The study on radiation grafting of acrylic acid onto fluorine-containing polymers. III. Kinetic study of preirradiation grafting onto poly(tetrafluoroethylene–hexafluoropropylene)

A kinetic study has been made on the preirradiation grafting of acrylic acid (AAc) onto poly(tetrafluoroethylene–hexafluoropropylene) (FEP) film. The effect of grafting conditions was investigated. The dependencies of the grafting rate on preirradiation dose and monomer concentration were found to be 0.58 and 1.25 order, respectively. The overall activation energy for the graft polymerization was 7.4 kcal/mol. The final degree of grafting increased with preirradiation dose and monomer concentration and slightly decreased as the grafting temperature was elevated. The relationship between the grafting rate and film thickness gave a negative first-order dependency, which is in agreement with that obtained for polytetrafluoroethylene—AAc grafting system. It was reasonably concluded that this grafting proceeds from the surface to the center of film with progressive monomer diffusion through the grafted layer which swells in the monomer solution.     

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     

Study on radiation grafting of acrylic acid onto fluorine-containing polymers. II. Properties of membrane obtained by preirradiation grafting onto poly(tetrafluoroethylene)

Some properties of the membranes obtained by the preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene) (PTFE) film have been studied. The dimensional change by grafting and swelling, water uptake, electric conductivity, and mechanical properties of the grafted PTFE films were measured and were found to increase as the grafting proceeds. These properties were found to be dependent mainly on the degree of grafting regardless of grafting conditions except higher monomer concentration (80 wt %). The electric conductivity and mechanical properties of the membranes at 80 wt % monomer concentration is lower than those at a lower monomer concentration. The results suggest that the membranes obtained at 80-wt % acrylic acid solution have a somewhat heterogeneous distribution of electrolyte groups as compared with those prepared at a monomer concentration less than 60 wt %. X-ray microscopy of the grafted films revealed that the grafting begins at the part close to the film surface and proceeds into the center with progressive diffusion of monomer to give finally the homogeneous distribution of electrolyte groups. The membranes show good electrochemical and mechanical properties which make them acceptable for the practical uses as cation exchange membrane.     

Radiation grafting of α,β,β-trifluoroethylenesulfonyl fluoride onto low-density polyethylene film by simultaneous irradiation method. I. Kinetic study of simultaneous-irradiation grafting

α,β,β-Trifluoroethylenesulfonyl fluoride (TFESF) was grafted onto polyethylene (PE) film by a simultaneous-irradiation method. The influences of the grafting conditions were analyzed kinetically. The dependencies of the grafting rate on the dose rates and monomer concentrations ranging from 10 to 75% were found to be of 1 and 0 order, respectively. The overall activation energy for the graft polymerization was 2.05 × 10⁴ J/mol. The grafting rate was found to be independent of the film thicknesses ranging from 25 to 100 μm.     

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.     

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     

Radiation grafting of vinyl monomers onto wood pulp cellulose. Part I

The effect of dose, dose rate, monomer type, and monomer concentration on the water transport behavior in grafted cellulose pulp and hand sheets was studied. At low dose rates, grafting rates of styrene onto wood pulp were less with hand sheets than with the pulp itself. Grafting was also found to be decreased by increasing the dose rate. Grafting mixtures of styrene and acrylonitrile gave better yields than styrene alone. Excellent grafting yields were obtained by treating the pulp or hand sheets with water before adding vinyl monomers. In this way, solvents such as dioxane could be eliminated from the grafting mixture. The hand sheets, grafted with mixtures of acrylonitrile and styrene, had good mechanical properties although less than the corresponding ungrafted sheets. Grafting decreased the moisture regain in pulp and hand sheets. Gamma irradiation of wood pulp under ambient conditions without additives reduced the water sorption considerably.     

Radiation grafting of vinyl monomers onto wood pulp cellulose. II

The effect of radiation dose rate and beating time on the mutual radiation grafting of styrene to unbleached and bleached kraft wood pulp was studied. Companion studies on the effect of beating time, peroxidation grafting, and order of monomer addition on the preirradiation graft copolymerization of acrylamide and diethylaminoethyl methacrylate were conducted on bleached wood pulp. The grafting rate of styrene increased with dose rate, but the kinetics suggests a significant diffusional resistance to the observed grafting rate. The per cent graft measured at fixed grafting conditions decreased markedly as pulp beating (effected prior to grafting) was increased. It is suggested that the decrease in grafting with beating is due to an increase in the accessibility and swelling of the beaten fibers. Dimethylaminoethyl methacrylate appeared to inhibit the grafting of acrylamide, and double grafting had to be used to graft both hydrophilic polymers to the pulp. The mechanical properties of high-yield pulp and groundwood were improved by the addition of the grafted pulps. The double grafts appeared to show promise as fibrous beaten additives for dry strength improvement. The styrenegrafted pulps were found not to respond at all to the beating process.     

聚丙烯无纺布预辐射法固相接枝甲基丙烯酸甲酯的研究

研究了以预辐射聚丙烯无纺布为基材,甲基丙烯酸甲酯为单体,采用固相接枝聚合的方法制备接枝共聚物的接枝反应过程。详细讨论了反应温度、反应时间、阻聚剂、单体浓度和交联剂等对接枝率的影响。结果表明,该接枝反应的最佳条件为:温度65℃、时间2 h、单体浓度20%、交联剂5%、阻聚剂(FeSO4.7H2O)0.3 g,在此条件下的接枝率为6.64%。     

Radiation initiated grafting of acrylic acid onto tetrafluoroethylene–ethylene copolymers

Hydrophilic carboxyl containing fluoropolymers was obtained by radiation grafting of acrylic acid onto tetrafluoroethylene—ethylene copolymers with different compositions. By using simultaneous (⁶⁰Co) and preirradiation (electron beam) techniques, the effect of the grafting conditions (monomer concentration, dose rate, dose, film thickness, etc.) on the degree of grafting was studied. A considerable effect of the polymer compositions, especially the C? F bonds content, and the batch irradiation on the degree of grafting was found. It was observed by scanning electron microscopy that the grafting took place mainly on the polymeric film surface and developed inward with increasing diffusion of the acrylic acid through the grafted layers. © 1993 John Wiley & Sons, Inc.     

PP无纺布预辐射法固相接枝4-VP的研究

以预辐射聚丙烯无纺布为基材,4-乙烯基吡啶为单体,二乙烯基苯为交联剂,采用固相接枝聚合的方法制备接枝共聚物。讨论了反应温度、反应时间、阻聚剂、单体浓度和交联剂等对接枝率的影响。结果表明,接枝反应的最佳条件为:温度50℃,时间3 h,单体浓度10%,交联剂5%,阻聚剂(FeSO4.7H2O)0.08%,最佳条件下的接枝率为7.5%。     

Proton exchange membranes by grafting of styrene–acrylic acid onto FEP by preirradiation technique. I. Effect of synthesis conditions

Grafting of styrene–acrylic acid (sty–AA) polymer onto fluorinated ethylene propylene copolymer (FEP) was carried out by preirradiation of FEP with γ‐rays. Effect of reaction conditions on the degree of grafting such as total radiation dose, monomer concentration, temperature, and time of grafting has been studied. From the study, it is seen that the degree of grafting is strongly dependent on the reaction conditions. The rate dependence of 0.53 (～0.5) and 1.03 (～1) have been obtained with respect to total dose and monomer concentration, respectively indicating that radiation induced grafting follows free radical polymerization. The activation energy for the grafting in the temperature range of 60–90°C is found to be 33 kJ/mol. The results indicate that the grafting takes place by the front mechanism where the grafting starts at surface and slowly proceeds inwards by diffusion of the monomer through the swollen grafted chains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2572–2577, 2003     

Radiation grafting of α,β,β-trifluorostyrene onto poly(ethylene–tetrafluoroethylene) film by preirradiation method. I. Effects of preirradiation dose,monomer concentration,reaction temperature,and film thickness

Preirradiation grafting of α,β,β-trifluorostyrene onto poly(ethylene–tetrafluoroethylene) film was studied. The trapped radicals formed upon irradiation were able to induce graft polymerization under appropriate conditions. The influences of the grafting conditions were analyzed kinetically. The grafting rate dependency on the preirradiation dose was found to be of order 0.3, and the monomer concentrations, 1.0. The overall activation energies for this grafting were calculated to be 6.2 × 10⁴ and 9.3 × 10³ J/mol below and above 50°C. The grafting rate was found to be independent of the film thickness, which ranged from 25 to 100 μm.     

Graft polymerization of acrylic acid onto polyethylene film by preirradiation method. I. Effects of preirradiation dose,monomer concentration,reaction temperature,and film thickness

Low-and high-density polyethylenes were irradiated by electron beams with dose of 2–50 Mrad and then immersed in aqueous solution of acrylic acid (monomer concentration from 30 to 100 wt %) for 10 min?5 h at a temperature of 25–40°C. The degree of grafting increases with time and levels off. High density polyethylene shows lower grafting rate and higher final % grafting in compared with low-density polyethylene. Both grafting rate and final % grafting increase with total dose of preirradiation, but show some saturation at high doses. The highest grafting rate was observed at 60 wt % of monomer concentration where the grafted polyethylene swells to the largest extent in the monomer mixture. Apparent activation energies for the grafting are 19.6 and 27.3 kcal/mol for low- and high-density polyethylenes, respectively, reflecting the proces of monomer diffusion in the film. Grafting rate decreases with increasing film thickness. Graft polymerization starts on the surface of the film and proceeds to the inner part with monomer diffusion through the grafted layer.     

Radiation grafting of acrylic and methacrylic acids onto poly(tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) TFB films

A study has been made for the preparation of membranes by the direct radiation grafting of acrylic and methacrylic acids onto poly(tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) TFB films. The appropriate reaction conditions were selected under which the graft polymerization was carried out successfully. In this grafting system, ammonium ferrous sulfate (Mohr's salt), ferric chloride, and cuppric chloride were used as inhibitors to minimize the homopolymerization of acrylic acid and methacrylic acid. Also, the effect of monomer concentration on the rate of grafting was investigated. The dependence of the grafting rate on monomer concentration was found to be of the order of 1.1 and 1.0 for acrylic acid and methacrylic acid, respectively. This grafting system was proceeded by a front mechanism. Some selected properties of the grafted films such as swelling behavior, dimensional change, and mechanical and electrical properties were investigated. It was found that the grafted membranes possess good hydrophilic properties that may make them promising in some practical applications. © 1993 John Wiley & Sons, Inc.     

Chemically induced graft copolymerization of acrylic acid onto polyester fabrics. I. Kinetic investigation of grafting

The kinetics of grafting of acrylic acid onto poly(ethylene terephthalate) fabrics initiated by benzoyl peroxide has been studied. Extent of grafting depended upon time, concentration of the initiator and the monomer, as well as the presence of the activator used. From the temperature dependence of the initial rate of grafting the overall activation energy for grafting was found to be 90 kJ/mol. The results of the monomer and temperature dependence found in this study are consistent with the rate expression derived from a normal kinetic scheme for grafting.     

Ceric-induced grafting of ethyl-acrylate onto sodium alginate

Sodium alginate was graft-copolymerized with ethyl acrylate using ceric ammonium nitrate as an initiator. In order to optimize the conditions for grafting, the concentrations of nitric acid, initiator and monomer together with temperature, time and amount of substrate were varied. The kinetic scheme of free radical graft copolymerization has been proposed and the equations relating the values of rate of polymerization, rate of graft copolymerization and rate of homopolymerization are also suggested. The experimental results agree very well with the proposed kinetic scheme.     

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     

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     

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