Radiation-induced grafting of N,N′-dimethylaminoethylmethacrylate onto chitosan films

Chitosan films were grafted with N,N ′-dimethylaminoethylmethacrylate using the ⁶⁰Co gamma irradiation method. The effect of solvent composition, monomer concentration, dose rate, and total dose on grafting was studied. The solvent composition has a marked effect on the degree of grafting. Maximum yield was obtained in the water-methanol (1 : 1) system. The percent grafting increased with monomer concentration and was found to be higher at a lower dose rate for a constant total dose of 0.216 Mrad. The tensile strength, crystallinity, and degree of swelling of grafted films decreased on increasing graft level. However, the graft copolymers showed improved thermal stability. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 869–877, 1997     

Electron-beam irradiation-induced grafting of acrylonitrile onto polyethylene

Low- and high-density polyethylene (PE) films were grafted with acrylonitrile (AN) by electron beam prior to irradiation. The distribution of graft chains over the cross section of the sample film was analyzed in terms of the distribution of nitrogen atoms contained in the AN by means of an electron probe microanalyzer (EPMA), and graft sites were studied in relation to the effect of grafting temperature on the percent graft and the oxygen permeability of the sample films. It was found that diffusion of AN into the film was the rate-limiting step in the grafting process, thus restricting the grafting to the surface of the film in the initial grafting stages. However, the grafting shifted to the center of film as the graft process proceeded, until a uniform distribution of graft chains was observed across the entire film thickness. High-density polyethylene (HDPE) was found to display a higher percent graft than did low-density polyethylene (LDPE), and percent graft tended to increase with increasing grafting temperature. On the other hand, film oxygen permeability decreased with increasing percent graft, but this decreasing trend decreased with increasing percent graft. These findings suggest that the grafting is initiated by radicals trapped in the amorphous phase near the crystalline regions and at the surface of crystallites and that graft chains grow toward the amorphous regions. As for the radicals contributing to graft polymerization, it appears that AN permeates deeper near the crystalline surface and that graft chains grow from these sites.     

Electron beam initiated grafting of methyl methacrylate onto polyethylene: Structure and properties

Polyethylene (PE, 100 parts by weight) was mixed with methyl methacrylate (MMA, up to 5 parts by weight) at 120°C and subsequently exposed to electron radiation of different doses (up to 20 Mrad) to prepare PE/MMA graft copolymers. Successful grafting was verified by IR spectroscopy. Gel formation indicated crosslinking. Grafting increased with increasing MMA concentration and increasing irradiation dose. Crystalline melting temperature and percent crystallinity were lower than those of untreated PE. Tensile strength, elongation at break and dielectric constant of grafted samples were measured and discussed.     

Radiation-induced grafting onto wool. A kinetic analysis

The radiation-induced graft copolymerization of styrene onto wool in aqueous methanol was studied over a temperature range of 0°C to 45°C and a radiation dose-rate range of 0.05 to 2.0 Mrad/hr. The rate of grafting was found to obey the classical polymerization equation. Chain transfer to wool was found to play an important role in the grafting process, and the molecular weight of the resulting graft copolymer was found to be independent of the irradiation dose. The activation energy of the graft process changed from a value of 4.7 kcal/mole below 19°C to a value of 18.7 kcal/mole above this temperature. This phenomenon is ascribed to the formation of hydrogen-bonded systems between the protic solvent molecules and the protein chain in the wool.     

Cation exchange membranes by radiation-induced graft copolymerization of styrene onto PFA copolymer films. I. Preparation and characterization of the graft copolymer

PFA-g-polystyrene graft copolymers were prepared by simultaneous radiation-induced graft copolymerization of styrene onto poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA) films. The effects of grafting conditions such as monomer concentration, dose, and dose rate were investigated. Three solvents, i.e., methanol, benzene, and dichloromethane, were used as diluents in this grafting system. Of the three solvents employed, dichloromethane was found to greatly enhance the grafting process, and the degree of grafting increased with the increase of monomer concentration until it reached its highest value at a styrene concentration of 60 (vol %). The dependence of the initial rate of grafting on the monomer concentration was found to be of the order of 1.2. The degree of grafting was found to increase with the increase in irradiation dose, while it considerably decreased with the increase in dose rate. The formation of graft copolymers was confirmed by FTIR analysis. The structural investigation by X-ray diffraction (XRD) shows that the degree of crystallinity content of such graft copolymers decreases with the increase in grafting, and consequently, the mechanical properties of the graft copolymers were influenced to some extent. Both tensile strength and elongation percent decreased with the increase in the degree of grafting. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2095–2102, 1999     

Effects of synthesis conditions on radiation-induced graft copolymerization of methacrylic acid on to poly(vinyl chloride) films

Poly(vinyl chloride) (PVC) films were grafted with methacrylic acid (MAA) using a simultaneous-irradiation technique. The effect of solvent ratio (methanol-water) on grafting was studied and maximum grafting was found for an equivolume mixture of methanol and water. The graft level increased with increase of the plasticizer (dioctylphthalate) content in PVC. Grafting was found to be higher at low dose rate and increased linearly up to 0.25 Mrad for all dose rates and then levelled off. Grafting also increased continuously with increasing monomer concentrations up to 5.4mol/litre, but a linear increase in grafting was observed only up to 2.5 mol/litre. The dependences of rate of grafting on dose rate and monomer concentration were found to be 0.62 and 1.20 respectively.     

Permeation of gases through modified polymer films. I. Polyethylene–styrene graft copolymers

The permeabilities of nitrogen, oxygen, and carbon dioxide through polyethylene–styrene graft copolymer films were measured by means of a gas permeability apparatus based on a modification of Barrer's high vacuum technique. Polyethylene–styrene grafts were prepared by mutual γ-ray irradiation of low-density polyethylene films in styrene–methanol solution. Densities and thicknesses of the graft copolymer films were determined. It was observed that the gas permeability constants decreased with increasing grafting to minimum values at 20–30% styrene grafting and increased again above 30% grafting. These results are explained in terms of a decrease in the free volume of the amorphous regions of the polyethylene by a “filling in” effect of the grafted polystyrene chains. Above 30% grafting, disruption of the crystallites may occur resulting in increased gas permeation. Activation energies for gas permeation through polyethylene–styrene graft copolymer films were calculated and found to decrease with increasing per cent styrene grafting. For nitrogen permeation, the activation energy decreased from 11.7 kcal/mole for unirradiated polyethylene to 9.5 kcal/mole for a 50.5% graft. Corresponding values for oxygen and carbon dioxide were 10.2–8.2 kcal/mole for a 48.7% graft and 8.4–6.5 kcal/mole for a 50.5% graft.     

Radiation-induced reactions with cellulose. II. The Trommsdorff effect: Dose and dose rate studies involving copolymerization with monomers in methanol

The radiation-induced grafting to cellulose of styrene, methyl methacrylate, vinyl acetate, 2-vinylpyridine, and 4-vinylpyridine in methanol has been studied. All monomers exhibit appreciable grafting at room temperature in either vacuum or air for total doses up to 10 Mrad and at dose rates as high as 1.4 Mrad/hr. in a spent fuel or ⁶⁰Co facility. The magnitude of the grafting depends upon both the total dose and dose rate. Under certain experimental conditions, the grafting experiences a maximum which has been attributed to the Trommsdorff effect. A novel mechanism involving charge-transfer bond formation is proposed to account for the observed data in the grafting reactions.     

Investigation of radiation grafting of vinyl acetate onto (tetrafluoroethylene–perfluorovinyl ether) copolymer films

A study has been made of radiation-induced grafting of vinyl acetate (VAc) on to (tetrafluoroethylene–perfluorovinyl ether) copolymer (PFA). Effects of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield were investigated. In this grafting system, ammonium ferrous sulphate (Mohr′s salt) was added to the monomer-solvent mixture to minimize the homopolymerization of VAc and the most suitable concentration was found to be 2.0 wt%. It was found that the dependence of the initial grafting rate on monomer concentration is of the order 1.5. The degree of grafting tends to level off at high irradiation doses due to the recombination of formed free radicals without initiating graft polymerization. Some properties of the prepared graft copolymer such as swelling behaviour, electrical conductivity, thermal and mechanical properties were also investigated. The electrical conductivity was improved by hydrolysis of poly(vinyl acetate) in the grafted chains to their respective vinyl alcohols. The tensile properties were improved by grafting; however, the elongation percent decreased. The DTA data showed thermal stability of such graft copolymers for temperatures up to 300°C, but stability decreased at higher temperatures.     

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-grafted polymers for biomaterial applications. I. 2-hydroxyethyl methacrylate: Ethyl methacrylate grafting onto low density polyethylene films

Studies were conducted on the radiation grafting of 2-hydroxyethyl methacrylate (HEMA) and ethyl methacrylate (EMA) by the mutual irradiation technique onto low density polyethylene. Four different solution concentrations were used, and radiation doses ranged from 0.03 to 0.05 Mrad. Four copolymer compositions having different HEMA:EMA ratios were also studied using two total monomer concentrations. The kinetics of the grafting process demonstrated by the two monomers were basically different. While EMA showed a typical diffusion-controlled kinetic pattern, HEMA exhibited a more complex behavior, the main features of which were an induction period, a slight autoacceleration and a significant drop in graft level after a maximum is reached. The difference in behavior was interpreted in terms of partitioning of monomers into the polyethylene substrate. The surface topography of the grafted films was studied by means of scanning electron microscopy. A mechanism based on osmotic cell formation was suggested for the HEMA graft system. The copolymer systems investigated showed that the graft reaction is faster in the initial stages for higher percentages of EMA in the monomer mixtures; as grafting proceeds the trend is reversed.     

Radiation grafting of acrylic acid on to polypropylene filaments. I: Effect of reaction conditions

Graft copolymerization of acrylic acid on to polypropylene filaments was investigated by a simultaneous irradiation technique. The effect of various solvents and solvent combinations on swelling behaviour and on percentage grafting was studied. At a constant dose, the percentage grafting was found to be higher at low dose rates and it increased linearly up to 0.25 Mrad and then saturated. It was also observed that grafting increases with increasing monomer concentration up to 2 mole/litre. Graft copolymers were characterized by infrared spectroscopy and colour formation with methylene blue.     

Effects of gamma irradiation,irradiation environment,and postirradiation aging on thermal and tensile properties of ultrahigh molecular weight polyethylene fibers

The effects of gamma irradiation in four types of irradiation environment on the thermal and tensile properties of gel-spun, ultrahigh molecular weight polyethylene fibers (Spectra™ 1000) have been investigated. The gamma irradiation was conducted at 2.5 Mrad and in air, nitrogen, acetylene, and vacuum to study the effects of irradiation media on the aforementioned properties. Thermal and tensile properties of virgin and irradiated fiber samples were examined using differential scanning calorimetry and an Instron tensile tester, respectively. The results indicate that both gamma irradiation and irradiation environment affected the properties of the polyethylene fibers, and substantial changes were observed for the oxygen-containing environment. The tensile-fractured surfaces of the fibers were examined by scanning electron microscopy. The properties of irradiated fibers were further evaluated at 160 days postirradiation and found to be affected, substantially. The postirradiation aging significantly decreased the tensile strength and elongation of the irradiated fibers, indicating that polyethylene fibers should not be exposed to gamma irradiation. © 1996 John Wiley & Sons, Inc.     

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.     

辐照交联PVC／EVA共混物的形态结构与性能

以电子束为辐照源，以三羟甲基丙烷三丙烯酸酯（TMPTA）单体为交联敏化剂，对聚氯乙烯与乙烯－醋酸乙烯共聚物（EVA）的共混物进行辐照交联。采用红外吸收光谱、扫描电镜方法分析了添加改性EVA的共混物形态结构。通过凝胶含量、力学性能的测定，得到结论：EVA共聚物与PVC共混可以促进PVC辐照交联，改性EVA促进效果更明显；辐照剂量增大、体系凝胶含量增加，力学性能及热延伸性能提高，但辐射剂量高于5Mrad之后，体系降解程度明显增加。     

Application of radiation curing in the preparation of polycarbosilane-derived SiC fibers

Polycarbosilane fibers were irradiated by gamma-rays under vacuum and by electron beam in He gas flow or under vacuum at room temperature. Free radicals on Si and C atoms were produced. Most radicals reacted with each other, causing cross-links between polycarbosilane molecules. Some radicals, which did not contribute to cross-linking, were fairly stable under vacuum or in inert gas at room temperature but oxidized on exposure to air. The number of stable radicals under vacuum could be decreased by annealing. The remaining radical concentration was about 1% after annealing at 513 K. By a combination of radiation curing and annealing, SiC fibers with smaller quantities of oxygen were prepared. The mechanical properties of the SiC fibers showed a high tensile strength of 2.5 GPa after heat treatment at 1773 K. On the other hand, polycarbosilane fibers could be cured by radiation oxidation at room temperature, that is, gamma-ray or electron irradiation in oxygen, and the oxygen content could be well controlled by irradiation dose and dose rate. The SiC fibers obtained by the radiation oxidation had an oxygen gradient from the surface to the center which was dependent on the radiation oxidation conditions.     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Radiation effects of an electron beam on the microhardness of poly(methyl methacrylate): Poly(chlorotrifluoroethylene) polyblends

Specimens of poly(methyl methacrylate) (PMMA): poly(chlorotrifluoroethylene) (PCTFE) polyblends with different weight percentage ratios were subjected to electron beam irradiation (1–10 Mrad). The effect of irradiation on the strength of the blend specimens was studied by measuring the surface microhardness using a Vicker's microhardness tester attached to a Carl Zeiss NU 2 Universal research microscope. Significant changes were observed in the Vicker's hardness number, H_v. An irradiation dose of 3 Mrad was found to enhance greatly the microhardness level of the specimens. An increase of approximately 78% in microhardness was observed as the radiation dose was increased from 1 to 3 Mrad. Electron irradiation was also found to induce crosslinking and degradation in the material. The degree of crosslinking was found to be maximum at a dose of 3 Mrad. Specimens incorporating 10 wt% PCTFE were found to exhibit the highest level of microhardness at all radiation doses.     

Surface properties of polyethylene grafted with triallyl cyanurate in the presence of an electron beam

The surface energy and thermodynamic work of adhesion of polyethylene grafted with triallyl cyanurate in the presence of an electron beam have been determined. The surface energy increased with the grafting level and with the irradiation dose up to 10 Mrad. A similar trend was observed with the work of adhesion. The changes in these surface properties were correlated with the concentration of the polar groups as measured by IR (infrared) spectroscopy and ESCA (electron spectroscopy for chemical analysis) studies.     

Synthesis of acrylic acid grafted silicone rubber via preirradiation graft copolymerization and its physical and dielectric properties

The hydrophilic monomer, acrylic acid (AA), has been grafted onto hydrophobic silicone rubber (SR) film via the γ-ray preirradiation graft technique. The AA percent graft in SR-g-AA film increases with increasing irradiation dose rate. The iron powder in monomer solution serves as one source of ferrous ion that is generated by the oxidation reaction with water. The swelling effect shows that the amount of chloroform taken up by an SR-g-AA membrane decreases with the increasing AA grafting, and the amount of water, alcohol, and glycerol taken up by an SR-g-AA film increases with increasing AA percent grafting. The contact angle, ultimate stress, and elongation at break of SR and SR-g-AA copolymers decrease with increasing AA percent grafting. The oxygen/nitrogen selectivity in these films can be enhanced by the graft modification. The thermal behaviors of SR-g-AA copolymers show the characteristics of SR and polyacrylic acid. Finally, the dielectric properties show that the SR-g-AA film has a superior dielectric property than the original SR and poly(AA) matrix. © 1996 John Wiley & Sons, Inc.