Radiation-induced graft polymerization of acrylic acid onto fluorinated polymers. I. Kinetic study on the grafting onto poly(tetrafluoroethylene-ethylene) copolymer

Direct radiation-induced grafting of aqueous acrylic acid (AAc) onto poly(tetrafluoroethylene-ethylene) (ET) film has been studied. The effect of grafting conditions such as monomer concentration, exposure dose, dose rate, and film thickness on the grafting yield was investigated. The dependence of the grafting rate on monomer concentration was found to be 1.2 order. The dependence of the grafting rate on dose rate was found to be 0.6 order regardless of the film thickness. The relationship between the grafting rate and film thickness gave a negative first-order dependence. The results suggest that the grafting process is mainly controlled by monomer diffusion, and it was concluded that this grafting system proceeded by the front mechanism. The swelling behavior increases linearly with degree of grafting. The electrical conductivity and mechanical properties for the trunk and grafted polymer were investigated at different irradiation doses in air and under vacuum irradiations. © 1992 John Wiley & Sons, Inc.     

Radiation-induced grafting of styrene onto ultra-high molecular weight polyethylene powder and subsequent film fabrication for application as polymer electrolyte membranes: I. Influence of grafting conditions

Ultra-high molecular weight polyethylene (UHMWPE) powder was irradiated by gamma rays using a ⁶⁰Co source. Simultaneous and pre-irradiation grafting was performed in air and in inert atmosphere at room temperature. The monomer selected for grafting was styrene, since the styrene-grafted UHMWPE could be readily post-sulfonated to afford proton exchange membranes (PEMs). The effect of absorbed radiation dose and monomer concentration in methanol on the degree of grafting (DG) is discussed. It was found that the DG increases linearly with increase in the absorbed dose, grafting time and monomer concentration, reaching a maximum at a certain level. The order of rate dependence of grafting on monomer concentration was found to be 2.32. Furthermore, the apparent activation energy, calculated by plotting the Arrhenius curve, was 11.5 kJ/mole. Lower activation energy and high rate dependence on monomer concentration shows the facilitation of grafting onto powder substrate compared with film. The particle size of UHMWPE powder was measured before and after grafting and found to increase linearly with increase in level of grafting. FTIR-ATR analysis confirmed the styrene grafting. The grafted UHMWPE powder was then fabricated into film and post-sulfonated using chlorosulfonic acid for the purposes of evaluating the products as inexpensive PEM materials for fuel cells. The relationship of DG with degree of substitution (DS) of styrene per UHMWPE repeat unit and ion exchange capacity (IEC) is also presented.     

Preparation of cation-exchange membrane containing bi-functional groups by radiation induced grafting of acrylic acid and sodium styrene sulfonate onto HDPE: Influence of the synthesis conditions

Electron beam radiation induced grafting of acrylic acid (AA) and sodium styrene sulfonate (SSS) onto high-density polyethylene (HDPE) membranes was investigated by the pre-irradiation method, and a cation-exchange membrane containing bifunctional groups was synthesized. The effects of grafting conditions such as monomer concentration, radiation dose and temperature on grafting yield were studied. The dependence of grafting yield on pre-irradiation dose and monomer concentration was found to be 0.54 and 2.21, respectively. The activation energy for the grafting was calculated to be 22.2 kJ/mol. Infrared spectroscopy analysis of the grafted membrane confirmed the existence of sulfonate and carboxylic acid groups.     

Kinetic study of preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene–perfluorovinyl ether) copolymer

A kinetic study has been made on the preirradiation grafting of acrylic acid (AAc) onto poly(tetrafluoroethylene–perfluorovinyl ether) (PFA) film. The effect of grafting conditions was investigated. The dependences of the grafting rate on preirradiation dose and monomer concentration was found to be of the order of 0.5 and 1.3, respectively. The final degree of grafting was found to increase with dose and monomer concentration. However, it decreases as the grafting temperature increase. The overall activation energy for the graft polymerization was calculated from Arrhenius plots to be 5.6 kcal/mol. The activation energy for this grafting system was found to be independent of preirradiation dose used in the range from 10 to 100 kGy. The relationship between the grafting rate and film thickness gave a negative first-order dependence. The results suggest that the grafting proceeds by radical mechanism with bimolecular termination of growing chain radicals. It was reasonable 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.     

Radiation-induced grafting of styrene vapor to polyethylene

The radiation-induced grafting of styrene vapor to low-density polyethylene film of 0.063 mm thickness was studied at 23°C at a dose rate of 1.98 × 10⁴ rad/hr. The concentration C of monomer in the film was measured as a function of pre-irradiation exposure time to monomer vapor. The concentration-dependent diffusion coefficient of styrene in polyethylene was calculated to be 4.9 × 10^?9 exp {2.0C/C₀} cm²/sec, where C₀ is the saturation concentration of styrene in the film, and a linear boundary diffusion coefficient for styrene vapor into polyethylene film was found to be 2.0 × 10^?7 cm/sec. The rate of grafting was determined as a function of the concentration of styrene absorbed in the film. The maximum graft yield was obtained with an initial styrene concentration in the film of 4 wt-%. Under conditions of low initial monomer concentration, the grafting rate increases with irradiation time. The results are compared with previously published data on grafting of polyethylene from methanol–styrene solutions. They are explained in terms of the viscosity of the amorphous region as a function of styrene content and the resistance to the diffusion of monomer at the film–vapor interface.     

Graft polymerization of acrylamide onto LLDPE film by electron beam pre-irradiation in air and argon. II. Influence of mohr's salt

LLDPE film pre-irradiated by electron beam (EB) in air and argon was grafted in an aqueous acrylamide solution containing Mohr's salt in the concentration range 0.0025–2% The grafting rate and yield were strongly dependent on the Mohr's salt concentration, mainly as a result of chain termination. The exponential grafting rate dependence on the pre-irradiation dose was quite insensitive to a hundred-fold variation in Mohr's salt concentration. © 1995 John Wiley & Sons, Inc.     

Pre-irradiation grafting of span 60-IAH onto polyethylene to improve dripping properties of water on polyethylene films

A reactive type dripping anti-condensation agent, Span 60-IAH, was grafted onto linear low density polyethylene (LLDPE) by β-ray pre-irradiation and reactive extrusion. Effects of total dose, monomer concentration and extrusion temperature and rate on the degree of grafting were studied in detail. It was shown that the optimum conditions for grafting were the extrusion temperature of 130–220°C, screw run speed of 90 rpm and total β-ray dose of 12.5 kGy. The structure of the LLDPE-g-(Span 60-IAH) (LS) was characterized by Fourier-transform infrared spectroscopy (FT-IR). The tensile properties and light transmission properties of extruded films were determined. The thermal behavior of the LS was investigated by using differential scanning calorimetry (DSC). Compared with pure LLDPE, the crystallization temperature (T_c) of LS increased about 3°C. Accelerated dripping properties of film samples were investigated. The dripping duration of the LS film and a commercial anti-fog dripping film at 60°C were 45 days and 17 days, respectively, indicating a significant improvement.     

Synthesis of perfluorinated cation exchange membranes by preirradiation grafting of acrylic acid onto ethylene-tetrafluoroethylene films

Hydrophilic carboxyl-containing fluoromembranes were obtained by preirradiation grafting of acrylic acid onto ethylene-tetrafluoroethylene film. The dependence of the grafting reaction on temperature, monomer concentration, nature and concentration of inhibitor, crosslinking agent, solvent, and on the preirradiation dose was investigated. The grafting rates increase with temperature, whereas the saturation degree of grafting (SDG) decreases. Addition of inhibitor minimizes homopolymerization and at the same time hinders the grafting reaction. The SDG increases markedly with monomer concentration until it reaches a maximum and thereafter decreases. The grafting rates increase with preirradiation dose. Addition of crosslinking agent initially decreases the SDG, and thereafter increases. The highest grafting rates are obtained using water as solvent followed by methanol and ethanol. The results are discussed on the basis of various parameters: interaction between monomer diffusibility and the viscosity of the monomer bath, the mutual reactivity of monomer, and the crosslinking agent. An agreement is observed between the values of the electrical resistance and the saturation degree of grafting. © 1996 John Wiley & Sons, Inc.     

Preirradiation grafting of N-vinyl-2-pyrrolidone onto poly(tetrafluoroethylene) and poly(tetrafluoroethylene-hexafluoropropylene) films

Preirradiation grafting of N-vinylpyrrolidone (NVP) onto poly(tetrafluoroethylene) (PTFE) and poly(tetrafluoroethylene-hexafluoropropylene) (FEP) films was investigated. The influence of grafting parameters such as preirradiation dose, monomer concentration, and grafting temperature on the rate and grafting yield was studied. Different solvents were used for diluting the monomer and it was found that the aqueous monomer solution at a concentration of 80 wt% was suitable for this grafting system. However, the graft polymerization of NVP in benzene terminated within a short time without significant grafting yield. The dependence of the grafting rate on preirradiation dose and monomer concentration was 1.2 and 1.07 order, respectively, for grafting onto PTFE films and 1.1 and 1.2 order, respectively, for grafting onto FEP films. Arrhenius plots for grafting onto PTFE films showed a breaking point at ca. 35°C and the overall activation energies were calculated as 23.6 and 9.0 Kcal/mol below and above 35°C, respectively. For grafting onto FEP films, however, no break was observed in the Arrhenius plots; the overall activation energy was 11.9 Kcal/mol. The swelling behavior and electric resistance of the grafted materials were investigated.     

Chemical reactive filter paper prepared by radiation-induced graft polymerization—I

Chelating filter papers with chemically bonded amidoxime groups were synthesized by radiation-induced grafting of acrylonitrile onto filter paper (W3) followed by chemical treatment with hydroxylamine. The effect of grafting conditions such as absorbed dose, dose rate, monomer concentration and filter paper thickness on the grafting yield was studied. It was found that the degree of grafting increases with increasing absorbed dose and dose rate, and then tends to level off at high doses. The order of the dependence of the initial grafting rate on the dose is found to be of 0.33. An increasing monomer concentration was accompanied by a significant increase in grafting. At high monomer concentration the initial rate of grafting is fast followed by a slow rate. The rate of grafting is controlled by the filter paper thickness and the diffusion of monomer into the interior of the filter paper. Mechanical properties of the prepared filter paper were improved over the ungrafted paper. The amidoxime filter papers were examined for adsorption of uranium concentration ranging between 10–100 ppm.     

γ-Ray-induced grafting of DMAEMA and AAc onto PP by two step method

Binary graft copolymerization of thermosensitive 2-(dimethylamino) ethyl methacrylate (DMAEMA) and pH sensitive acrylic acid (AAc) monomers onto polypropylene (PP) films was carried out by a two step method using a ⁶⁰Co gamma radiation source. The PP film was initially modified by grafting of DMAEMA through a direct method. The DMAEMA-g-PP film obtained was then subjected to radiation grafting of AAc by the pre-irradiation method to give (DMAEMA-g-PP)-g-AAc. The optimal conditions, such as reaction time, reaction temperature, monomer concentration, and dose were studied. The grafted samples were verified by the FTIR-ATR spectroscopy and swelling; thermal properties were analyzed by DSC and TGA.     

Preirradiation grafting of acrylonitrile onto polypropylene monofilament for biomedical applications: I. Influence of synthesis conditions

Graft polymerization of acrylonitrile onto polypropylene (PP) monofilament was carried out by a preirradiation method using a ⁶⁰Co gamma radiation source. The influence of synthesis conditions, such as preirradiation dose, reaction time, monomer concentration, reaction temperature and additives was determined. The grafting was considerably influenced by the instantaneous swelling of the monofilament in the reaction mixture during the course of the grafting process. The order of dependence of the rate of grafting on monomer concentration was found to be 1.04. The nature of the medium of the grafting and the additives had profound influence over the grafting reaction. The accelerative effects of solvent medium on the grafting were higher in methylethyl ketone (MEK) and dimethylformamide (DMF) as compared to methanol. At the same time, partial replacement of DMF with water led to acceleration in the grafting with peak maxima at 20% solvent composition. The addition of a small amount of sulfuric acid to the reaction mixture also resulted in a significant acceleration of the degree of grafting.     

Development of reinforced hydrogels — I. Radiation induced graft copolymerization of methylmethacrylate on non-woven polypropylene fabric

Polypropylene (PP) fibers were grafted with methylmethacrylate. Effects of direct and pre-irradiation method and monomer concentration on the degree of grafting were investigated. The grafted PP fibers were characterized by swelling measurements, IR spectroscopy and by its mechanical and thermal properties. It was found that the direct method was more efficient than the indirect or pre-irradiation method and the monomer concentration for highest degree of grafting was 40% of MMA. Mechanical properties (tensile strength) and thermal stability decrease with grafting yield. Those changes were related to degradation of tie molecules between crystals and formation of rigid branches of PMMA on PP amorphous phase.     

Diffusion-controlled reaction. VI. Radiation graft polymerization of 4-vinylpyridine to polyethylene

The radiation-initiated graft polymerization of 4-vinylpyridine to high-density polyethylene was studied over a wide range of reaction conditions of radiation intensity I, monomer concentration M₁, and polymer film thickness L. The conditions included both diffusion-free and diffusion-controlled graft polymerizations. The results corroborate our previous theoretical predictions on the effect of I, M₁, and L on the experimental grafting rate. The grafting rate is inverse first order in L for diffusion-controlled reaction and independent of L for diffusion-free reaction. The dependence of grafting rate on radiation intensity decreases from 1/2 to 1/4 order for diffusion-controlled reaction. Diffusion control results in a decrease in the dependence of rate on monomer concentration. The observed decrease is somewhat greater than theoretically predicted.     

Radiation-grafting of 4-vinylpyridine and N-isopropylacrylamide onto polypropylene to give novel pH and thermo-sensitive films

Here 4-vinylpyridine (4VP) was grafted onto polypropylene films (PP) by mutual irradiation method to give PP-g-4VP; N-isopropylacrylamide (NIPAAm) was then grafted onto the PP-g-4VP films to give (PP-g-4VP)-g-NIPAAm by pre-irradiation method, using a ⁶⁰Co γ-source. The dependence of grafting percentage on radiation dose, temperature, reaction time, and monomer concentration was studied. (PP-g-4VP)-g-NIPAAm films were characterized by infrared spectroscopy (FTIR-ATR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The critical pH point and lower critical solution temperature (LCST) were determined by swelling and water contact angle measurements. The LCST also was determined by DSC. The binary graft copolymer films are shown to be thermo-pH sensitive.     

辐射接枝医用水凝胶的研究Ⅰ.硅橡胶辐射接技N-乙烯基吡咯烷酮

采用填加SiO_2增强的甲基乙烯基硅橡胶混炼压片。通过~(60)Co-γ射线引发辐射硫化,利用共辐照方法,将N-乙烯基吡咯烷酮接枝到该硅橡胶上,制备了高纯度医用水凝胶。本文较系统地研究了接枝单体浓度、辐照剂量率、剂量、温度和接枝试片厚度等因素对接枝共聚反应的影响。建立了接枝速率与单体浓度、剂量率之间的动力学关系式:R_g=k[M]~(4/5)D~(1/2)。讨论了反应机制和接枝区域。     

Preparation of Cationic Membrane of Polyethylene Film by γ-Irradiation

Grafting of acrylic acid onto PE film by a pre-irradiation method was studied. In order to prevent formation of homopolymer, Mohr salt (NH₄)₂Fe(SO₄)₂ · 6H₂O was used, and the reaction was carried out in the presence of a swelling agent, such as methanol. The influence of different factors, such as dose, dose rate, and temperature, on the kinetics of the reaction was studied. The infrared spectrum of the grafted acrylic acid onto PE shows bands characteristic of carboxylic acids, which demonstrates that grafting has occurred. The grafting sites were shown to be of a semi-spongy shape and irregular structure which is thought to be due to the copolymerization of acrylic acid onto PE film.     

Part I. On the synthesis and pyrolysis of a tetrafluoroethylene–acrylonitrile graft copolymer

Radiation-induced grafting of acrylonitrile onto films of polytetrafluoroethylene has been studied. Irradiation has been carried out in a ⁶⁰Co gamma source at ?78°C., and the graft polymerization was facilitated by being held at 100°C. for 150 hr. The amount of acrylonitrile grafted per unit surface area apparently increases with the thickness of the film. Grafting is also accompanied by slight swelling. This indicates that the reaction occurs in depth. The relative decrease of the amount of grafted acrylonitrile with thickness of the film, referred to the weight of the film, shows that grafting is controlled by the diffusion of the monomer. The rate of grafting was found to be lower in a material with a higher degree of crystallinity; i.e., grafting occurs faster in the amorphous areas of the polymer. The final yield of graft decreases with the temperature at which the reaction is carried out. This may be explained on the basis of kinetics or by assuming a simultaneous disappearance of free polymer radicals.     

Graft copolymers obtained by radiation grafting of methacrylic acid onto polypropylene films

Direct radiation grafting of methacrylic acid (MAA) onto polypropylene films (PP) was studied. The effect of different solvents such as benzene, distilled water, dimethyl formamide, isopropanol, isopropanol/water-mixture, on the swelling and the grafting process of MAA onto (PP) films was investigated. It was found that the grafting process was enhanced under vacuum irradiation in benzene as a diluent for MAA as compared with other solvents examined. The dependence of the grafting rate on such monomer concentrations was found to be 1.2 order. The relationship between the grafting rate and film thickness gave a negative first order dependence. This grafting system proceeded by a diffusion controlled process. Some selected properties of the grafted films such as mechanical and electrical properties, swelling behaviour, and gel determination, were also investigated.     

Diffusion-controlled reaction. VI. Radiation graft polymerization of styrene to polyethylene

The radiation graft polymerization of styrene to polyethylene was studied under diffusion-controlled conditions of radiation intensity I, monomer concentration M₁, and polymer sample thickness L. The results of the present study together with previous work under diffusion-free conditions verify our theoretical model for the diffusion-controlled reaction. The grafting rate is inverse first order in L for diffusion-controlled reaction and independent of L for diffusion-free reaction. The order of dependence of grafting rate on radiation intensity for diffusion-controlled reaction is one-half that for diffusion-free reaction. Diffusion control leads to a decrease in the order of dependence of grafting rate on monomer concentration. The decrease is greater than theoretically predicted; possible reasons for this effect are described.