Radiochemical graft copolymerization of methacrylonitrile and binary mixture of methacrylonitrile with 4-vinylpyridine onto isotactic polypropylene fiber

Graft copolymerization of methacrylonitrile (MAN) and its binary mixture with 4-vinylpyridine (4-VP) onto isotactic polypropylene (IPP) fiber has been studied in aqueous medium by the preirradiation method. Optimum conditions for obtaining the maximum percentage of grafting have been evaluated. Rate of grafting (Rg) has been determined as a function of total initial monomer concentration. The graft copolymers are characterized by IR spectroscopy, by thermogravimetric analysis, and by isolating the polymer from the graft copolymer. The effect of MAN, an acceptor monomer, on percentage of grafting of 4-VP, a donor monomer, has been discussed in the light of the mechanism proposed for grafting by the radiochemical method. © 1994 John Wiley & Sons, Inc.     

Graft copolymerization of 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method

An attempt has been made to graft copolymerize 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method in an aqueous medium. Polypropylene hydroperoxide has been prepared by irradiating recrystallized polypropylene beads from a Co⁶⁰ source in the presence of air. The resulting polypropylene hydroperoxide beads have been used as the backbone polymer and grafting of 4-vinyl pyridine has been studied as a function of various reaction parameters. Optimum conditions for maximum percentage of grafting have been evaluated. Rate of grafting (R_g) has been determined as a function of preirradiation dose and initial monomer concentration. Water has been found to affect percentage of grafting. The graft copolymers have been characterized by spectroscopic method and isolation of the grafted poly(4-VP) from the graft copolymer. A plausible mechanism is proposed to explain the mutual grafting of 4-vinyl pyridine onto polypropylene hydroperoxide. © 1993 John Wiley & Sons, Inc.     

Radiation-induced graft polymerization of acrylonitrile onto isotactic polypropylene and poly(tetrafluoroethylene–ethylene) copolymer films

Direct radiation-induced grafting of acrylonitrile (AN) onto both isotactic polypropylene (IPP) and (tetrafluoroethylene–ethylene) copolymer (ET) films has been studied. The effect of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield was investigated. Homopolymerization of acrylonitrile was reduced to a minimum using ferric chloride (FeCl₃), and the suitable optimum concentration of the inhibitor was found to be 0.1 wt%. The higher the monomer concentration, the higher the degree of grafting obtained. It was observed that the degree of grafting onto IPP was higher than onto ET, at given grafting conditions. The effect of aging on IPP was also examined. IR spectroscopy showed that IPP was susceptible to photooxidation by aging. The swelling behaviour and electrical conductivity of the graft and hydrolysed graft films were investigated. The electrical conductivity was improved by hydrolysis of polyacrylonitrile in the graft chains.     

Radiation synthesis of polypropylene-acrylate grafted fiber and its remediation in the spillage of water-insoluble organic chemicals

A new kind of functionalized polypropylene(PP)-acrylate grafted fiber were prepared by radiation-induced graft polymerization of methyl acrylate (MA), ethyl acrylate(EA) and butyl acrylate (BA) monomer onto the PP fiber matrix, as a recovery adsorbent for insoluble organic chemicals. The grafting conditions of monomer concentration and irradiation time on the grafting degree were optimized. The obtained grafted fiber sample was identified by Fourier transform infrared (FT-IR) spectrometer and scanning electron microscopy (SEM) to characterize the chemical and morphological changes of the polypropylene fiber surface. The adsorption results indicated that the grafted fiber could be used to remove organic chemicals from water surface. The adsorption capacity of grafted fiber with different acrylate monomer was obviously different for the same chemicals, therefore, investigations with respect to organic removal, dynamic oil retention, and reusability, the effect of monomer polarity on the adsorption capacity of grafted fiber was especially highlighted in this study.     

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.     

Ceric(IV) ion‐induced graft copolymerization of acrylamide and ethyl acrylate onto cellulose

Graft copolymerization of acrylamide (AAm) and ethyl acrylate (EA) onto cellulose has been carried out from their binary mixtures using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 25 ± 1 °C. The extent of acrylamide grafting increased in the presence of the EA comonomer. The composition of the grafted chains (F_AAm = 0.52) was found to be constant during the feed molarity variation from 7.5 × 10^?2 to 60.0 × 10^?2 mol L^?1, whereas the composition of the grafted chains (F_AAm) was found to be dependent on feed composition (f_AAm) and reaction temperature. The effects of ceric(IV ) ion concentration, reaction time and temperature on the grafting parameters have been studied. The grafting parameters showed an increasing trend up to 6.0 × 10^?3 mol L^?1 concentration of CAN at a feed molarity of 30.0 × 10^?2 mol L^?1 and showed a decreasing trend on further increasing the concentration of CAN (>6.0 × 10^?3 mol L^?1) at a constant concentration of nitric acid (5.0 × 10^?2 mol L^?1). The composition of the grafted chains (F_AAm) was determined by IR spectroscopy and nitrogen content and the data obtained then used to determine the reactivity ratios of the acrylamide (r₁) and ethyl acrylate (r₂) comonomers by using a Mayo and Lewis plot. The reactivity ratios of acrylamide and ethyl acrylate were found to be r₁ = 0.54 and r₂ = 1.10, respectively, and hence the sequence lengths of acrylamide (m?M₁) and ethyl acrylate (m?M₂) in the grafted chains are arranged in an alternating form, as the product of the reactivity ratios of acrylamide and ethyl acrylate (r₁ × r₂) is less than unity. The rate of graft copolymerization of the comonomers onto cellulose was found to be dependant on the ‘squares’ of the concentrations of the comonomers and on the ‘square root’ of the concentration of ceric ammonium nitrate. The energy of activation (ΔE_a) of graft copolymerzation was found to be 5.57 kJ mol^?1 within the temperature range from 15 to 50 °C. On the basis of the results, suitable reaction steps have been proposed for the graft copolymerzation of acrylamide and ethyl acrylate comonomers from their mixtures. Copyright © 2005 Society of Chemical Industry     

Grafting of 2-HEMA on IPP and in situ chlorinated PP through solution polymerization

Grafting of 2-hydroxyethyl methacrylate (2-HEMA) on isotactic polypropylene (IPP) and in situ chlorinated polypropylene (CPP) by free radical process was carried out at 110°C using toluene as solvent. Various conditions for grafting were optimized. The maximum percent of grafting of 2-HEMA achieved on IPP was 3.6%, whereas that on in situ CPP was 8.7%. The products were characterized by Fourier transform infrared spectroscopy and thermal and contact angle measurements. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2107–2113, 1998     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatoargentate(III)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) using potassium diperiodatoargentate(III) [Ag(III)]–PVA redox system as initiator was studied in an alkaline medium. Some structural features and properties of the graft copolymer were confirmed by Fourier‐transfer infrared spectroscopy, scanning electron microscope, X‐ray diffraction and thermogravimetric analysis. The grafting parameters were determined as a function of concentrations of monomer, initiator, macromolecular backbone (X?_n = 1750, M? = 80 000 g mol^?1), reaction temperature and reaction time. A mechanism based on two single‐electron transfer steps is proposed to explain the formation of radicals and the initiation profile. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate and n‐butyl acrylate, were also used to produce graft copolymerizations. It has been confirmed that grafting occurred to some degree. Thermogravimetric analysis was performed in a study of the moisture resistance of the graft copolymer. Copyright © 2004 Society of Chemical Industry     

Development and assessment of the advanced graft copolymers obtained from Hibiscus sabdariffa biomass

In this article, the morphological transformation in Hibiscus sabdariffa stem fiber through graft copolymerization with effective ethyl acrylate (EA) and its binary vinyl monomeric mixtures using ceric ammonium nitrate—nitric acid initiator system has been reported. Different reaction parameters such as temperature, time, initiator concentration, monomer concentration, and pH were optimized to obtain the maximum graft yield (117.3%). The optimized reaction parameters were then used to screen the additive effect of EA with n‐butyl acrylate (BA), acrylic acid (AA), and 4‐vinyl pyridine (4‐VP) in binary vinyl monomer mixtures on percentage grafting, properties, and the behavior of the fiber. The graft copolymers were characterized by FTIR, SEM, XRD, TGA, and DTA techniques and evaluated for physico‐chemical changes. With increase in the P_g a significant physico‐chemico‐thermal resistance, miscibility in organic solvents, hydrophobicity were found to increase, whereas crystallinity, crystallinity index, dye‐uptake, and hydrophylicity decreased, however, the cellulose form I remained unchanged. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dyeing of chrome tanned collagen modified by in situ grafting with 2‐EHA and MAC

The aim of this study deals with the modification of the chrome tanned collagen (leather) by in situ grafting with 2‐ethyl hexyl acrylate (2‐EHA) and methacrylic acid (MAC) to improve its dyeability using Amecid Floxine 2GN (C.I. Acid Red 1) and Remazol Black B (C.I. Reactive Black 5). The optimum condition of in situ grafting has been evaluated. FTIR spectra of the ungrafted and the in situ grafted chrome tanned collagen showed that the corresponding band of the acrylate carbonyl ester occurs at 1730–1735 cm^?1 when compared with the ungrafted ones. The colorimetric data of the in situ grafted and dyed samples exhibited improvement in color shade, dye bath exhaustion, wash and light fastness relative to the ungrafted and dyed ones. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 174–179, 2006     

Optimized conditions for the grafting reaction of poly(methyl acrylate) onto rubberwood fiber

Graft copolymerization of poly(methyl acrylate) (PMA) onto rubberwood fiber (RWF) was carried out by free radical initiation. Hydrogen peroxide and ferrous ions were used as an initiator system. Effects of various parameters (reaction temperature and reaction time, as well as hydrogen peroxide, ferrous ammonium sulfate and monomer concentrations) on the grafting percentage were investigated. A high percentage of grafting was achieved when optimum reaction conditions were used. The optimum temperature of the reaction was determined to be about 55 °C and the reaction time was 120 min. The optimum concentration of H₂O₂ was 0.03 M and the amounts of Fe²⁺ and MA were 0.4 mmol and 0.05 mol, respectively. The PMA homopolymer was removed from the graft copolymer by Soxhlet extraction using acetone. The presence of PMA on the fiber was confirmed by FT-IR spectroscopy and gravimetry. The surface morphology of the poly(methyl acrylate)-graft-(rubberwood fiber) was studied by means of scanning electron microscopy. Copyright © 2004 Society of Chemical Industry     

Flame retardant polypropylene fibers with good dyeability

Polypropylene has been grafted with pentabromobenzyl acrylate by reactive extrusion. The degree of grafting is about 4% by weight of the polypropylene independent of the weight of brominated monomer in the feed. Ungrafted monomer remains largely unreacted. Fibers spun from the grafted polypropylene display good mechanical properties and are easily dyed with anthraquinone type disperse dyes. The dyed cloths have good color stability even after laundering. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 601–606, 1997     

Modification of polypropylene via the free‐radical grafting ternary monomer in water suspension systems

Maleic anhydride, styrene, and butyl acrylate were grafted onto polypropylene (PP) via free‐radical polymerization. The grafted product, polypropylene‐g‐(maleic anhydride–styrene–butyl acrylate) (PP‐g‐PMSB), was prepared in a water suspension system, and a nongrafted polymer, poly(maleic anhydride–styrene–butyl acrylate) (PMSB′), was produced at the same time. The optimal synthesis conditions were determined by orthogonal experiments. The crystallinity, thermal stability, melt flow rate, and hydrophilicity of the grafting samples were investigated in the presence or absence of PMSB′. The results indicate that the grafting percentage (G_p) of PP‐g‐PMSB and the content of PMSB′ (C_m) increased as the monomer content increased under the optimum reaction conditions. All of these ternary monomers were grafted onto the PP backbone as long‐chain branches. With increasing G_p, PP‐g‐PMSB's polarity and thermal stability increased, the crystallinity decreased, and the molecular distribution became narrower. The contact angle decreased to 72.12° when G_p was 6.87%. With increasing C_m, the crystallinity and thermal stability of the grafting products decreased compared to PP‐g‐PMSB and the molecular distribution grew wider. The contact angle decreased to 63.51° when C_m was 3.64%; this indicated that the presence of PMSB′ further improved the hydrophilicity of the grafted products. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Radiation‐induced graft copolymerization of 2‐vinylpyridine and styrene onto isotactic polypropylene fiber

Isotactic polypropylene fiber (IPP) was graft‐copolymerized using 2‐vinyl pyridine (2‐VP) and styrene (sty) as the monomers by the mutual irradiation method in air. The percentage of grafting was determined as a function of various reaction parameters and it was found that the maximum grafting of 2‐VP (114%) and sty (76%) was obtained at an optimum dose of 1.08 × 10⁴ and 0.64 × 10⁴ Gy using 1.8 × 10⁻² mol of 2‐VP and 4.3 × 10⁻² mol of sty, respectively. The graft copolymers were characterized by differential scanning calorimetric analysis and isolation of the grafted chains from the grafted iPP samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2959–2969, 1999     

Analysis on the dyeing of polypropylene fibers in supercritical carbon dioxide

Polypropylene fibers were dyed in supercritical carbon dioxide system and the results were compared with those of fiber dyed in water system. Dye uptake value calculated by a UV spectrum indicated that polypropylene fiber dyeing was much better in carbon dioxide than in water. Optical microscopical analysis showed that dye molecules had diffused thoroughly into fiber in CO₂ because of the excellent compatibility between the dye and the CO₂. X-ray and birefrigence analysis demonstrated that plastification caused by the implementation of CO₂ made molecular chain more mobile and led to an increase in the dyeing of polypropylene fibers. Moreover a mechanical test and DSC analysis indicated that the fiber structure was not damaged when the fabric was dyed at 100 °C. Hence dyeing polypropylene using CO₂ as a transport medium was very feasible and worthy of further development.     

Photoinitiated surface grafting of synthetic fibers,IV. Applications of textile dyes onto surface-photografted synthetic fibers

High-strength polyethylene (HSPE), polypropylene (PP), poly(ethylene terephthalate) (PET), and poly(vinyl alcohol) (PVA) textile yarns have been surface-photografted with various functional monomers, such as acrylic acid (AA), acrylamide (AM), glycidyl acrylate (GA) and 4-vinyl pyridine (VP), by means of the continuous presoaking process developed. The dyeing of these surface-modified yarns with various textile dyes has been investigated. In general, considerable improvements of dyeability have been observed. The dye adsorption of the surface-photografted fibers is influenced by many factors, such as type of fiber, amount and properties of the functional monomer grafted on the surface of the fibers, type of textile dye, etc. The fibers surface-grafted with a monomer containing basic groups, such as acrylamide and 4-vinyl pyridine, are efficiently dyed with an acid dye. Conversely, a fiber surface-grafted with acidic functional monomer is easily dyed to deep shades with basic dyes. The dye adsorption increases monotonically with increasing grafting measured in ESCA spectra as relative intensities of relevant lines. The ungrafted HSPE, PP and PET fibers can be dyed to some extent with certain dyes. In the present work, the dye adsorption increased by 3.4 times for HSPE fiber grafted with GA and dyed with the metal complex dye IO, by 7.9 times for PP fiber grafted with AA and dyed with the basic dye MB, by 6.1 times for PET with AM and with the direct dye SL, and by about 15.3 times for PVA with VP and with the acid dye TE.     

Biodegradation of gelatin–g-poly(ethyl acrylate) copolymers

Gelatin-g-poly(ethyl acrylate) copolymers were prepared in an aqueous medium, using K₂S₂O₈ initiator. The composition of the graft copolymers was dependent upon temperature and duration of the reaction. The number of grafting sites was small and molecular weight of the grafted poly(ethyl acrylate) branches was high. Three copolymer samples with grafting efficiencies of 33.3%, 61.0%, and 84.0%, were tested for their microbial susceptibility in a synthetic medium employing a mixed inoculum of Bacillus subtilis, Pseudomonas aeruginosa, and Serratia marcescens and the percent weight losses were 12%, 10.1%, and 6.0%, respectively, after 6 weeks of incubation. The extent of degradation seems to decrease with increasing grafting efficiency. There was initial rapid weight loss accompanied by the exponential increase in bacterial population and pH of the culture medium during the first week. The nitrogen analysis also showed the utilization of the polymer. A parallel set of experiments, carried out by employing the samples as the only source of both carbon and nitrogen, showed a marginal but definite increase in the utilization of the polymer.     

Grafting onto wool. XIV. Graft copolymerization of vinyl monomers by use of Mn(AcAc)3 as an initiator

Ethyl acrylate (EA), butyl acrylate (BA), and vinyl acetate (VAc) have been graft copolymerized onto Himachali wool fiber in an aqueous medium by using Mn(AcAc)₃ as an initiator. Graft copolymerization was studied at 45°, 55°, 65° and 75°C for various reaction periods. Percentage of grafting and percent efficiency were determined as functions of concentration of monomer, concentation of initiator, concentration of nitric acid, time, and temperature. Several grafting experiments were carried out in the presence of various additives which included: (i) pyridine and (ii) Et₃ N. EA, BA, and VAc were found to differ in reactivity towards grafting and followed the order: EA > BA > VAc.     

Kinetics and mechanism of free radical grafting of methyl acrylate onto sago starch

The graft copolymerization was carried out by methyl acrylate with sago starch in which ceric ammonium nitrate was used as an initiator. It has been found that the rates of graft polymerization and grafting efficiency were dependent upon the concentration of ceric ammonium nitrate (CAN), methyl acrylate (MA), sago starch (AGU, anhydro glucose unit), mineral acid (H₂SO₄), and as well as reaction temperature and period. A rate equation of polymerization was established from the proposed reaction mechanism, and the rate of polymerization (R_p) was the first‐order dependence of the MA monomer concentration and square root of the CAN concentration. A new kinetic model of the grafting reaction has been proposed, and a normal kinetics of methyl acrylate polymerization was observed. An equation of a predicted model relating the graft fraction of poly(methyl acrylate) with the sago starch has been derived, and validity of the predicted model was verified by the experimental results. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 784–791, 2000     

Functionalisation of polypropylene by solid phase graft polymerisation and its effect on the mechanical properties of silica nanocomposites

Abstract

To prepare macromolecular compatibiliser for grafted nano-SiO₂/polypropylene (PP) composites, solid phase graft copolymers of PP with styrene and ethyl acrylate were synthesised, respectively. It was found that both percentage grafting and grafting efficiency can be adjusted by changing initiator concentration, reaction temperature and reaction time. Due to partial chain scission and deterioration of the ordered structure of PP during the graft polymerisation, the grafted PP exhibits worse thermal stability and crystallisability than the unmodified PP. Mechanical tests of grafted nano-SiO₂/PP composites indicated that the addition of PP copolymer with the same species of grafting polymer as that on the nanoparticles further improves the ductility of the composites. Molecular rigidity of the grafting polymers, presence of the homopolymer produced during the graft polymerisation, and strain rate of the load applied have important influences on the toughening effect of the functionalised PP.