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     

Grafting of acrylic acid onto flax fibers using Mn(IV)‐citric acid redox system

When the flax fibers (machine tow) were treated with KMnO₄ solution, MnO₂ was deposited over‐all the fiber surface. The amount of MnO₂ deposited relied on the KMnO₄ concentration. Subjecting the flax‐containing MnO₂ to a solution consisting of monomer (acrylic acid, AA) and citric acid, CA (or any acid used in this work) resulted in formation of poly(AA)‐flax graft copolymer. Dependence of the polymer criteria, namely, the total percentage conversion (%TC) and the carboxyl content of the grafted flax fibers on various grafting parameters, viz., concentrations of the redox pair as well as AA, material‐to‐liquor ratio (M/R), duration and temperature of polymerization, kind of the acid and kind of the flax fibers pretreatment was studied systematically. The results indicated that the polymerizability of AA molecules, expressed as %TC (i.e., counting both grafting and homopolymerization) and thence the carboxyl content (i.e., evaluating the extent of AA grafting along the flax backbone) was optimized with the following conditions: [AA], 100% (based on weight of flax fibers, owf); [CA], 0.4 meq/1 g flax; [MnO₂], 0.4 meq/1 g flax; polymerization temperature, 40°C; polymerization time, 30 min; and the M/R, 1 : 50. A tentative mechanism for grafting of flax fibers with AA using MnO₂‐acid redox system was elucidated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3028–3036, 2006     

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.     

Elucidation of the nanoparticle effect on the grafting of vinyl monomers onto cotton fabric

The grafting emulsion polymerization of vinyl monomers onto cotton was carried out in the presence of double‐modified montmorillonite clay. The obtained results show that grafting with glycidyl methacrylate/montmorillonite gave a higher rate of grafting than grafting with methyl methacrylate/montmorillonite in all clay percentages, and also, the grafting yield of glycidyl methacrylate monomer onto cotton in the presence of montmorillonite clay had a higher value than that in the absence of the clay for all factors studied. Cotton grafted with glycidyl methacrylate/montmorillonite with a graft yield of about 50% was prepared according to the emulsion polymerization technique and was treated with different concentrations of dibutylamine solutions ranging from 1 to 4%. The obtained samples were characterized according to nitrogen content, thermal stability, scanning electron microscopy, mechanical properties, water absorption, and color strength according to acid, basic, and reactive dyes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modification of acrylonitrile–butadiene–styrene terpolymer by grafting with maleic anhydride in the melt. I. Preparation and characterization

The graft copolymerization of maleic anhydride (MAH) onto acrylonitrile–butadiene–styrene terpolymer (ABS) was carried out with dicumyl peroxide (DCP) and benzoyl peroxide (BPO) as the binary initiators and with styrene as the comonomer in the molten state. IR spectra confirmed that MAH was successfully grafted onto the ABS backbone. A reaction mechanism was proposed: the grafting most likely took place through the addition of MAH radicals to the double bond of the butadiene region of ABS. Influences such as the MAH concentration, the initiators and their concentrations, the reaction temperature, the rotating speed, and the comonomer concentration were studied. The results indicated that using styrene as a comonomer and DCP/BPO as binary initiators was beneficial for the graft copolymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1249–1254, 2003     

Grafting of methyl methacrylate onto sodium alginate initiated by potassium ditelluratoargentate(III)

Sodium alginate (SA) was graft‐copolymerized with methyl methacrylate in an alkali aqueous solution with potassium ditelluratoargentate(III) (DTA) as the initiator. Graft copolymers with both a high grafting efficiency (>90%) and a high percentage of grafting were obtained, which indicated that the DTA–SA redox pair was an efficient initiator for this grafting. The grafting parameters, including total conversion, grafting efficiency, and percentage grafting, were evaluated comparatively. The dependence of these parameters on temperature and time, monomer concentration, initiator concentration, and SA backbone concentration was also investigated. The overall activation energy of this grafting was calculated as 37.50 kJ/mol. Proof of grafting was obtained from gravimetric analysis and IR spectra. A tentative mechanism involving a two‐step, single‐electron‐transfer process of DTA is proposed to explain the generation of radicals and the initiation of grafting. Some basic properties of the grafted copolymer were studied by instrumental analyses, including thermogravimetry, X‐ray diffraction, and scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1688–1694, 2005     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatonickelate(IV)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) with a potassium diperiodatonickelate(IV) [Ni(IV)]–PVA redox system as an initiator was investigated in an alkaline medium. The grafting parameters were determined as functions of the temperature and the concentrations of the monomer and initiator. The structures of the graft copolymers were confirmed by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The Ni(IV)–PVA system was found to be an efficient redox initiator for this graft copolymerization. A single‐electron‐transfer mechanism was proposed for the formation of radicals and the initiation. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate, n‐butyl acrylate, and n‐butyl methacrylate, were used as reductants for graft copolymerization. These reactions definitely occurred to some degree. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 529–534, 2003     

Radical polymerization of vinyl monomers in the presence of carbon black initiated by 2,2'‐azobisisobutyronitrile and benzoyl peroxide in ionic liquid

The radical polymerization behavior of vinyl monomers, such as styrene, methyl methacrylate (MMA), and vinyl acetate (VAc), in the presence of carbon black initiated by benzoyl peroxide (BPO) and 2,2'‐azobisisobutyronitrile (AIBN) in ionic liquid (IL) was compared with those in toluene. 1‐Butyl‐3‐methylimidazolium hexafluorophosphate was used as IL. The radical polymerization of vinyl monomers initiated by BPO and AIBN in the presence of carbon black was remarkably retarded in toluene. On the contrary, the retardation of the polymerization by carbon black was considerably reduced in IL. During the radical polymerization in the presence of carbon black, a part of polymer formed was grafted onto carbon black surface based on the termination reaction of the growing polymer radicals with carbon black surface. The percentage of grafting and molecular weight of polymer in IL were much higher than those in toluene. This may be due to the fact that lifetime of the growing polymer radical is prolonged because of high viscosity of IL. Therefore, the growing polymer radicals with higher molecular weight were trapped by carbon black surface, because of stabilization of polymer radicals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Graft copolymerization of acrylic acid onto methylcellulose by potassium permanganate‐p‐xylene redox pair

Poly(acrylic acid) was grafted onto methylcellulose in aqueous media by a potassium permanganate‐p‐xylene redox pair. Within the concentration range from 0.93 × 10^?3 to 9.33 × 10^?3M, p‐xylene, the graft copolymerization reaction exhibited minimum and maximum graft yields and was associated with two precursor‐initiating species, a p‐xylyl radical and its diradical derivative. The efficiency of the graft was low, not higher than 12.9% at a p‐xylene concentration of 0.93 × 10^?3M and suggested the dominance of a competitive homopolymerization reaction under homogeneous conditions. The effect of permanganate on the graft yield was normal and optimal at 135% graft yield, corresponding to a concentration of the latter of 33.3 × 10^?3M over the range from 8.3 × 10^?3 to 66.7 × 10^?3M. The conversion in graft yield showed a negative dependence on temperature in the range 30–60°C and suggested a preponderance of high activation energy transfer reaction processes. The calculated composite activation energy for the graft copolymerization was 7.6 kcal/mol. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 278–281, 2004     

Graft copolymerization of acrylate monomers onto sulfonated jute–cotton blended fabric

Graft copolymerization of acrylate monomers, e.g., methyl methacrylate and ethyl methacrylate, onto bleached sulfonated jute–cotton‐blended fabric was carried out in an aqueous medium, using potassium persulfate as an initiator under the catalytic influence of ferrous sulfate in a nitrogen atmosphere. The parameter variables, e.g., concentrations of monomer, potassium persulfate, ferrous sulfate, reaction time, and reaction temperature, directly influenced the percent graft yield. The percent graft yield increased to a certain value in each variable, and the percent graft yield of methyl methacrylate and ethyl methacrylate was about 15.9 and 17.1%, respectively. Polymer grafting was characterized by thermogravimetric analysis, infrared spectroscopy, and X‐ray diffractometry. Grafting improved the thermal stability, protected from photo‐oxidative degradation, decreased the dyeability, and had positive impact on fastness characteristics. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4393–4398, 2006     

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 methyl methacrylate onto starch using a Ce(IV)–glucose initiator system

Graft copolymerization of methyl methacrylate onto starch was carried out in aqueous medium using Ce(IV)–glucose initiator in the temperature range 40–60°C. Effects of concentration of Ce(IV), glucose, H₂SO₄, monomer, and starch on grafting were investigated. Percentages of grafting were evaluated and compared. The overall energy of activation was calculated from the effects of time and temperature of polymerization. The reaction mechanism was also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 981–990, 2004     

Grafting of acrylonitrile onto allylated caesarweed fibers by potassium permanganate – N,N′‐dimethylacetamide redox pair

Caesarweed fiber, Urena lobata, was modified by successive treatment with sodium hydroxide and allylchloride in diethylether to yield an average degree of substitution of 2.73 allyl moieties per anhydroglucose unit. The presence of allyl moieties on the fiber was confirmed by infrared spectroscopy. Graft copolymerization of acrylonitrile onto the unmodified and allyl‐modified fibers was initiated by potassium permanganate –N,N′‐dimethylacetamide redox pair in aqueous medium. The allyl fiber was markedly less reactive than the unmodified fiber with graft yields for the latter a factor of 2.3 higher than those of the former. This was attributed to resonance stabilization of allylic macroradicals of the fiber. The graft yield showed positive dependence on N,N′‐dimethylacetamide concentration in the range, 9.0–45.0 × 10^?4M with P_g/P_go of up to 1.39 at the highest concentration. The conversion in graft yield was however characterized by a plateau at the latter concentration and was ascribed to termination of grafted polymer chains by methylacetylaminomethyl radical initiating species. Spectroscopic evidence in support of the latter was the absorption peak at 1680 cm^?1 for the graft copolymers, characteristic of C?O stretching vibration for tertiary amide. Acetic acid, at concentrations in the range 0.28–2.22M, was inimical to grafting of acrylonitrile onto allylfibre with P_g/P_go, of less than one. Grafting onto allylfiber showed positive temperature dependence in the range, 30–50°C with calculated activation energy of 12.3 kcal mol^?1 for the graft polymerization reaction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cotton fabric graft copolymerization using microwave plasma. I. Universal attenuated total reflectance–FTIR study

The effect of microwave plasma on lightweight cotton fabric was investigated. N₂‐plasma, O₂‐plasma, and Ar‐plasma were obtained using a microwave generator at 2.45 GHz under vacuum. The universal attenuated total reflectance–Fourier transform infrared (UATR–FTIR) instrument was used to monitor the changes created after N₂‐, O₂‐, and Ar‐plasma treatments. The exposure of cotton fabrics to the plasma for 240 s with a microwave power of 500 W was sufficient to create active carbonyl groups, as shown by the presence of a peak around 1725 cm^?1 in the FTIR spectra of the treated cotton fabrics. Ar‐plasma was found to generate more active groups than N₂‐ and O₂‐plasmas. The active centers created within the cellulose chains were used to initiate copolymerization reactions with vinyl monomers to impart hydrophobic character to lightweight cotton fabric. The efficiency of the grafting process and the presence of grafted monomers on fabric surface were confirmed using UATR–FTIR. Testing of treated fabric revealed that excellent water repellency was obtained. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 145–154, 2004     

Chemically induced graft copolymerization of vinyl monomers onto cotton fibers

We investigated the chemically induced graft copolymerizations of acrylic acid (AA), acrylamide, crotonic acid, and itaconic acid (IA) onto cotton fibers. Benzoyl peroxide was used as an initiator. The effects of grafting temperature, grafting time, and monomer and initiator concentrations on the grafting yields were studied, and optimum grafting conditions were determined for the sample material. The maximum grafting yield value obtained was 23.8% for AA. Swelling tests, Fourier transform infrared spectroscopy, and scanning electron microscopy analyses of grafted and ungrafted fibers were also performed to characterize fiber properties. IA‐grafted fibers were measured as the most swollen fibers, with a swelling value of 510%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2343–2347, 2006     

Effect of grafting methacrylate monomers onto jute constituents with a potassium persulfate initiator catalyzed by Fe(II)

The graft copolymerization of methyl methacrylate and ethyl methacrylate monomers onto jute fiber was carried out in an aqueous medium with potassium persulfate as an initiator under the catalytic influence of ferrous sulfate in the presence of air. The effects of parameter variables, such as the monomer, initiator, and catalyst concentrations, the reaction time, and the temperature, on grafting and the effect of grafting the monomers onto jute constituents were studied. The degree of grafting depended on the kinds of monomers and the parameter variables. The maximum graft yield percentages with methyl methacrylate and ethyl methacrylate under optimized conditions were 18.9 and 38.8%, respectively, and the grafting onto jute fiber was largely affected by one of its main constituents, such as hemicellulose. The graft copolymers were characterized, and their improved properties were also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2369–2375, 2007     

Graft copolymerization of methyl methacrylate onto oil palm empty fruit bunch fiber using H2O2/Fe2+ as an initiator

Graft copolymerization of methyl methacrylate (MMA) onto oil palm empty fruit bunch fiber (OPEFB) was successfully carried out in aqueous medium using hydrogen peroxide as an initiator. Results from the investigation of the optimum conditions for grafting are presented. Maximum percentage of grafting was achieved when the amount of initiator, cocatalyst, and nitric acid were 5.877 × 10^?3 mol, 2.63 × 10^?4 mol, and 3.24 × 10^?3 mol, respectively. The optimum reaction temperature was 50°C and the reaction period was 120 min. The highest percentage of grafting and grafting efficiency were 220 and 47%, respectively, under optimum conditions. The grafted copolymer was characterized by FTIR spectroscopy and scanning electron microscopy. The presence of a band at 1730 cm^?1 provides strong evidence of grafting. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2233–2238, 2003     

Graft copolymerization of N‐vinyl‐2‐pyrrolidone onto sodium carboxymethylcellulose with azobisisobutyronitrile as the initiator

Graft copolymers of sodium carboxymethylcellulose with N‐vinyl‐2‐pyrrolidone were prepared in aqueous solutions with azobisisobutyronitrile as the initiator. The graft copolymers [sodium carboxymethylcellulose‐g‐poly(N‐vinyl‐2‐pyrrolidone)] were characterized with Fourier transform infrared spectroscopy, elemental analysis, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and scanning electron microscopy. The grafting parameters, including the graft yield of the graft copolymer and the grafting efficiency of the reaction, were evaluated comparatively. The effects of reaction variables such as the time, temperature, and monomer and initiator concentrations on these parameters were studied. The graft yield and grafting efficiency increased and then decreased with increasing concentrations of N‐vinyl‐2‐pyrrolidone and azobisisobutyronitrile and increasing polymerization temperatures. The optimum temperature and polymerization time were 70°C and 4.30 h, respectively. Further changes in the properties of grafted sodium carboxymethylcellulose, such as the intrinsic viscosity, were determined. The overall activation energy for the grafting was also calculated to be 10.5 kcal/mol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 936–943, 2007     

Free‐radical graft copolymerization of phosphonated methacrylates onto low‐density polyethylene

Dimethyl 2‐methacryloxyethylphosphonate, its monosodium salt, and methyl 2‐methacryloyloxyethylphosphonic acid were synthesized, characterized, and grafted onto low‐density polyethylene (LDPE) powder under melt‐processing conditions in a Rheocord batch mixer (Karlsruhe, Germany). We studied the graft copolymerization onto LDPE in the presence of free‐radical initiators, benzoyl peroxide, and dicumyl peroxide, and we performed grafting onto ozone‐pretreated LDPE without any free‐radical initiator. Effects of reaction time, initiator concentration, and reaction temperature were studied. The possibility of modifying LDPE in the molten state with phosphonated methacrylates was clearly demonstrated. Graft copolymers were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, scanning electron microscopy, and water contact angles. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2011–2020, 2002