Photo-induced graft copolymerization: XVI: Graft copolymerization of methyl methacrylate onto nylon-6 using isoquinoline-sulfur dioxide and α-picoline-sulphur dioxide charge-transfer complexes as photoinitiators

The photo-induced graft copolymerization of methyl methacrylate onto nylon-6 fiber was investigated using isoquinoline-sulfur dioxide and α-picoline-sulfur dioxide charge-transfer complexes as the photoinitiators. The graft copolymerization was carried out within the temperature range of 35–50°C and from the corresponding Arrhenius plot, the energy of activation has been evaluated. The effect of monomer, initiators, inhibitors, etc. on the graft yield has been investigated. The effect of solvent on the rate of grafting has also been investigated from which the chain-transfer constant (C_s) of the solvent has been evaluated. The kinetic data and other evidence indicate that the overall polymerization takes place by a radical mechanism. The suitable mechanism has been suggested and the kinetic rate expression has been derived.     

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.     

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 vinyl monomers into nylon-6. II. Graft copolymerization of methyl methacrylate onto nylon-6 by hexavalent chromium ion

The feasibility of chromium(VI) to induce graft copolymerization of methyl methacrylate onto nylon-6 was investigated in the presence of nitrogen. The rate of grafting was determined by varying monomer concentration, chromium(VI) concentration, temperature, acidity of the medium, solvents, inorganic salts, and redox system. The graft yield increases significantly by increasing the monomer concentration. The graft yield increases with increase of [Cr(VI)] up to 0.025 mole/liter. With further increase of [Cr(VI)], the graft yield decreases. The increase of acid concentration up to 0.395 mole/liter results the increase in graft yield. Beyond this concentration the graft yield decreases. The graft yield increases with increase in temperature up to 55°C and thereafter it decreases. The graft yield is medium dependent. The graft yield increases with increasing thiourea concentration upto 0.0025 mole/liter but beyond this concentration, the percentage graft yield decreases. 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.     

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.     

Radiation-induced graft copolymerization of methacrylic acid onto polypropylene fibers VI. Dyeing behavior

The dyeing behavior of polypropylene-g-polymethacrylic acid fibers prepared by graft copolymerization of methacrylic acid onto polypropylene fibers by gamma-ray irradiation was evaluated for their dyeability characteristics using two basic dyes, rhodamine B and methylene blue. An increase in the dye uptake and moisture regain with the increase in graft content was observed. Such behavior has been attributed to the hydrophilicity imparted to polypropylene fiber by the presence of polar carboxyl groups in polymethacrylic acid grafts. The dependence of rate of dyeing on the percentage graft was evaluated. The diffusion coefficient of the fiber showed an increase with the increase in graft content and has been related to the structural changes occurring during grafting.     

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.     

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).     

Studies on graft copolymerization of methyl methacrylate onto chemically modified tussa silk fibers. Peroxydisulfate-thiourea redox system

The graft copolymerization of methyl methacrylate (MMA) onto chemically modified tussa silk fibers in aqueous media using potassium peroxodisulfate-thiourea redox initiator system was studied at 60°C. The effects of time of reaction, concentrations of oxidant, thiourea (TU), monomer (M), amount of silk fibers on graft yield have been studied. The effects of reaction medium, acid concentration, and some inorganic salts and organic solvents on grafting have also been investigated. A significant increase in percent of grafting was observed with increasing monomer concentration to 65.86 · 10^?2 mol · 1^?1; a further increase of monomer concentration is associated with the decrease of graft yield. The graft yield increases with an increase of thiourea concentration up to 10 · 10^?1 mol · 1^?1, beyond which it decreases very significantly. A measurable increase of the graft yield was also observed with an increase of the oxidant concentration up to 0.08 mol · 1^?1 beyond which the graft yield decreased. The graft yield was medium dependent. The reaction mechanism of the grafting process has been proposed and a rate expression has been derived on the basis of experimental findings. IR spectra of the grafted fiber and original fiber have been taken and their characteristic bands have been identified. The thermal behaviour of the original and grafted silk fibers has been studied by TGA and DTG analysis. Grafting has improved thermal stability as well as the light fastness of silk dyed with Rhodamine B.     

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.     

Peroxydisulfate initiated graft copolymerization of aniline onto poly(propylene) fiber—A kinetic approach

A novel method for the preparation of electrically conducting fibers through chemical grafting of electrically conducting polymer onto poly(propylene) (PP) fiber is described. The graft copolymerization of aniline (ANI) was performed in aqueous acidic medium by using a chemical oxidant such as peroxydisulfate (PDS). Grafting occurred with simultaneous homopolymer formation. The content of polyaniline in the backbone fiber was found to vary by varying [monomer], [initiator], and amount of PP fiber. Various graft parameters such as rate of grafting (R_g), % grafting, and % grafting efficiency were evaluated. The rate of homopolymerization (R_h) was also determined. Both R_h and R_g showed first‐order dependency on [ANI], [PDS], and amount of PP fiber variation. The chemical grafting was confirmed by use of cyclic voltammetry and conductivity measurements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3827–3834, 2003     

Radiation-Induced graft copolymerization of methacrylic acid onto polypropylene fibers. V. Mechanical properties

Mechanical properties of polypropylene-g-poly(methacrylic acid) fibers, prepared by graft copolymerization of methacrylic acid onto polypropylene fiber using simultaneous gamma ray irradiation technique, were evaluated. In general, an improvement in the mechanical behavior of the polypropylene fiber by grafting was observed. Denier and initial modulus of the fiber showed a linear increase with the percent graft, and elongation showed an opposite trend. The results have been explained in terms of reinforcing effect of poly(methacrylic acid) grafts and reduction in the segmental mobility of the polymeric chains. Tenacity also increases up to certain graft level, beyond which a sharp decrease occurs, probably due to the influence on the compactness of the macromolecular chains with the further grafting.     

Peroxomonosulphate initiated graft copolymerization of o‐toluidine onto nylon 6 and wool fibers—A kinetic approach

Chemical polymerization of o‐toluidine (OT) in the presence of nylon 6 and wool fibers initiated by peroxomonosulphate (PMS) in an aqueous acidic medium was carried out under nitrogen atmosphere. During the polymerization process, graft copolymers were formed along with homopolymers of OT. A procedure is given for the separation of poly(o‐toluidine) (POT) grafted fiber from the homopolymer. Rate of homopolymerization (R_h), rate of grafting (R_g), percentage grafting, and percentage grafting efficiency were determined. Rate constants were evaluated from the experimental results. The chemical grafting of POT onto nylon 6 and wool fibers was confirmed through Fourier transform infrared (FTIR) spectroscopy and electrical conductivity measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2317–2326, 2002     

In situ Polymerization of Multi-Walled Carbon Nanotube/Nylon-6 Nanocomposites and Their Electrospun Nanofibers

Multiwalled carbon nanotube/nylon-6 nanocomposites (MWNT/nylon-6) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC₆H₄-NH₂) groups onto the side wall. Scanning electron microscopy (SEM) images obtained from the fractured surfaces of the nanocomposites showed that the F-MWNTs in the nylon-6 matrix were well dispersed as compared to those of the P-MWNTs. Both nanocomposites could be electrospun into nanofibers in which the MWNTs were embedded and oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The specific strength and modulus of the MWNTs-reinforced nanofibers increased as compared to those of the neat nylon-6 nanofibers. The crystal structure of the nylon-6 in the MWNT/nylon-6 nanofibers was mostly γ-phase, although that of the MWNT/nylon-6 films, which were prepared by hot-pressing the pellets between two aluminum plates and then quenching them in icy water, was mostly α-phase, indicating that the shear force during electrospinning might favor the γ-phase, similarly to the conventional fiber spinning.     

Graft copolymerization of nitrile monomers onto bleached jute fiber using potassium persulfate system and their textile characteristics

Graft copolymerization of nitrile monomers, such as acrylonitrile and methacrylonitrile, onto bleached jute fiber was carried out by using K₂S₂O₈/FeSO₄ redox system in nitrogen atmosphere and their effect on the textile characteristics was also investigated. Percent graft yield increased with the increase of concentrations of monomer, initiator, and catalyst, reaction time, and reaction temperature up to a certain value, and, thereafter, it decreased. The effect of percent grafting efficiency was similar to that of percent graft yield, except for the monomer concentration. The increase of percent graft yield was dependent on the availability of jute‐macroradicals as well as monomer radicals. Sometimes the predominancy of homopolymerization over grafting and the premature termination of growing grafted chains occurred because of the higher monomer radicals and excess primary radicals, SO₄^?? and ^?OH, from K₂S₂O₈ initiator. The percent graft yield of acrylonitrile and methacrylonitrile was 20.5 and 29.1%, respectively. Higher graft yield for methacrylonitrile might be due to the methyl group present in it. Infrared spectra at 2229–2235 cm^?1 of acrylonitrile‐ and methacrylonitrile‐grafted jute strongly supported the graft formation. Grafting of jute fiber improved the thermal stability, protected from photooxidative degradation, and decreased swellability as well as dyeability, etc. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3622–3629, 2004     

REDOX INITIATED GRAFT COPOLYMERIZATION OF 4-VINYL PYRIDINE ONTO WOOL FIBER

The graft copolymerization of 4-Vinyl Pyridine (4VP) onto wool fiber in aqueous medium by peroxomonosulphate (PMS)—thioglycolic acid (TGA) redox pair in an inert atmosphere has been investigated. The effect of concentrations of 4VP, PMS, TGA on R_h, and graft parameters have been studied. In addition, the effect of time, temperature, and amount of wool fiber on R_h and graft parameters were also determined. Chemical grafting of 4VP onto wool fiber was confirmed by FTIR spectroscopy. The tensile strength of the grafts have been analyzed.     

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.     

Effect of partial delignification of kenaf bast fibers for radiation graft copolymerization

Malaysian kenaf bast fiber was treated by acidic chlorite to be applied for a trunk polymer radiation‐induced graft copolymerization. The delignification conditions such as temperature, reaction time, and sodium chlorite (NaClO₂) loading were optimized from the viewpoints of density, tensile strength, and reactivity of grafting. It was found that delignification condition at 80°C for 6 h with 0.5% NaClO₂ gave 91% of lignin removal from the kenaf bast fibers. In this case, the density, fineness, and tensile strength of the kenaf fiber decreased about 46, 44, and 87%, respectively. Reactivity of grafting was evaluated using 4‐chloromethyl styrene to obtain widely available precursor materials. The partial delignified kenaf with residual lignin less than 2% resulted in degree of grafting of 134%, which is enough for precursor materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Graft copolymerization of glycidylmethacrylate onto modified nylon‐6 fibers

The graft copolymerization of glycidylmethacrylate (GMA) onto modified nylon‐6 fibers containing polydiallyldimethylammonium chloride (PDADMAC) groups in the presence of (Cu ²⁺–K₂S₂O₈) as a redox initiating system was carried out, with very high extent and almost without homopolymer formation. The mechanism of the graft polymerization induced by this system was suggested. The rate of grafting was determined by varying the monomer, K₂S₂O₈, and cupric ion concentrations as well as the amount of PDADMAC. The kinetic investigation revealed that the rate of grafting (Rp) of GMA onto modified nylon‐6 fibers is proportional to [GMA]^1.83, [CuSO₄·5H₂O]^0.46, [PDADMAC]^0.4, and [K₂S₂O₈]^1.43. The overall activation energy was 134.7 kJ/mol. The fine structure and thermal properties of the grafted nylon‐6 fibers were investigated. investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 613–618, 2006