Radiation-initiated graft copolymerization of individual monomer and comonomer onto polyethylene and polytetrafluoroethylene films

Preparation and some properties of the graft copolymers obtained by radiation-induced graft polymerization of methacrylic acid (MAA) and (acrylonitrile/MAA) comonomer onto polyethylene and polytetrafluoroethylene films, were investigated. The effect of reaction conditions, solvent, monomer, and inhibitor concentration, comonomer composition, and comonomer concentration, on the graft copolymerization process was studied. The grafting process was enhanced in the presence of comonomer (AN/MAA) as compared with individual grafting of MAA or acrylonitrile (AN). The optimum comonomer composition, at which the highest grafting yield was obtained, was found to be (80/20) wt % of (AN/MAA) comonomer. The graft copolymerization of (AN/MAA) comonomer was enhanced in presence of AN due to its higher polarity strength. The electrical and swelling properties of the graft copolymers were greatly affected by the contents of PAN and PMAA graft chains. Mechanical properties of the graft copolymers were significantly changed with the grafting yield.     

Preparation of conductive nylon 6 film

Electrically conducting nylon 6 films was prepared by introducing amide group or cyan group into the nylon 6 film and then introducing Cu_xS, which is known as the p-type semiconductor, into the grafted nylon films. The graft copolymerization of acrylamide (AM) and acrylonitrile (AN) onto nylon 6 film was investigated using ceric salt as the initiator. The graft yield was influenced by the concentration of ceric salt, sulfuric acid and monomer, and the reaction time. The optimum conditions for the introducing of Cu_xS were studied. Electrical conductivity of Cu_xS-treated nylon film was found to be higher by order of 10⁹ than that of the original nylon 6 film, and then properties of the resulting modified films were investigated.     

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.     

三元乙丙橡胶溶液接枝丙烯腈

对三元乙丙橡胶在二甲苯中与丙烯腈的接枝共聚进行了研究,结果表明AIBN可以有效引发接枝共聚,并且正交实验发现单体用量、引发剂浓度和反应温度均对接枝率有重要影响,条件适当接枝率可达15％以上。实验证明,接枝共聚物对丁腈橡胶／三元乙丙橡胶并用具有明显的增容作用。     

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.     

Gamma radiation‐induced graft copolymerization of styrene onto poly(ethyleneterephthalate) films

Gamma radiation‐induced graft copolymerization of styrene onto poly(ethylene terephthalate) (PET) films was studied using simultaneous irradiation technique. The effects of grafting conditions on the degree of grafting were investigated. The grafting conditions include monomer concentration, irradiation dose, dose rate, and the type of solvent. Moreover, the effect of the addition of crosslinking agents [i.e., divinylbenzene (DVB) and triallyl cyanurate (TAC)] having various concentrations were also investigated. The degree of grafting was found to be greatly dependent on the grafting conditions. Of the three diluents employed, methylene chloride was found to drastically enhance the degree of grafting. The order of dependence of the initial rate of grafting on the monomer concentration was found to be 2.2. The grafted PET films were identified by FTIR spectroscopy and characterized by X‐ray diffraction (XRD). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1003–1012, 2000     

Preparation and properties of cationic membranes obtained by radiation grafting of vinyl monomers onto poly(tetrafluoroethylene-perfluoropropylvinyl ether) (PFA) films

Cationic membranes were prepared by direct radiation grafting of acrylic acid (AAc) and methacrylic acid (MAA) onto poly(tetrafluoroethylene-perfluoropropylvinyl ether) (PFA) films, followed by alkaline treatment to confer ionic character in the graft copolymer. The addition of inhibitor such as Mohr's salt, FeCl₃ and CuCl₂ was used to achieve the complete inhibition of homopolymerization of the monomer. The dependence of the grafting rate on AAc and MAA concentration was found to be of the order of 1.3 and 0.62, respectively. Investigation of the mechanical properties, electrical conductivity, dimensional change and swelling behaviour of the grafted films revealed that such a copolymer could be acceptable in practical use as a cation-exchange membrane.     

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     

Graft copolymerization of acrylonitrile onto bagasse and wood pulps

Graft copolymerization of acrylonitrile onto bagasse and wood pulps has been studied using ceric ammonium nitrate as initiator. The effect of order of reactants addition on grafting was examined: three methods were studied. Addition of the pulp to a mixture of initiator and monomer (method A) resulted in more efficient grafting than the other two methods. The reaction produced more grafting at 50°C than at 30°C or at 40°C. The results showed that the monomer and initiator concentrations are the major factors influencing the grafting rate of acrylonitrile. Increasing the acrylonitrile or initiator concentration was accompanied by a substantial increase in graft yields. Increasing the initiator concentration is more effective on polymerization rate than the increase in monomer concentration. The extent of grafting of this monomer can best be controlled by reaction time. Water swelling of pulps significantly affected the grafting rate of acrylonitrile as well as the ceric consumption during grafting. The reactivity of bagasse pulp towards grafting of acrylonitrile is higher than that of wood pulp due to a more open structure of cellulose in bagasse pulp as well as the presence of some lignin which accelerates grafting. Ceric consumption during grafting depends on the nature of the pulp as well as the monomer and initiator concentrations, time, temperature, and the method of grafting. More Ce(IV) is consumed during grafting than during oxidation of the pulps under identical reaction conditions, due to homopolymer formation which accompanied grafting. The ceric consumption by bagasse during grafting or oxidation is somewhat greater than that consumed by wood pulp under similar reaction conditions.     

Modification of polypropylene fiber by radiation-induced graft copolymerization of acrylonitrile monomer

Modification of polypropylene fiber was carried out by graft copolymerization of acrylonitrile monomer using the preirradiation method. The influence of synthesis conditions (preirradiation dose, monomer concentration, temperature, draw ratio, and storage) on the degree of grafting was investigated. For all preirradiation doses, the degree of grafting was found to increase with the reaction time. The higher the preirradiation dose, the higher the degree of grafting was. The dilution of monomer with DMF showed peak maxima for the degree of grafting at 80% monomer concentration. Both the initial rate of grafting and the final degree of grafting were found to increase with an increase in the reaction temperature. An activation energy of 31.2 kJ/mol was found for the grafting reaction. The degree of grafting in the drawn fiber showed different behavior as compared to the undrawn fiber. The storage of the irradiated fiber at −4°C prior to the grafting showed a decrease in the degree of grafting initially for a period of 8 days, beyond which the degree of grafting remained constant. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1343–1348, 1998     

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.     

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     

Preparation and properties of cationic membranes obtained by radiation grafting of methacrylic acid onto PTFE films

Cationic membranes were prepared by direct radiation grafting of methacrylic acid (MAA) onto poly(tetrafluoroethylene) (PTFE) films followed by alkaline treatment to confer ionic character in the graft copolymer. The complete inhibition of homopolymerization of MAA by using ammonium ferreous sulfate (Mohr's salt) failed. However, the addition of 0.5 wt % FeCl₃ to the monomer solution effectively inhibited the homopolymerization process and higher grafting yield was obtained. It was found that the graft polymerization proceeded successfully in presence of methanol/water mixture (30/70 wt %), and much higher degrees of grafting were obtained as compared with those in the presence of other diluents used here. The influence of irradiation atmosphere (air, N₂ gas, and vacuum) on the grafting process was investigated. The dependence of the grafting rate on MAA concentration was found to be of orders 2.9 and 0.72 in the presence of 0.5 wt % Mohr's salt or 0.5 wt % FeCl₃, respectively. This grafting system proceeds by the front mechanism. Investigation of mechanical properties, electrical conductivity, and swelling behavior of the grafted films revealed that such a copolymer could be acceptable in practical use as a cation-exchange membrane.     

Grafting of long‐chain unsaturated carboxylic acids onto acrylonitrile–butadiene–styrene terpolymer

The graft copolymerization of undecylenic acid, oleic acid, and crotonic acid onto acrylonitrile–butadiene–styrene terpolymer (ABS) was initiated by benzoyl peroxide (BPO) in 1,2‐dichloroethane solution. The infrared spectra confirmed that undecylenic acid, oleic acid, and crotonic acid were successfully grafted onto the ABS backbone. The grafting occurred at the butadiene region of the ABS. The grafting degree increased with increasing monomer concentration, but it decreased after monomer concentration, reaching 0.30 mol/L in undecylenic acid and oleic acid systems. The grafting degree increased rapidly with increasing initiator concentration, but slowed down at about 0.012 mol/L of initiator concentration. The grafting degree decreased considerably with increasing ABS concentration; however, the total amount of grafted monomer increased. Increasing reaction time and temperature led to an increase in grafting degree. The chain length of the monomer has a great influence on grafting. The grafting degree decreases with increasing the chain length due to a steric hindrance and monomer cage effect, which is in agreement with activation energy calculation. The overall activation energy of crotonic acid, undecylenic acid, and oleic acid systems are 118, 122, and 134 kJ/mol, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1934–1939, 2002     

Chemical modification of jute fibers. II: A study on the Fe2+/H2O2-initiated graft copolymerization of methyl methacrylate,acrylonitrile, and acrylamide onto jute fibers

The study of graft copolymerization of methyl methacrylate, acrylonitrile, and acrylamide onto both defatted and bleached jute fibers using the ferrous ammonium sulfate / H₂O₂ redox initiator system has been made. To determine the optimum conditions of grafting, the effects of concentrations of ferrous ammonium sulfate, monomer, H₂O₂; time and temperature on percentage of graft yield have been studied. Acrylamide was found to graft onto the fiber only at a fixed ferrous ammonium ion concentration (5 × 10^?4M). Kinetic studies showed that the rates of grafting follow the second-order mechanism. The activation energies of the reactions were found to be 3.351 and 2.53 kcal/mol in the methyl methacrylate and acrylonitrile systems, respectively. The grafted fibers have been characterized by thermogravimetric analysis, IR spectroscopy, and XRD studies.     

Graft copolymerization of nitrile monomers onto bleached jute fiber using potassium persulfate system and their textile characteristics

Graft copolymerization of nitrile monomers, such as acrylonitrile and methacrylonitrile, onto bleached jute fiber was carried out by using K₂S₂O₈/FeSO₄ redox system in nitrogen atmosphere and their effect on the textile characteristics was also investigated. Percent graft yield increased with the increase of concentrations of monomer, initiator, and catalyst, reaction time, and reaction temperature up to a certain value, and, thereafter, it decreased. The effect of percent grafting efficiency was similar to that of percent graft yield, except for the monomer concentration. The increase of percent graft yield was dependent on the availability of jute‐macroradicals as well as monomer radicals. Sometimes the predominancy of homopolymerization over grafting and the premature termination of growing grafted chains occurred because of the higher monomer radicals and excess primary radicals, SO₄^?? and ^?OH, from K₂S₂O₈ initiator. The percent graft yield of acrylonitrile and methacrylonitrile was 20.5 and 29.1%, respectively. Higher graft yield for methacrylonitrile might be due to the methyl group present in it. Infrared spectra at 2229–2235 cm^?1 of acrylonitrile‐ and methacrylonitrile‐grafted jute strongly supported the graft formation. Grafting of jute fiber improved the thermal stability, protected from photooxidative degradation, and decreased swellability as well as dyeability, etc. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3622–3629, 2004     

Graft copolymerization of vinyl monomers on cellulosic materials

Graft copolymers of acrylonitrile, ethyl acrylate, methyl acrylate, ethyl methacrylate and methyl methacrylate and of acrylonitrile/ethyl methacrylate and acrylonitrile/methyl methacrylate monomer mixtures on carboxymethylcellulose (degree of substitution 0.4–0.5) were prepared by use of ceric ion initiator in aqueous medium. The extent of graft polymer formation was measured in terms of graft level, molecular weight of grafted polymer chains and frequency of grafting as function of ceric ion concentration. It was found that at comparable reaction conditions, the molecular weight and frequency of grafting were not of the same order of magnitude. For the monomer mixtures, the copolymer compositions obtained from the total nitrogen content of the acrylonitrile/alkyl methacrylate copolymer samples showed that a relativity low amount of the acrylonitrile monomeric units were incorporated into the graft copolymer even at high acrylonitrile content of the feed.     

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     

Studies on graft copolymerization of acrylonitrile onto jute fiber with permanganate ion initiation system in presence of air

The graft copolymerization of acrylonitrile with jute using potassium permanganate as the initiator has been studied in the presence of air. To establish reaction conditions for the graft copolymerization of acrylonitrile (AN) onto jute, the effect of different variables such as the residual lignin content of bleached jute (after bleaching with sodium chlorite), initiator concentration, monomer concentration, time of polymerization, reaction temperature, and amount of bleached jute fiber have been studied. As evidence of polymer grafting, some instrumental analyses such as scanning electron microscopy, infrared, and thermogravimetry have been carried out. The extent of grafting of acrylonitrile depends on how much lignin is present on the jute fiber. Percent grafting and grafting efficiency have also been studied. © 1995 John Wiley & Sons, Inc.     

Radiochemical graft copolymerization of methacrylonitrile and binary mixture of methacrylonitrile with 4-vinylpyridine onto isotactic polypropylene fiber

Graft copolymerization of methacrylonitrile (MAN) and its binary mixture with 4-vinylpyridine (4-VP) onto isotactic polypropylene (IPP) fiber has been studied in aqueous medium by the preirradiation method. Optimum conditions for obtaining the maximum percentage of grafting have been evaluated. Rate of grafting (Rg) has been determined as a function of total initial monomer concentration. The graft copolymers are characterized by IR spectroscopy, by thermogravimetric analysis, and by isolating the polymer from the graft copolymer. The effect of MAN, an acceptor monomer, on percentage of grafting of 4-VP, a donor monomer, has been discussed in the light of the mechanism proposed for grafting by the radiochemical method. © 1994 John Wiley & Sons, Inc.