Pentavalent vanadium ion–cellulose thiocarbonate redox-system induced grafting of methyl methacrylate and other vinyl monomers onto cotton fabric

Cellulose thiocarbonate was prepared by reacting cotton cellulose fabric with carbon disulphide in the presence of sodium hydroxide. The treated fabric formed, with pentavalent vanadium ion, an effective redox system capable of initiating grafting of methyl methacrylate (MMA) and other monomers no+o the cotton fabric. The dependence of grafting on vanadium concentration, pH of the polymerization medium, temperature and duration of grafting, nature and concentration of monomer, and solvent/water ratio was studied. The results indicated that increasing the pentavalent vanadium (V^v) concentration up to 60 mmol/L was accompanied by enhancement in the rate of grafting; the latter was not affected by further increase in V^v concentration. Maximum grafting yield was achieved at pH 2; grafting fell greatly at higher pH. The rate of grafting followed the order: 70° > 60° > 50°C. The graft yield increased significantly by increasing the MMA concentration from 0.5 to 5%. Of the solvents studied, n-propanol and isopropanol enhanced the grafting rate provided that a solvent/water ratio of 5 : 95 was used; a higher solvent ratio decreased the magnitude of grafting. Other solvents, namely, methanol, ethanol, n-butanol, and acetone, in any proportion, decreased the rate of grafting. With the monomer used, the graft yield followed the order: methyl methacrylate > methyl acrylate > methacrylic acid > ethyl methacrylate > acrylic acid. Also reported was a tentative mechanism for vinyl-graft copolymerization onto cotton fabric using cellulose thiocarbonate-V^v. © 1993 John Wiley & Sons, Inc.     

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).     

Radiation‐induced graft polymerization of methyl methacrylate onto ultrahigh molecular weight polyethylene in the presence of a metallic salt and acid

An attempt was made to graft methyl methacrylate (MMA) onto ultrahigh molecular weight polyethylene preirradiated in air in the presence of a metallic salt and acid. The grafting yield increased with increasing monomer concentration. The maximum grafting yield was around a 60 vol % monomer concentration. The results showed that the inclusion of FeSO₄ · 7H₂O and sulfuric acid in MMA grafting solutions was extremely beneficial and led to a most unusual synergistic effect in the radiation grafting, much more than with only a metallic salt. However, CuSO₄ · 5H₂O led to a detrimental effect. It is believed that sulfuric acid accelerates the decomposition of hydroperoxides in the presence of metallic salts such as Fe²⁺, inhibiting homopolymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2348–2356, 2002     

Graft polymerization of methyl methacrylate on poly(ethylene terephthalate) fibers using H2O2 as initiator

The presence of poly(ethylene terephthalate) (PET) fibers during polymerization of methyl methacrylate (MMA) using H₂O₂ as initiator resulted in a substantial, constant increase in the weight of the fibers after repeated extraction with acetone. Fractional precipitation curves of the extracted PET—MMA polymerization product and a physical mixture of PET and PMMA were different, indicating that the interaction of MMA with PET involved grafting. The magnitude of the latter enhanced considerably by increasing H₂O₂ concentration up to 30 mequiv/L, then decreased by further increasing H₂O₂ concentration. There was also an optimal temperature (80°C) for grafting; below or above this temperature, lower grafting was obtained. Similarly, carrying out the polymerization reaction at different pH values revealed that pH7 constituted the optimal. On the other hand, grafting increased upon increase of the methyl methacrylate concentration within the range studied (8–20%). Incorporation of Cu²⁺ or Fe³⁺ ions in the polymerization medium caused a decrement in grafting, irrespective of the metallic ion concentrations. Using methylene chloride as a swelling agent for the fibers failed to enhance the susceptibility of the latter toward grafting. On the contrary, tetrachloroethane was quite promising in this regard. The homopolymer formed during grafting was also reported.     

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     

Graft copolymerization of methyl methacrylate onto rubber‐wood fiber using H2O2 and Fe2+ as an initiator system

Methyl methacrylate (MMA) was successfully grafted onto rubber‐wood fiber in a free‐radical solution polymerization initiated by ferrous ion and hydrogen peroxide. The effects of the reaction parameters (reaction temperature, reaction period, influence of hydrogen peroxide, ferrous ammonium sulfate, and monomer concentrations) were investigated. The grafting percentage showed dependency on H₂O₂, Fe²⁺, and monomer concentrations, as well as reaction temperature and reaction period. The optimum reaction temperature was determined to be about 60°C and the reaction period was 60 min. The optimum concentration of H₂O₂ was 0.03M and optimum amounts of Fe²⁺ and MMA were 0.26 mmol and 2.36 × 10^?2 mol, respectively. Poly(methyl methacrylate) (PMMA) homopolymer was removed from the graft copolymer by Soxhlet extractor using acetone. The presence of PMMA on the fiber was shown by FT‐IR spectroscopy and gravimetric analysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2499–2503, 2003     

Graft copolymerization of nylon 6 with methyl methacrylate using dimethylaniline/Cu2+ ion system

The ability of dimethylaniline (DMA)/Cu²⁺ ion initiator to induce grafting of methyl methacrylate (MMA) onto nylon 6 was investigated under a variety of conditions. It was found that the graft yield is dependent on the concentration of the Cu²⁺ ion, of DMA, and of MMA. While the graft yield increases as the monomer concentration increases, there are optimal concentrations of DMA and Cu²⁺ ion. Below or above these concentrations, lower grafting occurred. The type of cupric salt also affects grafting to varying degrees. While the presence of CuSO₄ and Cu(NO₃)₂ accelerates grafting, the presence of CuCl₂ offsets the reaction. Increasing the reaction temperature and reaction time favorably influences grafting. Addition of acetic acid enhances grafting, whereas formic acid decreases grafting. Preswelling of nylon with formic acid leaves the susceptibility of nylon toward grafting practically unaltered. Studies of the copolymerization reaction was not confined to the graft yield but was extended to homopolymer formation and total conversion.     

Synthesis and characterization of oil sorbers based on docosanyl acrylate and methacrylates copolymers

Docosanyl acrylate (DCA) monomer was copolymerized with different monomer feed ratios of cinnamoyloxy ethyl methacrylate (CEMA) or methyl methacrylate (MMA) monomer to produce different compositions for DCA/CEMA or DCA/MMA copolymer with low conversions.¹H NMR spectroscopy was used to confirm the copolymer structure. DCA was crosslinked with different mol % of CEMA or MMA using dibenzoyl peroxide as initiator and various weight percentages of either 1,1,1‐trimethylolpropane triacrylates or 1,1,1‐trimethylolpropane trimethacrylates crosslinkers. The effects of monomer feed composition, crosslinker concentration, and the hydrophobicity of the copolymer units on swelling properties of the crosslinked polymers were studied through the oil absorbency tests. The network parameters, such as polymer solvent interaction (χ), effective crosslink density (υ_e), equilibrium modulus of elasticity (G_T), and average molecular weight between crosslinks (M_c), were determined and correlated with the structure of the synthesized copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of antisolvent carbon dioxide on the polymerization of methyl methacrylate in different solvents

Polymerization of methyl methacrylate (MMA) in chloroform (CF), ethyl acetate (EA), and iso-amyl acetate (iAA) with compressed CO₂ as antisolvent has been carried out at 333.2 K and different monomer concentrations. The results show that at the low monomer concentration (1 mol l⁻¹) the addition of the antisolvent CO₂ reduces the yield and the molecular weight of the poly(methyl methacrylate) (PMMA). At the higher monomer concentration (4 mol l⁻¹) the yield decreases initially, and then increases with the increase of CO₂ pressure or the volume expansion ratio (VER) of the solution. The molecular weight and the molecular weight distribution of the products also vary with VER.     

Grafting of methyl methacrylate onto guar gum by hydrogen peroxide initiation

Graft copolymerization of methyl methacrylate (MMA) onto guar gum (GG) in aqueous slurry has been carried out using hydrogen peroxide (H₂O₂) as initiator. The copolymers were characterized by infrared spectroscopy. The grafting parameters like percent grafting, grafting efficiency, percent add-on, and the grafting frequency were determined, and the effect of reaction time, concentration of initiator, and [GG]/[MMA] ratios on the grafting parameters have been discussed. The decrease in % add-on at increasing concentration of H₂O₂ indicated enhancement in the rate of homopolymerization of methyl methacrylate.     

Grafting of methyl methacrylate onto Antheraea pernyi silk fiber with the assistance of supercritical CO2

Graft copolymerization of methyl methacrylate (MMA) onto Antheraea pernyi silk fibers, initiated by benzoyl peroxide in the supercritical CO₂ was investigated. The grafting degree was determined as a function of impregnating pressure, impregnating time, monomer concentration, initiator concentration, and reaction time. The structural properties of MMA‐grafted fiber were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Grafted MMA was chemically bonded and/or physically adhered to the surfaces of the fibers. The grafted silk fibers exhibited two steps of weight loss according to the characteristic of each component as demonstrated by the thermogravimetric analysis. The water‐retention values indicated that the hydrophobic nature of the fibers was improved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1299–1305, 2006     

Graft copolymerization onto starch. IV. Grafting of methyl methacrylate to granular native potato starch by manganic pyrophosphate initiation

A study has been made of graft copolymerization of methyl methacrylate onto native potato starch in aqueous slurry at 30°C. As Mn³⁺ concentration was increased from 0.15 X 10^-3M to 1.0 X 10^-3M, conversion of monomer to polymer and add-on of polymer to starch increased and frequency of grafts (anhydroglucose units per grafted chain) decreased sharply. The average molecular weights of the PMMA grafts also decreased in this range. At Mn³⁺ concentrations from 1.0 X 10^-3M to 3.0 X 10^-3M, only minor changes in grafting parameters were observed. When the amount of starch charged per batch was increased threefold, the add-on decreased sharply, the molecular weight increased slightly, and the conversion of MMA monomer to polymer remained almost constant. The increase in frequency of grafts (AGU/chain) was almost directly proportional to the increase in the amount of starch charged. In all cases the average molecular weights of grafts were of the order of 10⁶ and the grafting efficiencies high, normally greater than 85%. These results were compared with those previously obtained for grafting of acrylonitrile onto starch. They were interpreted in terms of initial (Mn³⁺)/(AGU) ratio, total number of radicals initiating grafting, and compatibility of methyl methacrylate monomer with poly(methyl methacrylate) chains.     

Grafting vinyl monomers onto wool fibers: Graft copolymerization of methyl methacrylate onto wool fibers using vanadyl acetyl acetonate complex

The graft copolymerization of methyl methacrylate (MMA) onto native and reduced Indian Chokla wool fibers was studied in aqueous solution using the acetylacetonate oxovanadium (IV) complex. The rate of grafting was investigated by varying the concentration of the monomer and the complex, acidity of the medium, and the solvent composition of the reaction medium. The graft yield increases with increasing concentration of the initiator up to 8.75 × 10^?5 mol/L, of the monomer up to 0.5634 mol/L, and thereafter it decreases. MMA was found to be the most active monomer when compared to other vinyl monomers. Grafting increases with increasing concentration of HClO₄ and with increasing temperature. Reduced and oxidized wools were found to be better substrates than untreated, esterified, crosslinked, and trinitrophenylated wools. The extent of grafting was mostly dependent upon the concentration of ? SH groups in case of reduced wool. A suitable reaction scheme has been proposed and the activation energy was calculated from Arrhenius plot.     

Unexpected effect of the monomer concentration on the rate of a radical polymerization

The radical polymerization of vinyl monomers is usually initiated by physical and chemical means. After an increasing polymerization rate, R_p, at low monomer concentrations, some reactive systems show an unexpected minimum for R_p at high enough monomer concentrations. The radical polymerization of methyl methacrylate (MMA) initiated by the redox system D -glucose–ceric ion at varying MMA concentration is discussed. The peculiar behaviour of R_p is explained by the presence of two circumstances: the initiation rate from D -glucose radicals does not depend on MMA concentration when most of the D -glucose radicals formed react by adding to monomer, and the radical chains initiated by D -glucose radicals undergo mutual termination with a portion of the radical chains initiated by monomer radicals. Some information about the nature of the polymer end-groups is reached from the mechanistic approach.     

Synthesis and kinetics of ascorbic acid initiated graft copolymerized delignified cellulosic fiber

Graft copolymerization of delignified Grewia optiva fiber with methyl methacrylate (MMA) as vinyl monomer was attempted using ascorbic acid/H₂O₂ as redox initiator. Different reaction conditions affecting the grafting percentage (P_g) were optimized to get the maximum P_g (32.56%) of MMA onto delignified Grewia optiva fibers. Grafted and ungrafted fibers were subsequently subjected to evaluation of physico‐chemical properties such as swelling behavior and acid and alkali resistance. The rate expression for the grafting reaction (R_g = k [ASC]^0.12 [H₂O₂]^0.53 [MMA]^0.05) was evaluated and a suitable mechanism for grafting was suggested. The overall activation energy of the copolymerization reaction was found as 11.97 kJ mol^?1 at temperature range 25–65°C. Further, morphological and structural analysis of raw, delignified, and grafted Grewia optiva‐g‐poly(MMA) were studied by using Fourier‐transform Infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, and thermogravimetric analysis.The tensile properties of grafted and ungrafted fiber samples were also reported. POLYM. ENG. SCI., 55:474–484, 2015. © 2014 Society of Plastics Engineers     

Grafting onto wool fibers: Graft copolymerization of methyl methacrylate onto wool fibers initiated by KHSO5/Fe(III) couple

Graft copolymerization of methyl methacrylate (MMA) onto wool fibers has been carried out in an aqueous medium under deaerated condition initiated by potassium monopersulphate (KHSO₅/Fe(III) system, at varying concentration of the reactants and temperature. The effect of various salts and organic solvents on the extent of grafting has also been studied. Maximum graft percentage of 210.8% was obtained in 4 h at 40°C with the concentration of MMA (0.46 M), KHSO₅ (0.0195 M), Fe(III) (1.25 × 10^?4 M) in the presence of 50% formic acid. Various improved properties of the grafts have been studied and compared with the parent fiber.     

Preparation and properties of silicone‐containing poly(methyl methacrylate) gels

Poly(methyl methacrylate) (PMMA) gels with varying amounts of silicone and solvent and constant amounts of crosslinker were prepared by solution free radical crosslinking copolymerization of methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDM), tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTES) comonomer systems. They were then studied in benzene at a total monomer concentration of 3.5 mol L^?1 and 70 °C. The conversion of monomer, volume swelling ratio, weight fraction and gel point were measured as a function of the reaction time, silicone concentration and benzene content up to the onset of macrogelation. Structural characteristics of the gels were examined by using equilibrium swelling in benzene, gel fraction and Fourier‐transform infrared (FTIR) analysis. The morphology of the copolymers was also investigated by SEM. Based on the obtained results, it was concluded that the FTIR data did not have the capacity to show the presence of the VTES or TEOS moiety in these kinds of copolymers. On the other hand, the variation of weight fraction of gel, W_g, and its equilibrium volume swelling ratio in benzene, q_v, exhibited the same behaviour as that of MMA/EGDM copolymers. Also, the dilution of the monomer mixture resulted in an increase in the gel point and swelling degree and a decrease in the percent of conversion and gel fraction. Finally, TEOS is not an ideal silicone compound for reaction in the MMA/EGDM copolymerization system, whereas VTES is a suitable silicone comonomer for this system and it has been proved useful. Copyright © 2005 Society of Chemical Industry     

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.     

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.     

Grafting onto wool. XVI. Graft copolymerization of vinyl monomers by use of TBHP–FAS as redox initiator

Methyl acrylate (MA), methyl methacrylate (MMA), and n-butyl vinyl ether (n-BVE) have been graft-copolymerized onto Himachali wool in an aqueous medium by using tertiary butyl hydroperoxide ferrous ammonium sulfate (TBHP-FAS) redox system at 40°C, 50°C, 60°C, and 70°C for various reaction periods. Percentage of grafting and percent efficiency have been determined as functions of concentration of monomers, molar ratios of [TBHP]/[FAS], time and temperture. Molar ratios of [TBHP]/[FAS] were found to influence grafting of different monomers studied. Chemical evidence indicates that a covalent bond formation occurs between grafted polymeric chain and backbone polymer. The rate of grafting (R_p) and induction period (I_p) of different monomers towards graft copolymerization were determined as function of total initial monomer concentrations. R_p and I_p of n-BVE are independent of total initial monomer concentrations while R_p and I_p of both MA and MMA were found to depend on the total initial monomer concentrations. MA, MMA, and n-BVE were found to differ in reactivity towards grafting onto wool in the presence of (TBHP-FAS) redox system; the following reactivity order was observed: MMA > MA > n-BVE.