Radiochemical grafting of methacrylonitrile and its binary mixture with methyl acrylate onto gelatin

Methacrylonitrile (MAN) has been graft copolymerized individually and as a binary mixture with methyl acrylate (MA) onto gelatin by a simultaneous irradiation method. Percentage grafting has been studied as a function of total radiation dose, monomer concentration, amount of water and water–methanol system. It was found that addition of MA increased the grafting efficiency of MAN. A plausible explanation has been suggested to account for the trends in the results © 1998 SCI.     

Graft copolymerization of 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method

An attempt has been made to graft copolymerize 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method in an aqueous medium. Polypropylene hydroperoxide has been prepared by irradiating recrystallized polypropylene beads from a Co⁶⁰ source in the presence of air. The resulting polypropylene hydroperoxide beads have been used as the backbone polymer and grafting of 4-vinyl pyridine has been studied as a function of various reaction parameters. Optimum conditions for maximum percentage of grafting have been evaluated. Rate of grafting (R_g) has been determined as a function of preirradiation dose and initial monomer concentration. Water has been found to affect percentage of grafting. The graft copolymers have been characterized by spectroscopic method and isolation of the grafted poly(4-VP) from the graft copolymer. A plausible mechanism is proposed to explain the mutual grafting of 4-vinyl pyridine onto polypropylene hydroperoxide. © 1993 John Wiley & Sons, Inc.     

Modification of Tefzel film through graft copolymerization

The graft copolymerization of styrene (st) and methacrylonitrile (MAN) onto Tefzel film in aqueous media by the preirradiation method has been studied. In order to follow the effect of preswelling of the backbone polymer, grafting was attempted onto preirradiated Tefzel film and monomer preswollen, preirradiated Tefzel film. Optimum conditions pertaining to maximum percentage of grafting of st and MAN have been evaluated. Grafting onto preswollen, preirradiated Tefzel film displayed better results. The effect of different alcohols of increasing chain length on the percentage of grafting of st and MAN was also studied. Graft copolymerization of st showed an increase, while grafting with MAN exhibited a decrease, in the percentage of grafting in the presence of alcohols as compared to that obtained in the aqueous medium. Characterization of the graft copolymers was made by IR and thermogravimetric studies. Tefzel‐graft‐polystyrene showed improved thermal stability while the MAN grafted onto preswollen, preirradiated Tefzel film produced graft copolymer with poor thermal stability. Copyright © 2004 Society of Chemical Industry     

Graft copolymerization of acrylonitrile and methacrylonitrile onto gelatin by mutual irradiation method

In order to improve upon certain properties of gelatin graft copolymerization of acrylonitrile (AN) and methacrylonitrile (MAN) onto gelatin has been studied in aqueous medium using γ rays as a source of initiation. Optimum conditions for affording maximum percentage of grafting have been evaluated as a function of various reaction parameters. The grafted polyacrylonitrile (PAN) was isolated from the graft copolymer by acid hydrolysis, and the average molecular weight (M_v) of the isolated polymer has been determined viscometrically. The graft copolymers were characterized by IR spectroscopic methods and thermogravimetric analysis (TGA). Acrylonitrile was found to be more reactive than methacrylonitrile toward graft copolymerization. © 1994 John Wiley & Sons, Inc.     

Graft copolymerization of 4-vinylpyridine and methyl acrylate onto polyethylene film by radiochemical method

Graft copolymerization of 4-vinyl pyridine (4-VP) and methyl acrylate (MA) onto polyethylene (PE) was studied in aqueous medium in air by the mutual irradiation method. The percentage of grafting was determined as a function of the (i) total dose, (ii) monomer concentration, and (iii) amount of water. The effect of different alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and pentanol on the percentage of grafting of 4-VP and MA was studied. The effects of different amines on the percentage of grafting of 4-VP were also studied. The graft copolymers were characterized by IR spectroscopy and thermal analysis and by identifying the isolated polymer from the grafted film. Grafted PE film was tested for permeability behavior and was found to be permeable to a 0.5% aqueous sodium chloride solution. A plausible mechanism is suggested to explain the grafting of 4-VP and MA onto PE film. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 599–610, 1998     

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     

Graft copolymerization of acrylonitrile and its binary mixture with 4-vinyl pyridine onto isotactic polypropylene powder by preirradiation method

Graft copolymerization of acrylonitrile (AN) and its binary mixture with 4-vinyl pyridine (4-VP) onto isotactic polypropylene powder in aqueous medium, using γ-rays as an initiator, was studied. Optimum conditions for affording maximum percentage of grafting were evaluated. Rate of grafting (Rg) of AN and binary mixture (4-VP + AN) was determined as a function of total initial monomer concentrations. The graft copolymers were characterized by IR spectroscopy and thermogravimetric analysis. © 1995 John Wiley & Sons, Inc.     

Co(III) acetylacetonate-complex-initiated grafting of N-vinyl pyrrolidone on cellulose in aqueous media

The graft copolymerization of N-vinyl pyrrolidone (N-VP) onto cellulose was carried out with a cobalt acetylacetonate complex Co(acac)₃ as an initiator under a nitrogen atmosphere at 50 ± 0.1°C. The graft yield percentage (%G) obtained as a function of the concentrations of N-VP and Co(acac)₃ and the temperature was used to calculate various other grafting parameters and the grafting rate dependence on the concentrations of monomer, Co(acac)₃ and reaction temperature. The energy of activation (ΔE_a) for the grafting of N-VP onto cellulose was 22.7 kJ/mol within 40–60°C. The molecular weights of the grafted chains and homopolymers were determined viscometrically with a Ubbelohde-type viscometer. Graft yield (%G) in the presence of various additives such as sodium lauryl sulfate, cetyltrimethylammonium bromide, and methanol was studied, and the results are suitably explained. On the basis of the experimental results, a reaction scheme for graft copolymerization is proposed, and a kinetic rate expression is presented. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2286–2296, 2001     

Graft polymerization of 4-vinylpyridine onto cellulosic fibres by the ceric ion method,I. The reaction time effect

A study was made of the time affecting the ceric ion induced grafting of 4-vinylpyridine (4-VP) onto partially carboxymethylated cotton (PCMC) having different degrees of substitution (D.S.). For comparison the same monomer was grafted onto cotton and mercerized cotton. The grafting parameters of these copolymerization reactions were determined. The graft yields for PCMC were significantly higher than those for unmodified cotton and mercerized cotton. The degree of crystallinity of the graft copolymers and of the unmodified cotton and PCMC samples was determined by the X-ray method. The crystallinity index decreased with the presence of grafted polymer. The reaction time effect of the grafting of 2-VP on cotton was also studied.     

Radiation grafting of N,N-dimethylaminoethylmethacrylate and 4-vinylpyridine onto polypropylene by the one- and two-step methods

Summary Radiation grafting of N,N-dimethylaminoethylmethacrylate (DMAEMA) and 4-vinylpyridine (4-VP) from the 50% monomers solutions in toluene and dichloroethane onto polypropylene (PP) films was carried by their mutual γ-irradiation (one-step method). In the two-step method, the grafting of DMAEMA or 4-VP from their solutions in toluene was performed onto PP modified preliminary with the other polymer (poly4-VP or polyDMAEMA). It has been found that chemical structure of PP modified with the first grafted polymer affected the efficiency of the other monomer grafting by the second step. Received: 30 April 2001/Revised version: 21 October 2001/Accepted: 28 November 2001     

Changes in physical properties of methacrylonitrile (MAN)-grafted silk fibers

Changes in physical properties of silk fibers, grafted with methacrylonitrile (MAN), were investigated as a function of the weight gain. The weight gain increased steadily during the first 60 min of reaction and gradually attained an equilibrium value (60%) after about 4 h. The initial tensile resistance of silk fibers decreased by MAN grafting. The crystalline structure of silk fibers remained unchanged, regardless of MAN grafting, however. a minor and broad peak appeared in the X-ray diffraction curves of MAN-grafted silk fibers with a weight gain of 60%, corresponding to the unoriented MAN polymer attached inside the fibers. Molecular orientation of silk fibroin chains in the crystalline regions, evaluated from X-ray diffraction curves, did not change significantly, while both birefringence and isotropic refractive index decreased as the weight gain increased, implying that MAN polymer attached preferentially to the amorphous and not to the crystalline regions. Dynamic vis-coelastic measurements showed that the position at which the E′ value began to decrease shifted to a lower temperature as the weight gain increased. These findings suggest that the thermal movement of silk fibroin molecules was accelerated by the presence of the poly-MAN chains attached to the amorphous regions of silk fibroin fibers. © 1993 John Wiley & Sons, Inc.     

Grafting of vinyl monomers onto natural rubber,II. Graft copolymerization of methyl methacrylate onto natural rubber using tetravalent ceric ions

The use of tetravalent ceric ions to initiate graft-copolymerization of methyl methacrylate onto natural rubber (NR) has been investigated. The rate of grafting has been determined by varying the concentration of monomer and cerium(IV), the temperature and the solvents. The graft yield increases with increasing monomer concentration up to 1.877 M, with further increase of the monomer, the graft yield decreases. The percentage of grafting increases with increasing cerium(IV) concentration up to 0.035 M, thereafter it decreases. With increasing temperature the graft yield increases. The effect of CuSO₄ on the rate of grafting has also been investigated. A plausible mechanism has been suggested and the kinetic rate expressions have been derived.     

Graft copolymerization of methacrylonitrile on kenaf fibers by cerric ion-toluene redox pair

The graft copolymerization of methacrylonitrile onto kenaf fibers by a cerric ion-toluene redox pair was investigated in aqueous media. Graft yield of up to 212% was found, but the grafting efficiency was not greater than 17.6%. At varying concentrations of toluene, the conversion in graft yield passed through a maximum and thereafter decreased by as much as 46% for a two-half increase in the concentration of toluene. Similarly, acetic acid showed an initial increase in graft yield in the concentration range of 0.58-1.17M and a reduction to zero graft at a 11.67M concentration of the acid. Under identical reaction conditions, acetic acid and its derivatives decreased the graft yield in the order trichloroacetic acid > monochloroacetic acid > acetic acid > formic acid. The effect of the chlorinated acids was considered as a composite consisting of normal transfer reactions and a hydrolytic effect, as strong acids, on the grafted polymers. The percentage graft yield showed a normal temperature dependence over the range 30-60°C with a calculated activation energy of 6.52 kcal mol⁻¹. The amount of grafted polymer increased with monomer concentration, but the average molecular weight decreased with the latter, suggesting an enhanced utilization of more grafting sites on the fibers. The water-retention capacity of the graft copolymer showed an 85% reduction in its value over a three fold increase in the graft yield. © 1996 John Wiley & Sons, Inc.     

Modification of carbohydrate polymers via grafting of methacrylonitrile onto pregelled starch using potassium monopersulfate/Fe2+ redox pair

The graft copolymerization of reactive pregelled starch (PGS) with methacrylonitrile (MAN) was performed and the reaction conditions were optimized using potassium monopersulfate (PMPS) in the presence of ferrous ion redox pair as initiator. Emphasis was directed towards increasing the graft formation and decreasing homopolymerization. The grafting parameters were studied with respect to graft yield and graft reaction efficiency percent. In addition, the newly prepared polymethacrylonitrile (polyMAN)‐pregelled starch graft copolymers were applied to cotton textiles to see their suitability as a new sizing agent. Based on the results obtained, appropriate conditions for grafting MAN onto pregelled starch was established and the graft yield was higher under the following conditions: using 0.004 mol l^?1 potassium monopersulfate as initiator, 0.005 mol l^?1 ferrous ion concentration, 0.003 mol l^?1, sulfuric acid, 50 % MAN concentration (based on weight of substrate), material to liquor ratio 1:2.5, reaction time 60 min, and polymerization temperature 40 °C. Finally, fabric samples sized with polyMAN‐pregelled starch graft copolymers acquired higher tensile strength and abrasion resistance than that sized with original pregelled starch, while elongation at break was unaltered. Copyright © 2004 Society of Chemical Industry     

Designing a support for borohydride through grafting onto crosslinked polyvinylpyrrolidone

Crosslinked polyvinylpyrrolidone (PVPy) was grafted with polyvinylpyridine by irradiating the polymer beads in air from a Co⁶⁰ γ-radiation source and then heating with 4-vinylpyridine (4-VP) in water. The percentage of grafting was studied as a function of various reaction parameters and was determined from the increase in weight of PVPy and from the estimation of pyridine rings introduced into the polymer. PVPy-g-poly(4-VP) was treated with sodium in ethanol, which is known to reduce pyridine into piperidine together with small amounts of 1,2,5,6-tetrahydropyridine. On methylation with dimethyl sulfate and alkali, these are further converted into N,N-dimethylpiperidinium groups. The dimethylpiperidinium graft was used to support borohydride ions and the graft copolymer was shown to cleanly reduce several carbonyl compounds to the corresponding alcohols. © 1996 John Wiley & Sons, Inc.     

Grafting vinyl monomers onto silk fibers III. Graft copolymerization of methyl methacrylate onto silk using tetravalent cerium as initiator

The use of tetravalent ceric ions to initiate graft-copolymerization of methyl methacrylate onto silk has been investigated. The rate of grafting has been determined by varying monomer, cerium (IV), temperature, and nature of silk. The graft yield increases with increasing monomer concentration up to 0.65 mol/l and with further increase of monomer, the graft yield decreases. The percentage of grafting increases with increasing ceric ion concentration up to 0.03 mol/l and thereafter it decreases. The rate of reaction is temperature dependent, with increasing temperature, the graft yield increases. The grafting is considerably influenced by chemical modification prior to grafting. The effect of different species of ceric ion and CuSO₄ on the rate of grafting has also been investigated.     

Grafting vinyl monomers onto wool fibers. I. Graft copolymerization of methyl methacrylate onto wool using V5+–thiourea redox system

The graft copolymerization of methyl methacrylate in wool fibers was investigated in aqueous solution using V⁵⁺—thiourea redox system. The rate of grafting was determined by varying monomer, thiourea, acidity of the medium, temperature, nature of wool, different acrylic monomers, and reaction medium. The graft yield increases significantly by increasing reaction time in the initial stages of the reaction but it does slow down on prolonging the duration of grafting. The effect of increasing monomer concentration brings about a significant enhancement in the graft yield. The graft yield increases with increasing thiourea concentration, but beyond 0.0075M, the percentage graft yield decreases. The graft yields are considerably influenced by chemical modification prior to grafting. Wool reduced with thioglycolic acid is more susceptible to grafting than untreated wool; the opposite effect is noted in the case of trinitrophenylated and esterified wools. A suitable kinetic scheme has been proposed and the rate equation has been evaluated.     

Grafting of vinyl monomers onto nylon-6. 1. Graft copolymerization of acrylamide onto nylon-6 using trivalent manganese as initiator

The use of trivalent manganese to initiate graft-copolymerization of acrylamide onto nylon-6 has been investigated. The rate of grafting has been determined by varying monomer, manganese(III), temperature and solvent mixtures. The graft yield increases with increasing monomer concentration up to 0.8 M and with further increase of monomer concentration the graft yield decreases. The percentage of grafting increases with managanese (III) ion concentration up to 5.25 × 10^?3 M and thereafter it decreases. The rate of reaction depends on temperature. Among the solvent composition studied, a water/solvent mixture containing 25% of the solvent seems to constitute the most favourable medium for grafting and with further increase of solvent composition, the graft yield decreases.     

Chlorohydrin water swellable rubber compatibilized by an amphiphilic graft copolymer. I. Synthesis and characterization of compatibilizer PVA‐g‐PBA

The graft copolymerization of butyl acrylate onto poly(vinyl alcohol) with ceric ammonium nitrate as redox initiator in a aqueous medium has been investigated. The formation of graft copolymer was confirmed by means of IR, scanning electron microscopy (SEM), and wide‐angle X‐ray diffraction (WAXD). The percentage of mononer conversion and percentage of grafting varied with concentrations of initiator, nitric acid, monomer, macromolecular backbone (X_n = 1750, M = 80 000), reaction temperature and reaction time. Some inorganic salts and organic solvents have a great influence upon grafting. The reaction mechanism has been explored, and rate equations for the reaction are established. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 977–986, 2000     

Synthesis of a cellulose‐grafted polymeric support and its application in the reductions of some carbonyl compounds

The reduction of carbonyl compounds by borohydride supported on a cellulose–anion exchange resin is known. The synthesis of a graft copolymer of cellulose and poly(4‐vinyl pyridine) [CellO‐g‐poly(4‐VP)] has been carried out with ceric ions as a redox initiator. A postgrafting treatment of CellO‐g‐poly(4‐VP) with sodium borohydride has produced CellO‐g‐poly(4‐VP) borane, a polymer‐supported reducing agent. Optimum conditions pertaining to the maximum percentage of grafting have been evaluated as a function of the concentrations of the initiator, monomer, and nitric acid, amount of water, time, and temperature. The maximum percentage of grafting (585%) has been obtained with 0.927 mol/L of 4‐vinyl pyridine and 0.018 mol/L of ceric ammonium nitrate in 120 min at 45°C. The polymeric support, CellO‐g‐poly(4‐VP) borane, has been used for reduction reactions of different carbonyl compounds such as benzaldehyde, cyclohexanone, crotonaldehyde, acetone, and furfural. The graft copolymer has been characterized with IR and thermogravimetric analysis. The grafted cellulose has been found to be thermally stable. The reduced products have been characterized with IR and NMR spectral methods. The reagent has been reused for the reduction of a fresh carbonyl compound, and it has been observed that the polymeric reagent reduces the compounds successfully but with a little lower product yield. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008