Photo-induced graft copolymerization. XV. Graft copolymerization of methyl methacrylate onto nylon-6 using erythrosin as photoinitiator

The photo-induced graft copolymerization of methyl methacrylate onto nylon-6 was investigated using erythrosin as the photoinitiator. The systems were buffered with phosphate citrate buffer (Na₂HPO₄/citric acid). The graft copolymerization was carried out within the temperature range of 35–50°C and from the corresponding Arrhenius plot, the energy of activation was evaluated. The effect of monomer, initiator, ascorbic acid, etc. on the graft yield has been investigated. Further, the effect of solvent on the rate of grafting has been investigated and the chain transfer constant (C_s) of the solvent has been evaluated. The kinetic data and other events indicate that the overall polymerization takes place by a radical mechanism. A suitable mechanism has been suggested and rate expressions have been derived.     

Radiation induced graft copolymerization V. Graft copolymerization of methyl acrylate onto nylon-6 fiber

The radiation induced graft copolymerization of methylacrylate onto nylon-6 fiber at room temperature and in nitrogen medium was investigated. The effects of monomer, dose rate, inhibitor etc. on the graft yield have been investigated. The effect of solvents on the rate of grafting was studied from which the chain-transfer constant (C_s) of the solvent has been evaluated. Addition of certain inorganic salts was found to act as scavengers. The value of G_b, the number of branches per 100 eV of energy absorbed in the substrate polymer, was calculated. The density, moisture regain, alkali solubility, dyeability and thermal properties of the grafted nylon-6 fiber have been evaluated.     

Trivalent manganese chelate-initiated graft copolymerization of methyl methacrylate onto silk fibers

The graft copolymerization of methyl methacrylate onto silk fibers was investigated in aqueous solution using Mn³⁺ acetyl acetonate [Mn(acac)₃] as initiator. The rate of grafting was determined by varying monomer, acidity of medium, temperature, and reaction medium. The graft yield increases significantly with increase of [Mn(acac)₃] concentration up to 0.01M, and with further increase of [Mn(acac)₃] the graft yield decreases. The effect of the increase of monomer concentration brings about a significant enhancement in the graft yield, and with further increase the graft yield decreases. The rate of reaction is temperature dependent; with increasing temperature, the graft yield increases. Among the solvent composition studied, a water/solvent mixture containing 10% of the solvent seems to constitute the most favorable medium for grafting, and, with further increase of solvent composition, the graft yield decreases. The effect of some inorganic salts, organic solvents, and complexing agents has been investigated.     

Grafting vinyl monomers onto silk fibers: Graft copolymerization of methyl methacrylate onto silk using acetylacetonate Mn(III) complex

The graft copolymerization of methyl methacrylate onto Mulberry silk fibers was studied in aqueous solution using Mn(acac)₃ as initiator. Perchloric acid was found to catalyze the reaction. The rate of grafting was investigated by varying the concentration of the monomer and the complex, acidity of the medium, the solvent composition of the reaction medium, the surfactants, and the inhibitors. The graft yield increases with increasing concentration of Mn(acac)₃ up to 0.01 mol/L, decreasing thereafter. Increase of MMA concentration up to 0.56 mol/L increases graft yield, and thereafter it decreases. Among the various vinyl monomers studied, MMA was found to be most suitable for grafting. Grafting increases up to 7.5 × 10^?3 mol/L of HClO₄ concentration, and thereafter it decreases. A suitable reaction scheme has been proposed and a rate equation has been derived. The energy of activation has been calculated from the Arrhenius plot. The chain transfer constants for various chain transfer solvents have been evaluated from the average molecular weight (M?) of grafted poly(methyl methacrylate).     

Grafting vinyl monomers onto silk fibers. X. Graft copolymerization of methyl methacrylate onto silk using hydrogen peroxide–thiourea redox system

The graft copolymerization of methyl methacrylate onto silk fibers initiated by a hydrogen peroxide–thiourea redox system was investigated under various conditions. The effects of monomer, initiator, temperature, acidity of the medium, and solvent on the rate of grafting were studied. The graft yield increases with the increase of monomer and initiator concentration. The graft yield also increases with the increase of acid concentration upto 22.50 × 10^?2M and thereafter it decreases. The effect of some inorganic salts on the rate of grafting has also been investigated, and a suitable mechanism has been suggested.     

Atom transfer radical copolymerization of methyl methacrylate with N‐cyclohexylmaleimide

Atom transfer radical polymerization has been applied to simultaneously copolymerize methyl methacrylate (MMA) and N‐cyclohexylmaleimide (NCMI). Molecular weight behaviour and kinetic study on the copolymerization with the CuBr/bipyridine(bpy) catalyst system in anisole indicate that MMA/NCMI copolymerization behaves in a ‘living’ fashion. The influence of several factors, such as temperature, solvent, initiator and monomer ratio, on the copolymerization were investigated. Copolymerization of MMA and NCMI in the presence of CuBr/bpy using cyclohexanone as a solvent instead of anisole displayed poor control. The monomer reactivity ratios were evaluated as r_NCMI = 0.26 and r_MMA=1.35. The glass transition temperature of the resulting copolymer increases with increasing NCMI concentration. The thermal stability of plexiglass could be improved through copolymerization with NCMI. © 2000 Society of Chemical Industry     

A study on graft copolymerization of methyl methacrylate onto jute fiber

A kinetic study of the graft copolymerization of methyl methacrylate onto jute fiber using KMnO₄–malonic acid redox initiator system has been made. Effects of the concentrations of malonic acid, monomer, and KMnO₄ on graft yield have been studied. Besides, the effects of temperature, acid, and reaction medium, some inorganic salts on graft yield have been investigated. The most remarkable features of the investigation include the proposition of a mechanism, derivation of rate expression for the grafting process, and characterization of the grafted fiber by thermogravimetric analysis.     

Grafting of vinyl monomers onto silk fibers: Trivalent-manganese-initiated graft copolymerization of acrylamide onto silk fibers

Graft copolymerization of acrylamide (AM) onto silk fibers, using Mn(III)–sulphate as initiator, has been investigated, in aqueous sulphuric acid in the temperature range of 30–55°C. Grafting reaction has been studied by varying the concentration of monomer, Mn(III), sulphuric acid, temperature, and also with the modified silk. The graft yield increases significantly with increase of monomer concentrations to the extent of 0.85M, after which the rate falls. With increase in Mn(III) concentration and H⁺ ion concentration the graft yield increases, but after an optimum concentration a depression in the graft yield is noticed. The rate of the reaction is temperature-dependent; with increase of temperature the graft-on increases. Among the solvent composition studied a solvent/water mixture containing 10% of the solvent seems to constitute the most favorable medium for grafting, and a further increase of solvent composition decreases the graft yield. The effect of various additives such as transition metal salts, aromatic and heterocyclic amines on grafting reaction has been studied. A suitable mechanism for grafting has been proposed. Finally physical characterization such as thermal analysis (TGA) of the grafted samples has been carried out in order to ensure grafting and to study the change in the properties of the fibers.     

Grafting vinyl monomers onto polyester fibers. VI. Graft copolymerization of methyl methacrylate onto PET fibers using tetravalent cerium as initiator

The graft copolymerization of methyl methacrylate onto polyester fibers (PET) was investigated using tetravalent cerium as the initiator. The rate of grafting was found to increase progressively with the initiator and monomer concentrations up to 2.5 × 10^?2M and 70.41 × 10^?2M, respectively. The reaction was found to be catalysed by acid up to 15.0 × 10^?2M. The graft yield increased by increasing temperature. The effect of addition of some solvents and thiourea on the rate of grafting was also investigated. A suitable kinetic scheme has been pictured, and rate equations have been derived.     

Grafting vinyl monomers onto polyester fibers. III. Graft copolymerization of methyl methacrylate onto poly(ethylene terephthalate) using potassium permanganate–oxalic acid redox system

The use of the KMnO₄—oxalic acid redox system to initiate graft copolymerization of methyl methacrylate (MMA) onto poly(ethylene terephthalate) (PET) fiber has been investigated. The rate of grafting was determined by varying the concentrations of monomer, KMnO₄, oxalic acid, acidity of the medium, and temperature. The graft yield increases steadily with increasing KMnO₄ concentration. The graft yield is also influenced with concentration. The graft yield is also influenced with temperature. The effect of certain solvents on the rate of grafting has been investigated, and a suitable reaction mechanism has been proposed.     

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.     

Radiation-Induced graft copolymerization,I. Graft copolymerization of methyl methacrylate onto nylon-6

The radiation-induced graft copolymerization of methyl methacrylate onto nylon fibers was investigated at room temperature. The homopolymer was separated by soxhlet extraction. The graft yield increases with increase of dose rate from 0.1768 to 0.7072 Mrad. The percentage of grafting increase with increasing monomer concentration. Addition of copper sulphate and a non-ionic surfactant, sodium lauryl sulphate, supresses the formation of homopolymer. The value of G_b, the number of branches per 100 eV of energy absorbed in the substrate polymer, and the value of α, the fraction of substrate polymer grafted, have been computed. A kinetic scheme has been suggested.     

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 acrylamide–methylacrylate comonomers onto cellulose using ceric ammonium nitrate

The graft copolymerization of acrylamide–methylacrylate comonomers was carried out using ceric ammonium nitrate as initiator in the presence of nitric acid at 25 ± 1°C. The effects of feed molarity, feed composition, reaction time, and temperature on graft yield (%G) and other grafting parameters were investigated. The determination of rate of ceric (IV) ions disappearance as a function of feed molarity and reaction time was useful in the determination of the rate of ceric (IV) ions consumption during graft copolymerization. The graft yield (%G) in the presence of acrylamide increases because of the synergistic effect of acrylamide comonomer. The composition of the grafted chains (F_AAm) varies on varying the feed composition and reaction temperature but is almost constant during feed molarity variation. The Mayo and Lewis method was used to determine the reactivity ratios of acrylamide (r₁) and methylacrylate (r₂), which are 0.65 and 1.07, respectively. The product of reactivity ratio (r₁ r₂) is less then unity; hence, an alternate arrangement of comonomer blocks in the grafted copolymer chain is proposed. The rate of graft copolymerization of comonomers onto cellulose is second power to the concentration of comonomers and square root to the concentration of ceric ammonium nitrate. Suitable reaction steps for graft copolymerization of comonomers onto cellulose are proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2631–2642, 2002     

Vanadium-cyclohexanone–initiated graft copolymerization of methyl methacrylate onto jute fibers

Graft copolymerization of methyl methacrylate (MMA) was carried out on jute fibers using a V⁵⁺ -cyclohexanone redox initiator system. The effect of the concentration of acid, monomer, and V⁵⁺ on graft yield have been studied. In order to obtain optimum conditions of grafting, the effects of temperature, acid, reaction medium, solvent, and some inorganic salts on graft yield have been investigated. The most remarkable features of the investigation include the proposition of a mechanism and derivation of rate expression for the grafting process. More than 100% grafting could be achieved with the present system.     

Graft copolymerization of methyl methacrylate onto wool by use of ferrous ion–peroxodiphosphate

Polymethyl methacrylate has been graft copolymerized onto wool using a ferrous ion–peroxodiphosphate initiator system in an aqueous methanol medium. Graft copolymerization was carried out at 20°C, 30°C, 40°C, and 50°C. The rate of grafting was found to be dependent on the concentrations of monomer (MMA), ferrous ion (Fe²⁺), peroxodisphosphate (PP), wool (w), and reaction temperature. [Acid], solvent composition and ionic strenghth were also varied to study their effect on grafting. Based on the experimental results, a suitable kinetic scheme was proposed. Rate and thermodynamic parameters were also varied to study their effect on grafting. Based on the experimental results, a suitable kinetic scheme was proposed. Rate and thermodynamic parameters were also evaluated.     

Free‐radical copolymerization kinetics of acrylonitrile and methyl acrylate in [BMIM]BF4

The copolymerization of acrylonitrile (AN) and methyl acrylate (MA) was carried out in ionic liquid [BMIM]BF₄ in the presence of azobisisobutyronitrile (AIBN) as an initiator to investigate the polymerization kinetic, including the copolymerization rate, reactivity ratios, and activation energy. The copolymerization rate equation was established according to the effect of initiator and monomer concentrations on the conversion. The copolymerization rate R_p can be noted as , when the copolymerization was in the steady state. The apparent activation energy is 87.94 kJ/mol, while the value of that in the conventional organic solvent (DMF) is ∼ 81 kJ/mol. The reactivity ratios of the investigate system are r_AN = 0.36 and r_MA = 0.68. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4254–4257, 2006     

Kinetics of ylide-initiated radical copolymerization of 4-vinylpyridine and methyl methacrylate

The ylide-initiated radical copolymerization of 4-vinylpyridine (4-VP) with methyl methacrylate (MMA) at 60°C using carbon tetrachloride as inert solvent yields non-alternating copolymers. The kinetic parameters, average rate of polymerization (R_p) and orders of reaction with respect to monomers and initiator, have been evaluated and the kinetic equation is found to be R_pα[ylide]^0.94 [MMA]^1.0 [4-VP]^1.5. The values of the energy of activation and k_p²/k_t are 48 kJ mol^?1 and 6.6 × 10^?5 litre mol^?1s^?1, respectively. The copolymers have been characterized by IR and NMR spectroscopy.     

Influence of N-acetylglycine on the kinetics of the ceric ion-initiated graft copolymerization of acrylonitrile and methyl methacrylate onto jute fibers

The influence of N-acetylglycine on the kinetics of graft copolymerization of acrylonitrile (AN) and methyl methacrylate (MMA) onto chemically modified jute fibers was studied in the temperature range 40–60°C. The optimum conditions for grafting have been determined by studying the effects of concentrations of monomers, Ce(IV), and N-acetylglycine on the rate of grafting. Besides the effect of time, temperature, and concentration of the acid, the amount of jute fibers and some organic solvents and inorganic salts on the rate of grafting has been investigated. On the basis of experimental findings, a kinetic scheme has been proposed. Infrared spectra of chemically modified jute and grafted jute have been investigated. More than 185% graft yield could be achieved with the present system. Grafting has improved the thermal stability of jute fibers. © 1994 John Wiley & Sons, Inc.     

Free radical copolymerization and kinetic treatment of styrene with N-phenylmaleimide

The copolymerization of styrene (M₁) with N-phenylmaleimide (M₂) in chloroform with 2,2′-azobis(isobutyronitrile) as an initiator was investigated. The kinetic parameters, such as reactivity ratios, overall activity energy, and the effect of molar fraction of monomers on the initial copolymerization rate, were determined. The bimolecular termination of the copolymerization was proved. The treatment method proposed by Yoshimura and colleagues was used to estimate quantitatively the contribution of the charge-transfer complex (CTC) and the free monomers in the copolymerization process. The propagation reactivity ratios of CTC and free monomers were calculated by a new method. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1535–1542, 1997