Thermal properties of the grafted polymer were investigated by the determination of dehydrochlorination rate, thermal gravimetric behavior, and UV stability.     

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     

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     

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     

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     

Study of radiation‐induced graft copolymerization of butyl acrylate onto chitosan in acetic acid aqueous solution

The graft copolymerization of butyl acrylate onto chitosan in acetic acid aqueous solution was investigated, using the γ‐ray of ⁶⁰Co γ‐irradiation method. Fourier transform infrared spectra analysis, X‐ray diffraction analysis, and scanning electron microscopy characterized the graft copolymer. The effect of synthesis variables in the graft copolymerization have been discussed in the light of grafting efficiency, grafting percentage, and homopolymer percentage. Hydrophilicity and impact strength of the films formed from copolymer solution were tested and their feasibility as seed coating was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2855–2860, 2003     

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.     

Ultraviolet‐radiation‐induced graft copolymerization of methyl acrylate onto the sodium salt of partially carboxymethylated guar gum

In an attempt to modify the sodium salt of partially carboxymethylated guar gum (Na‐PCMGG; degree of substitution = 0.291), we studied the ultraviolet‐radiation‐induced graft copolymerization of methyl acrylate with ceric ammonium nitrate as a photoinitiator. The influence of the grafting yield was studied as a function of the different reaction parameters, and the optimum reaction conditions for photografting were determined. The various reaction parameters included the photoinitiator, nitric acid, and monomer (methyl acrylate) concentrations, the reaction time, the temperature, and the amount of the substrate. A kinetic scheme for photografting copolymerization was proposed, and the results were in good agreement with the kinetic scheme. The graft copolymerization of methyl acrylate onto Na‐PCMGG (degree of substitution = 0291) in the presence and absence of ultraviolet radiation was also carried out for the study of the efficiency of the photoinitiator. The influence of carboxymethyl groups added to the guar gum molecule on its behavior toward ultraviolet‐radiation‐induced grafting with methyl acrylate was also investigated. The evidence of photografting was ascertained with IR spectroscopy and scanning electron microscopy techniques. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1977–1986, 2005     

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.     

Iron(III) complexed with radiation‐grafted acrylic acid onto poly(tetrafluoroethylene‐co‐perfluorovinyl ether) films

To introduce functional moieties to a poly(tetrafluoroethylene‐co‐perfluorovinyl ether) film, graft copolymerization of vinyl monomers such as acrylic acid was attempted by a simultaneous technique in aqueous solution using γ‐irradiation. The graft copolymers were complexed with the Fe(III) in aqueous solution. The grafted copolymer–metal complexes were examined by infrared (IR), ultraviolet/visible, energy‐dispersive X‐ray spectroscopy, and electron spin resonance techniques. The effect of temperature on the trunk copolymer, untreated grafted, and treated grafted copolymer films was investigated by IR and thermogravimetric analysis. The overall results suggest octahedral structure for Fe(III) and revealed the high stability of the obtained ligand–metal complexes. Furthermore, scanning electron microscope investigation of the grafted and modified films, both unheated and heated (200°C), showed changes in the structure and surface morphology. Promising results were achieved enhancing the practical applications of modified grafted membranes in the recovery of metal ions from aqueous systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4065–4071, 2007     

New aspects of graft copolymerization of styrene onto cellulose induced by gamma rays

Graft products of styrene onto cellulose prepared by simultaneous gamma-ray irradiation under various conditions were acid-hydrolysed to recover polystyrene produced within the cellulose matrix. The polystyrene was subjected to gel permeation chromatography to determine the molecular weight (M) and further separated with a thin-layer chromatographic (t.l.c.) technique into two components, i.e. the true grafted side-chain polymer and attendant homopolymer. This t.l.c. experiment allowed an estimation of the true percentage grafting (Y). Influences of changing the reaction conditions upon the values of M and Y were thus investigated, and some newer aspects on vinyl polymerization occurring within the cellulose matrix are presented.     

Ceric(IV) ion‐induced graft copolymerization of acrylamide and ethyl acrylate onto cellulose

Graft copolymerization of acrylamide (AAm) and ethyl acrylate (EA) onto cellulose has been carried out from their binary mixtures using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 25 ± 1 °C. The extent of acrylamide grafting increased in the presence of the EA comonomer. The composition of the grafted chains (F_AAm = 0.52) was found to be constant during the feed molarity variation from 7.5 × 10^?2 to 60.0 × 10^?2 mol L^?1, whereas the composition of the grafted chains (F_AAm) was found to be dependent on feed composition (f_AAm) and reaction temperature. The effects of ceric(IV ) ion concentration, reaction time and temperature on the grafting parameters have been studied. The grafting parameters showed an increasing trend up to 6.0 × 10^?3 mol L^?1 concentration of CAN at a feed molarity of 30.0 × 10^?2 mol L^?1 and showed a decreasing trend on further increasing the concentration of CAN (>6.0 × 10^?3 mol L^?1) at a constant concentration of nitric acid (5.0 × 10^?2 mol L^?1). The composition of the grafted chains (F_AAm) was determined by IR spectroscopy and nitrogen content and the data obtained then used to determine the reactivity ratios of the acrylamide (r₁) and ethyl acrylate (r₂) comonomers by using a Mayo and Lewis plot. The reactivity ratios of acrylamide and ethyl acrylate were found to be r₁ = 0.54 and r₂ = 1.10, respectively, and hence the sequence lengths of acrylamide (m?M₁) and ethyl acrylate (m?M₂) in the grafted chains are arranged in an alternating form, as the product of the reactivity ratios of acrylamide and ethyl acrylate (r₁ × r₂) is less than unity. The rate of graft copolymerization of the comonomers onto cellulose was found to be dependant on the ‘squares’ of the concentrations of the comonomers and on the ‘square root’ of the concentration of ceric ammonium nitrate. The energy of activation (ΔE_a) of graft copolymerzation was found to be 5.57 kJ mol^?1 within the temperature range from 15 to 50 °C. On the basis of the results, suitable reaction steps have been proposed for the graft copolymerzation of acrylamide and ethyl acrylate comonomers from their mixtures. Copyright © 2005 Society of Chemical Industry     

Gamma radiation-induced graft copolymerization of divinylbenzene onto cellulose fabric

The extent of DVB grafting onto cellulose fabric increases with total gamma radiation dose up to 10–15 kGy while it decreases with the radiation dose rate. A quantitative analysis of DVB grafting has been attempted by means of IR spectroscopy using the baseline method. Characteristic bands were selected in the spectra of copolymers, namely, the cellulose band at 1160 cm^?1 and DVB band at 798 cm^?1. The former band decreased and the latter increased with the degree of copolymerization, and the values were in accordance with the calibration straight line. An attempt to graft DVB onto cotton fabric previously grafted with styrene showed greater extent of copolymerization than with pure fabric.