Graft copolymerization of methyl methacrylate and other vinyl monomers onto cotton fabric using ferrous cellulose thiocarbonate–N-bromosuccinimide redox initiation system

The cellulose thiocarbonate, in the fabric from, was treated first with a freshly prepared ferrous ammonium sulphate (FAS) solution. The sotreated fabric formed, with N-bromosuccinimide (NBS), an effective redox system capable of initiating grafting of methyl methacrylate (MMA) and other vinyl monomers onto the cotton fabric. The effect of the polymerization conditions the polymer criteria, namely, graft yeild, homopolymer, total conversion, and grafting efficiency, was studied. These polymer criteria were found to depend extensively upon concentrations of the Fe²⁺ ion (activator), NBS (initiator), and MMA; pH of the polymerization medium, and duration and temperature of polymerization. Based on detailed investigation of these factors, the optimal conditions for grafting were as follows: Fe²⁺, 1 × 10⁻³ mol/L; NBS, 1 × 10⁻² mol/L; MMA, 4%; pH, 2: polymerization time, 150 min; polymerization temperature, 60°C; material/liquor ratio, 1: 100. Under these optimal conditions, the rates of grafting of different vinyl monomers were in the following sequence: methyl methacrylate ≫ methyl acrylate > acrylonitrile. Other vinyl monomers namely, acrylic acid, and methacrylic acid have no ability to be grafted to the cellulosic fabric using the said redox system. A tentative mechanism for the polymerization reaction is suggested. © 1996 John Wiley & Sons, Inc.     

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

The feasibility of a cellulose thiocarbonate–azobisisobutyronitrile (AIBN) initiation system to induce graft copolymerization of methyl methacrylate (MMA) and other acrylic monomers onto cotton fabric was investigated. Other acrylic monomers were acrylic acid, acrylonitrile, and methyl acrylate. The initiation system under investigation was highly activated in the presence of a metal‐ion reductant or a metal‐ion oxidant in the polymerization medium. A number of variables in the grafting reaction were studied, including AIBN concentration, pH of the polymerization medium, nature of substrate, monomer concentration, duration and temperature of polymerization, and composition of the solvent/water polymerization medium. The solvents used were methanol, isopropanol, 1,4‐dioxane, cyclohexane, benzene, dimethyl formamide, and dimethyl sulfoxide. There were optimal concentrations of AIBN (5 mmol/L), MMA (8%), Fe²⁺ (0.1 mmol/L), Mn²⁺ (8 mmol/L), and Fe³⁺ (2 mmol/L). A polymerization medium of pH 2 and temperature of 70°C constituted the optimal conditions for grafting. The methanol/water mixture constituted the most favorable reaction medium for grafting MMA onto cotton fabric by using the Fe²⁺–cellulose thiocarbonate–AIBN redox system. MMA was superior to other monomers for grafting. The unmodified cotton cellulose showed very little tendency to be grafted with MMA compared with the chemically modified cellulosic substrate. A tentative mechanism for the grafting reaction was proposed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1261–1274, 2004     

Pentavalent vanadium ion-induced grafting of methyl methacrylate onto cotton cellulose

Graft polymerization of methyl methacrylate (MMA) onto cotton cellulose using vanadium pentanitrate as initiator was studied under a variety of conditions. The graft yield increased with increasing initiator concentration up to 8 mmole/l. and then decreased upon further increase in initiator concentration. Increasing MMA concentration from 1 to 5% was accompanied by a significant increase in the degree of grafting. The latter was also affected by the kind and concentration of the acid incorporated in the polymerization medium. Based on graft yields, the efficiency of the acids follows the order H₂SO₄ > HNO₃ > HClO₄. Replacement of the acid with isopropyl alcohol was also examined. An isopropyl alcohol concentration of 10% constitutes the optimal concentration for grafting. Maximum graft yield depends upon the polymerization temperature; it follows the order 50°C ≥ 60°C > 40°C > 30°C > 70°C. Reaction mechanisms for grafting in the presence of acid as well as in the presence of isopropyl alcohol are proposed.     

Grafting of methyl methacrylate to nitrocellulose by ceric ions

Studies were carried out on grafting of various vinyl monomers to nitrocellulose by ceric ions. It was observed that graft copolymerization occurred only with methyl methacrylate (MMA) and methyl acrylate monomer. The variables such as initiator concentration, monomer concentration, time of grafting, and nitrocellulose content on grafting of MMA are discussed. By hydrolyzing away the nitrocellulose backbone, the grafted poly(methyl methacrylate) branches were isolated and the >c?o peak at 1740 cm^?1 in the infrared spectra of these isolated branches gave definite evidence of grafting. The molecular weight of isolated branches has been determined by viscometry. The probable mechanism of grafting may be at the α-carbon atom of primary alcohol or at a C₂-C₃ glycol group of the anhydro glucose unit or at the hemiacetal group of the end unit of nitrocellulose, as nitrocellulose is formed by the partial nitration of cotton cellulose.     

Thermal behavior of graft copolymers of cotton cellulose and acrylate monomers

Cotton cellulose yarn was grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate at various percentages of grafting. The effects of concentration of the initiator, concentration of the acid, and of temperature on grafting was studied and the mechanism discussed. The effect of reactivity of the monomer on the percentage graft-on is pointed out. Thermal behavior of natural and grafted cotton yarn was studied using dynamic thermogravimetry in air at a heating rate of 6°C/min up to a temperature of 500°C. The thermal stabilities of the samples grafted with various acrylate monomers to various percentages of grafting were computed from their primary thermograms by calculating the values of IDT, IPDT, and E^*. The results show that the thermal stability increases with increase in graft-on per cent, and the thermal stabilities of natural cotton and cotton grafted with different monomers are in the order ethyl > methyl > natural cellulose > methyl methacrylate > n-butyl acrylate.     

Graft polymerization of methyl methacrylate onto nylon 6 using pentavalent vanadium as initiator

Pentavalent vanadium ion (V^v)-induced graft polymerization of methyl methacrylate onto nylon 6 was investigated under a variety of conditions. Increasing the V^v-concentration up to 2 mmol/l was accompanied by an enhancement in grafting; the latter was not affected by further increase in V^v-concentration. Unlike grafting, the homopolymer and total conversion tended to increase by increasing V^v concentration. The graft yield enhanced significantly when the MMA-concentration was increased up to 3% further increase in MMA-concentration had no effect on grafting. Raising the polymerization temperature from 50° up to 70°C caused a significant increase in the rates of grafting, homopolymerization and total conversion. Using a solvent-water mixture as medium for polymerization affected considerably the magnitude of grafting. While using methyl alcohol, ethyl alcohol and acetone at any ratio in the solvent-water mixture resulted in decreased grafting, using an isopropyl alcohol-water mixture up to a ratio of 25 : 75 gave rise to increased grafting.     

Grafting of Methacrylic Acid and Other Vinyl Monomers Onto Cotton Fabric Using Ce (IV) Ion–Cellulose Thiocarbonate Redox System

Graft copolymerization of methacrylic acid (MAA) onto cotton fabric using tetravalent ceric ion (Ce^IV)–cellulose thiocarbonate redox system was investigated under different conditions including pH of the polymerization medium (1–4), ceric sulphate (CS) concentration (4–20 m mole/l), MAA concentration (1%–6%), polymerization time (1/4–2 h) and polymerization temperature (0–70°C). Results obtained indicated that the optimal conditions for MAA grafting onto cotton fabric using the said redox system consisted of: [CS], 20 m mole/l; [MAA], 4%; pH of the medium, 2; time, 2 h; temperature, 60 °C keeping a material-to-liquor ratio at 1:0. Applying optimized conditions to different monomers, namely, acrylic acid (AA), methacrylic acid (MAA), acrylamide (Aam), acrylonitrile (AN), butyl acrylate (BuA), methyl methacrylate (MMA), ethyl methacrylate (EMA) and glycidyl methacrylate (GMA) onto the same substrate, the rates of grafting followed the order:

A novel method for vinyl grafting onto cotton fabric using ceric-cellulose thiocarbonate redox system

Treatment of cotton fabric with carbon disulphide in presence of NaOH resulted in cellulose thiocarbonate. The latter formed a complex when treated with ceric ammonium nitrate (CAN). After being thoroughly washed, the Ce^IV cellulose thiocarbonate was capable of initiating vinyl graft polymerization onto cotton fabric without homopolymer formation. The graft yield obtained with methyl methacrylate was found to increase by increasing CAN from zero to 50 mmol/l at temperatures from 60 to 80°C. Grafting was greatly favoured at pH 2; alkaline pH offset grafting. Incorporation of up to 7% of methanol, ethanol, or isopropanol in the aqueous polymerization medium enhanced grafting significantly with the certainty that the highest graft yield was obtained with isopropanol; using higher alcohol percentages decreased grafting. The rate of grafting showed an initial fast rate followed by a slower rate; 60 minutes reaction time proved appropriate for grafting irrespective of the condition used. In addition to methyl methacrylate the ability of Ce^IV-cellulose thiocarbonate to induce grafting of acrylonitrile and acrylamide was also examined. The rate of grafting followed the order methyl methacrylate > acrylonitrile > acrylamide.     

Peroxydiphosphate–metal ion–cellulose thiocarbonate redox system‐induced graft copolymerization of vinyl monomers onto cotton fabric

The grafting of methacrylic acid (MAA) and other vinyl monomers onto cotton cellulose in fabric form was investigated in an aqueous medium with a potassium peroxydiphosphate–metal ion–cellulose thiocarbonate redox initiation system. The graft copolymerization reaction was influenced by peroxydiphosphate (PP) concentration, the pH of the reaction medium, monomer concentration, the duration and temperature of polymerization, the nature of vinyl monomers, and the nature and concentration of metallic ions (activators). On the basis of a detailed investigation of these factors, the optimal conditions for the grafting of MAA onto cotton fabric with the said redox system were as follows: [Fe²⁺] = 0.1 mmol/L, [PP] = 2 mmol/L, [MAA] = 4%, pH‐2, grafting time = 2 h, grafting temperature = 70°C, and material/liquor ratio = 1 : 50. Under these optimal conditions, the graft yields of different monomers were in the following sequence: MAA ? acrylonitrile > acrylic acid > methyl acrylate > methyl methacrylate. The unmodified cellulosic fabric (the control) had no ability to be grafted with MAA with the PP–Fe²⁺ redox system. The percentage of grafting onto the thiocarbonated cellulosic fabric was more greatly enhanced in the presence of iron salts than in their absence. This held true when the lowest concentrations of these salts were used separately. A suitable mechanism for the grafting processes is suggested, in accordance with the experimental results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1879–1889, 2003     

Gamma-induced polymerization and grafting of a novel phosphorous-, nitrogen-, and sulfur-containing monomer on cotton fabric to impart flame retardancy

Diethyl (acryloyloxy) ethylthiophosphoramidate (DEAETPN), a novel phosphorus-, nitrogen-, and sulfur-containing monomer, was synthesized in a two-step reaction. The monomer was polymerized and grafted onto cotton fabric by gamma radiation method. Effect of methyl methacrylate (MMA) on percentage grafting (Pg) of DEAETPN on cotton fabric was studied, and it was found that small amount of MMA increases Pg on cotton fabric. The monomer, polymer, and the grafted cotton fabric were characterized by spectroscopic and thermogravimetric techniques. Flame retardant property of the modified cotton fabric was studied by the Shirley Manual Flammability Tester. The flame retardancy of cotton-g-DEAETPN by gamma radiation method and living radical polymerization method was compared. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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 vinyl monomers onto modified cottons. VIII. Dimethylaniline–benzyl chloride-induced grafting of methyl methacrylate onto partially carboxymethylated cotton

The feasibility of dimethylaniline (DMA)–benzyl chloride (BC) mixture to initiate graft polymerization of methyl methacrylate (MMA) onto partially carboxymethylated cotton was examined. The graft yield depends on the nature of the solvent used along with water; ethanol proved to be the best at a water;ethanol ratio of 90:10. Considerable grafting occurred in the presence of acetic acid at a concentration of 200 mmol/l. Higher concentrations of this acid decrease grafting significantly. The graft yield obtained in the presence of formic acid was much lower than that obtained in the presence of acetic acid. Inclusion of hydrochloric or sulfuric acid in the graft polymerization system prevent grafting. A DMA–BC mixture at a concentration of 0.08:0.087 mole/l. constitutes the optimal concentration for grafting. This contrasts with 0.32:0.35 mole/l. for total conversion. The rate of grafting increases by raising the polymerization temperature; it follows the order 50°>60°>65°>70°>75°C. Furthermore, increasing the monomer concentration caused a significant enhancement in the graft yield and total conversion.     

Grafting onto wool,XVII. Graft copolymerization of methyl acrylate and ethyl acrylate by use of VO(acac)2 as initiator. Comparison of monomer reactivities

Graft copolymerization of acceptor monomers methyl acrylate and ethyl acrylate onto Himachali wool fiber has been studied in aqueous medium by using vanadium oxyacetyl acetonate as initiator at 40, 50, 60, and 70°C. Graft copolymerization was carried out for various reaction periods and nitric acid was found to catalyse the reaction. Percentage of grafting and percent efficiency have been determined as functions of concentration of nitric acid, concentration of initiator, concentration of monomer, time, and temperature. Under optimum conditions, methyl acrylate and ethyl acrylate afforded maximum grafting to the extent of 28.4 and 18.5%, respectively. Relative reactivities of methyl acrylate and ethyl acrylate towards grafting have been compared with those of methyl methacrylate, acrylic acid and vinyl acetate reported earlier from this laboratory. Different vinyl monomers showed the following reactivity order: MMA > MA > EA > AAc > VAc. Several grafting experiments were carried out in the presence of various additives which included tert-butylhydroperoxide (TBHP), dimethylsulfoxide, pyridine, and dimethylformamide. Only TBHP was found to enhance grafting to a considerable extent, other additives decrease percent grafting of both methyl acrylate and ethyl acrylate.     

Natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) blends

The grafting of the methyl methacrylate (MMA) monomer onto natural rubber using potassium persulfate as an initiator was carried out by emulsion polymerization. The rubber macroradicals reacted with MMA to form graft copolymers. The morphology of grafted natural rubber (GNR) was determined by transmission electron microscopy and it was confirmed that the graft copolymerization was a surface‐controlled process. The effects of the initiator concentration, reaction temperature, monomer concentration, and reaction time on the monomer conversion and grafting efficiency were investigated. The grafting efficiency of the GNR was determined by a solvent‐extraction technique. The natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) (NR‐g‐MMA/PMMA) blends were prepared by a melt‐mixing system. The mechanical properties and the fracture behavior of GNR/PMMA blends were evaluated as a function of the graft copolymer composition and the blend ratio. The tensile strength, tear strength, and hardness increased with an increase in PMMA content. The tensile fracture surface examined by scanning electron microscopy disclosed that the graft copolymer acted as an interfacial agent and gave a good adhesion between the two phases of the compatibilized blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 428–439, 2001     

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).     

Photografting of PVC containing N,N‐diethyldithiocarbamate groups with vinyl monomers

Poly(vinyl chloride) (PVC) with pendent N,N‐diethyldithiocarbamate groups (PVC–SR) was prepared through the reaction of PVC with sodium N,N‐diethyldithiocarbamate (NaSR) in butanone and used as a photoinitiator for the grafting polymerization of three vinyl monomers [styrene (St), methyl methacrylate (MMA), and acrylamide (Am)]. The effects of ultraviolet (UV) irradiation time, PVC–SR amount, and the monomer amount on grafting and grafting efficiency were investigated. The results showed that PVC–SR could initiate the polymerization of three vinyl monomers effectively and obtained crosslinked copolymers. The grafting and grafting efficiency of styrene and methyl methacrylate were higher than those of acrylamide. The polymerization activity of three monomers was acrylamide > methyl methacrylate > styrene. By analyzing the UV spectrum of PVC–SR with a different irradiation time, it was confirmed that PVC–SR was dissociated mainly into macromolecular the sulfur radical PVC–S · and the small molecular carbon radical · C(S)N(C₂H₅)₂; the grafting polymerization mechanism was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2569–2574, 2000     

Azobisisobutyronitrile-induced vinyl graft polymerization onto nylon 66

The presence of nylon 66 during polymerization of methyl methacrylate (MMA) under the influence of azobisisobutyronitrile (AIBN) produces a nylon-PMMA graft copolymer. The copolymerization reaction is greatly influenced by the reaction medium, temperature and time of the reaction, concentration of MMA, and addition of metallic ions. Polymerization in pure organic solvents brings about little or no grafting. Incorporation of water into the polymerization system enhances grafting significantly. A reaction medium of a water/solvent mixture in a ratio of 75:25 constitutes the most favorable medium for the grafting reaction in question. Of the solvents examined, methanol, ethanol, propanol, isopropanol, and acetone work extremely well. Increase in reaction time is accompanied by an increase in the graft yield. The same holds true for the reaction temperature; the graft yield is much higher at 70 than at 50°C and follows the order 70°C > 60°C > 50°C. Increasing MMA concentration also causes considerable enhancement of the graft yield. The presence of 0.01M cupric sulfate in the polymerization system brings about an eightfold increase in the graft yield, whereas the presence of ferric sulfate at the same concentration causes a sixfold increase. The mode of initiation of grafting seems to be different in the presence of metallic ions than in their absence. A mechanism for the reactions involved in the both cases has been proposed.     

Graft copolymerization with a new class of acidic peroxo salts as initiator. V. Grafting of methyl methacrylate onto jute fiber using potassium monopersulfate catalyzed by Fe(II)

Graft copolymerization of methyl methacrylate (MMA) onto jute fibers was studied in an aqueous solution using a new class of acidic peroxo salt, potassium monopersulfate, as initiator, under the catalytic influence of Fe(II) under nitrogen atmosphere. The grafting reaction was influenced by the reaction time, temperature, and concentrations of monomer, initiator, and jute fibers. The grafting reactions have also been studied in the presence of various salts and solvents. The maximum grafting percent (385.4%) has been observed at 35°C for the concentration of monomer (1.4082M), initiator (12.9 × 10^?3M), catalyst (2.5 × 10^?4M), and solvent (acetic acid) composition of (40:60) for a reaction time of 6 h. From the experimental results a suitable mechanism for the graft initiation and termination has been put forth. The graft copolymers have been characterized, and their improved properties such as tensil strength tested.     

Graft copolymerisation of vinyl monomers on modified cottons. VII. Grafting by chain transfer

Grafting of methyl methacrylate on cellulosic materials by chain transfer under the catalytic influence of azobisisobutyronitrile (AIBN) was extensively studied. The graft yield is influenced by reaction time, temperature, monomer and initiator concentration, reaction medium and nature of the substrate. In general, the grafting reaction shows an induction period after which the polymerisation proceeds rapidly. The graft yield increases and the induction period decreases by rising the reaction temperature from 50 to 70°C. This is also the case when the monomer concentration was increased from 2 to 6%. Increasing the AIBN concentration up to 0.01 M causes a significant enhancement in grafting while further increase brings about a marked fall in the graft yield. Among the reaction media studied, a water/solvent mixture containing 25% of either methanol, ethanol, propanol, butanol or acetone seems to constitute a reaction medium where the monomer and initiator are completely miscible and the swelling of cellulose by water is not hindered by the presence of these solvents. Increasing the solvent ratio in the water/solvent mixture causes a considerable decrease in the graft yield. The polymer content of the cellulosic materials, i. e. the graft yield, follows the order: partially carboxymethylated cotton > cotton treated with 12N sodium hydroxide > cyanoethylated cotton > cotton treated with 0.5 N sodium hydroxide > purified cotton. In addition, proof of grafting was provided by the fractional precipitation method.     

Graft polymerization of some vinyl monomers onto acrylic rubber. I. Chain transfer and grafting reaction

The grafting reactions of styrene (St), methyl methacrylate (MMA), and vinyl acetate (VAc) were investigated in the presence of n-butyl acrylate–acrylonitrile copolymer. Results showed that the nature of monomer and initiator were the major factors influencing the grafting activity. The grafting efficiency was 0.87 for St, 0.26 for MMA, and 0.18 for VAc under the most favorable conditions. Acrylic rubber reduced the rate of polymerization, and the retarding effect increased in the order St, MMA, VAc. The chain transfer constants for acrylic rubber were evaluated to be 4.8 × 10^?4 for St, 1.27 × 10^?3 for MMA, and 1.45 × 10^?3 for VAc. The rate of polymerization and the grafting efficiency decreased with increasing acrylonitrile content in acrylic rubber, while the chain transfer constant of St for acrylic rubber remained practically unchanged.