Grafting of polyacrylonitrile onto guar gum under microwave irradiation

Using microwave (MW) irradiation grafting of polyacrylonitrile (PAN) onto guar gum in water was done without using any radical initiator or catalyst within a very short reaction time. The extent of grafting could be adjusted by controlling the reaction conditions and maximum percentage grafting (%G) of about 188% was obtained under optimum conditions in 1.66 min. The average molecular weight of the grafted PAN chains and water‐retention power of the alkali hydrolyzed MW‐grafted gums were also determined and compared with those of the conventionally synthesized (cs) graft copolymer. A representative MW‐grafted copolymer, guar‐g‐polyacrylonitrile was characterized by IR, NMR, XRD, TGA, and elemental analysis. A plausible mechanism for the grafting under MW was proposed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1569–1575, 2004     

Persulfate/ascorbic acid initiated synthesis of poly(acrylonitrile)‐grafted tamarind seed gum: A potential commercial gum

Acrylonitrile was grafted on to tamarind seed gum using persulfate/ascorbic acid redox initiator and a representative sample of the graft copolymer (Tm‐g‐PAN) was characterized using infrared spectroscopy (FTIR), X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Grafting conditions were optimized where %G and %E were found to increase with the increase in the concentration of the monomer; initiator, and the reaction temperature, whereas increase in gum concentration decreased the %G in the concentration range of 4–12 g/L, The maximum % grafting (%G) and % efficiency (%E) achieved were 305 and 75%, respectively. Water/saline retention, gel forming ability, and the shelf life of the grafted gum solutions were also studied to explore the possibility of its commercial utilization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ceric ammonium sulfate/sodium disulfite initiated grafting of acrylamide on to Cassia reticulata seed gum

Ceric ammonium sulfate/sodium disulfite redox system was evaluated for the poly(acrylamide) (PAM) grafting on to Cassia reticulata (CR) seed gum. Grafting conditions were optimized and the maximum %Grafting (%G) and %Efficiency (%E) achieved were 152 and 97.2%, respectively, using [disulfite] 0.005M; [ceric ammonium sulfate] 0.026M; [acrylamide] 0.11M; [gum] 0.125 g/25mL at 40 ± 0.2°C. Representative CR‐grafted gum (CRPAM) was characterized by Fourier transform infrared spectrometry (FTIR), X‐ray diffraction (XRD), and thermogravimetric analysis (TGA). Under identical conditions, the redox initiator could result 142.6 %G and 91.2 %E on to guar gum (GG). Various physical properties of the CR gum/grafted CR gum, such as viscosity, water retention, and saline retention, were studied and compared with GG/grafted GG to find out the potential industrial use of CR gum and PAM‐grafted‐CR gum. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Microwave enhanced synthesis of chitosan-graft-polyacrylamide

Chitosan-graft-polyacrylamide (Ch-g-PAM) was synthesized without any radical initiator or catalyst using microwave (MW) irradiation. Under optimal grafting conditions, 169% grafting was observed at 80% MW power in 1.16 min. Conventionally under similar conditions a maximum grafting of 82% could be achieved in 1 h using K₂S₂O₈/ascorbic acid as redox initiator coupled with Ag⁺ ions as catalyst and atmospheric oxygen as co-catalyst on a thermostatic water bath at 35±0.2 °C. The representative microwave synthesized graft copolymer was characterized by Fourier transform-infrared spectroscopy, thermo gravimetric analysis and X-ray diffraction measurement, taking chitosan as a reference. The effects of reaction variables as monomer/chitosan concentration, MW power and exposure time on the graft co-polymerization were studied. A probable free radical mechanism for grafting under microwaves has been proposed. The solubility pH for the grafted samples with different extent of grafting was monitored. The adsorption capacity of chitosan was much enhanced after grafting. The microwave synthesized Ch-g-PAM in comparison to that prepared conventionally was found to have much more adsorption ability for Ca²⁺ and Zn²⁺ ions in aqueous solution.     

Homogeneous and heterogeneous grafting of 4‐vinylpyridine onto chitosan

Modification of chitosan by grafting with 4‐vinylpyridine (VP) was carried out both in homogeneous and heterogeneous phases, using potassium persulfate (K₂S₂O₈) and sodium bisulfite (NaHSO₃) as redox initiators. The effect of monomer concentration, initiator concentration and redox ratio, time and temperature on the extent of grafting (G%), homopolymer formation, and the efficiency of grafting were studied. Values of grafting percentages up to 96% were reached in heterogeneous conditions and up to 130% in homogeneous conditions (in 5% acetic acid). The grafting was confirmed by FTIR and ¹H NMR spectroscopy. The grafted samples were characterized by scanning electron microscopy, X‐ray diffraction, and thermogravimetric analysis. The crystallinity of the used chitosan was not affected by grafting, it even increased slightly. Dye uptake of the grafted samples towards the different types of dyes (acidic and basic) was investigated and was found to improve profoundly over the native chitosan with a higher uptake for the acidic dye. The grafted samples showed an increased swelling in water, which increased further upon quaternization of the graft copolymers. The extent of swelling is higher in acidic and basic media more than in neutral pH. The grafted copolymers are soluble with difficulty in warm acetic acid solution. The quaternized graft copolymer was found to be soluble in water. The biological activity of the quaternized graft copolymers (G = 130 and 80%) was investigated and was found to have an inhibition effect on both the Azotobacter fungus and the bacterium Fusarium oxysporium. The effect on the micro organisms is proportional to the amount of VP in the graft copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3308–3317, 2006     

Co(III) acetylacetonate-complex-initiated grafting of N-vinyl pyrrolidone on cellulose in aqueous media

The graft copolymerization of N-vinyl pyrrolidone (N-VP) onto cellulose was carried out with a cobalt acetylacetonate complex Co(acac)₃ as an initiator under a nitrogen atmosphere at 50 ± 0.1°C. The graft yield percentage (%G) obtained as a function of the concentrations of N-VP and Co(acac)₃ and the temperature was used to calculate various other grafting parameters and the grafting rate dependence on the concentrations of monomer, Co(acac)₃ and reaction temperature. The energy of activation (ΔE_a) for the grafting of N-VP onto cellulose was 22.7 kJ/mol within 40–60°C. The molecular weights of the grafted chains and homopolymers were determined viscometrically with a Ubbelohde-type viscometer. Graft yield (%G) in the presence of various additives such as sodium lauryl sulfate, cetyltrimethylammonium bromide, and methanol was studied, and the results are suitably explained. On the basis of the experimental results, a reaction scheme for graft copolymerization is proposed, and a kinetic rate expression is presented. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2286–2296, 2001     

Microwave promoted synthesis of chitosan‐graft‐poly(acrylonitrile)

Using microwave (MW) irradiation, polyacrylonitrile was grafted onto chitosan with 170% grafting yield under homogeneous conditions in 1.5 min in the absence of any radical initiator or catalyst. Under similar conditions a maximum grafting of 105% could be achieved when the K₂S₂O₈/ascorbic acid redox system was used as radical initiator in a thermostatic water bath at 35 ± 2°C. The representative graft copolymer was characterized by Fourier transform infrared spectra, thermogravimetric analysis, and X‐ray diffraction measurement, taking chitosan as a reference. The effects of such reaction variables as monomer/chitosan concentration, MW power, and exposure time on the graft co polymerization were studied. A probable mechanism for grafting without the redox system under microwaves was proposed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 820–825, 2005     

Alumina‐supported microwave synthesis of Cassia marginata seed gum‐graft‐polyacrylamide

In this article, we report the alumina‐supported, microwave (MW)‐induced synthesis of Cassia marginata seed gum‐graft‐polyacrylamide (MWS‐GP). No initiator or catalyst was required in the synthesis, and the conditions for the grafting were optimized by variation of the acrylamide concentration, MW power, and exposure time. At an identical monomer concentration, a higher level of grafting was observed in the solid‐supported method than under aqueous conditions (the MW‐assisted or redox‐initiated thermal method). The used alumina support was easily separated from MWS‐GP and reused for another three cycles without any significant loss in its efficiency as a solid support. MWS‐GP synthesized under optimum conditions was characterized with Fourier transform infrared spectroscopy, ¹³C‐NMR, thermogravimetric analysis, and X‐ray diffraction, with C. marginata gum as a reference. The properties of MWS‐GP and its saponified derivative were studied to explore the applicability areas of the copolymer in hydrogel formation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of graft copolymer (guar gum–g–N‐vinyl‐2‐pyrrolidone) and investigation of metal ion sorption and swelling behavior

Graft copolymer of N‐vinyl‐2‐pyrrolidone with guar gum was synthesized and its reaction conditions were optimized for better yield using potassium peroxymonosulfate (PMS) and glycolic acid (GA) as a redox initiator. The effect of PMS, GA, hydrogen ions, guar gum, and N‐vinyl‐2‐pyrrolidone (NVP) along with reaction time and temperature were studied by determining the grafting parameters: grafting ratio, efficiency, conversion, add‐on, homopolymer, and rate of grafting. It was observed that the maximum yield occurred at with a time of 120 min at a temperature of 45°C and a guar gum concentration of 0.4 g/L concentration. The graft copolymer was characterized by infrared spectroscopy and thermal analysis. The activation energy for the grafted and ungrafted gum was calculated. It was observed that the graft copolymer was thermally more stable than the pure gum. The swelling and metal ion sorption behavior of guar gum and guar gum‐g‐N‐vinyl‐2‐pyrrolidone also were studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2480–2489, 2006     

Synthesis of seaweed polysaccharide‐based polyvinylpyrrolidone copolymer with adhesive properties

Polyvinylpyrrolidone (PVP) grafted sulfated polysaccharide of the seaweed Cystoseira indica (CI_sps) (CI_sps‐graft‐PVP) was synthesized in aqueous medium under microwave irradiation in the presence of potassium persulfate (KPS), as a free radical initiator. Varying the reaction parameters, e.g., concentration of PVP and KPS, reaction time and temperature, optimum grafting condition was identified as the one having the highest grafting ratio (Gr 2.30) and grafting efficiency (Ge 0.92). The grafted copolymer was characterized by FT‐IR, ¹³C‐NMR and thermo gravimetric analysis (TGA). The 5% (w/v) dispersion of the new material CI_sps‐graft‐PVP in water exhibited comparable binding properties with papers, polyethylene sheets, and wood pieces as against that of a commercial adhesive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42383.     

Synthesis and characterization of xanthan gum‐g‐N‐vinyl formamide with a potassium monopersulfate/Ag(I) system

A xanthan gum‐g‐N‐vinyl formamide graft copolymer was synthesized through the graft copolymerization of N‐vinyl formamide (NVF) onto xanthan gum with an efficient system, that is, potassium monopersulfate (PMS)/Ag(I) in an aqueous medium. The effects of the concentrations of Ag(I), PMS (KHSO₅), hydrogen ion, xanthan gum, and NVF along with the time and temperature on the graft copolymerization were studied by the determination of the grafting parameters (grafting ratio, add‐on, conversion, grafting efficiency, and homopolymer) and the rate of grafting. The maximum grafting ratio was obtained at a 0.6 g/dm³ concentration of xanthan gum. All the parameters showed an increasing trend with an increasing concentration of peroxymonosulfate, except the homopolymer percentage, which showed a decreasing trend. The grafting ratio, add‐on conversion, grafting efficiency, and rate of grafting increased with the concentration of Ag(I) increasing from 0.8 × 10^?2 to 1.2 × 10^?2 mol/dm³. The optimum time and temperature for the maximum degree of grafting were 90 min and 35°C, respectively. The graft copolymer was characterized with IR spectral analysis, thermogravimetric analysis, and differential calorimetry analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1637–1645, 2006     

Synthesis and characterization of butyl acrylate graft sodium salt of partially carboxymethylated starch

Graft copolymers were synthesized by graft copolymerization of butyl acrylate (BA) onto sodium salt of partially carboxymethylated starch (Na‐PCMS). Ceric ammonium nitrate (CAN), a redox initiator, was used for initiation of graft copolymerization reaction. All the experiments were run with Na‐PCMS having degree of substitution, DS = 0.35. The grafting reaction was characterized by parameters such as % total conversion (%Ct), % grafting (%G), % grafting efficiency (%GE), and % add‐on. Graft copolymers were characterized by infrared spectral analysis and scanning electron microscopy. Variables affecting graft copolymerization reaction such as nitric acid concentration, reaction time, reaction temperature, and ceric ion concentration were investigated. The results revealed that 0.3M CAN as initiator, 0.3M HNO₃, with reaction time 4–4.5 h at 25–30°C were found as suitable parameters for maximum yield of graft copolymerization reaction. © 2006 Wiley Periodicals, Inc. JAppl Polym Sci 102: 3334–3340, 2006     

Graft copolymers of starch with mixtures of acrylamide and the nitric acid salt of dimethylaminoethyl methacrylate

Mixtures of acrylamide and the nitric acid salt of dimethylaminoethyl methacrylate (DMAEMA·HNO₃) have been graft polymerized onto unmodified wheat starch with ferrous ammonium sulfate–hydrogen peroxide initiation. Graft polymerizations were carried out with both unswollen starch granules and granules that had been swollen by heating in water to 60°C. Ungrafted synthetic polymers were removed from graft copolymers by cold-water extraction and were characterized by their M?_n and DMAEMA·HNO₃ content. Graft copolymers were characterized with respect to per cent add-on, M?_n and DMAEMA·HNO₃ content of grafted polymer, and grafting frequency. Ungrafted synthetic polymers contained a mole percentage of DMAEMA·HNO₃ equal to or greater than that present in the initial monomer mixtures; whereas in most grafted polymers the mole-% DMAEMA·HNO₃ in the grafted branches was less than that in the starting monomers. At all monomer ratios examined, polymer grafted to swollen starch granules contained a higher percentage of DMAEMA·HNO₃ then polymer grafted to unswollen starch. The influence of starch granule swelling on the molecular weight and frequency of grafted branches was correlated with the composition of the initial monomer mixture. It was determined that the effect of granule swelling on graft copolymer structure would be minimal when 25–30 mole-% DMAEMA·HNO₃ was used. In an acetonitrile–water solvent system, reactions with 20 and 50 mole-% DMAEMA·HNO₃ produced graft copolymers with less DMAEMA·HNO₃ in grafted branches than corresponding graft polymerizations run in water. The flocculation of 3% aqueous suspensions of diatomaceous silica was examined with selected starch graft copolymers.     

Graft copolymerization of acrylamide–methylacrylate comonomers onto cellulose using ceric ammonium nitrate

The graft copolymerization of acrylamide–methylacrylate comonomers was carried out using ceric ammonium nitrate as initiator in the presence of nitric acid at 25 ± 1°C. The effects of feed molarity, feed composition, reaction time, and temperature on graft yield (%G) and other grafting parameters were investigated. The determination of rate of ceric (IV) ions disappearance as a function of feed molarity and reaction time was useful in the determination of the rate of ceric (IV) ions consumption during graft copolymerization. The graft yield (%G) in the presence of acrylamide increases because of the synergistic effect of acrylamide comonomer. The composition of the grafted chains (F_AAm) varies on varying the feed composition and reaction temperature but is almost constant during feed molarity variation. The Mayo and Lewis method was used to determine the reactivity ratios of acrylamide (r₁) and methylacrylate (r₂), which are 0.65 and 1.07, respectively. The product of reactivity ratio (r₁ r₂) is less then unity; hence, an alternate arrangement of comonomer blocks in the grafted copolymer chain is proposed. The rate of graft copolymerization of comonomers onto cellulose is second power to the concentration of comonomers and square root to the concentration of ceric ammonium nitrate. Suitable reaction steps for graft copolymerization of comonomers onto cellulose are proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2631–2642, 2002     

Grafting of acrylonitrile and methyl methacrylate from their binary mixtures on cellulose using ceric ions

Ceric ion‐initiated grafting on cellulose from a binary mixture of acrylonitrile and methyl methacrylate was carried out in heterogeneous and acidic conditions at 30 ± 0.1°C in a nitrogen atmosphere. To avoid the complexation of water molecules with Ce(IV) ions, the concentration of the nitric acid was taken to be more than the concentration of ceric ions. The effect of the feed concentration, reaction time, and ceric ions concentration on grafting were investigated at a fixed composition. To investigate the effect of monomer–monomer interactions on grafting, the graft copolymerization was also studied, using different feed compositions (f_AN) ranging from 0.25 to 0.80. In this range of feed composition, the synergistic effect of methyl methacrylate molecules has shown an important effect on acrylonitrile monomer and facilitate the incorporation of the acrylonitrile monomer into the grafted chains. The reactivity ratios of acrylonitrile and methyl methacrylate were calculated using the Mayo and Lewis method and were found to be 0.74 and 1.03, respectively. The average sequence lengths of the monomers (m̄M) were found to be dependent on the feed compositions and found to be arranged in alternate fashion in the grafted chains. The probability of the addition of a monomer (P_1,1) to the growing radicals on cellulose ended with its own type of monomer was found to be dependent on the feed composition. The composition of the grafted copolymers, homocopolymers, was determined by IR and elemental analysis for nitrogen. None of the grafted chain on cellulose was found to be made of a single type of monomer. The ceric ion consumption during grafting was found to be independent of the molarity of the feed but shown an appreciable change in the initial few hours of grafting. The variation in the values of the grafting parameters as a function of the reaction conditions is suitably explained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 767–778, 2001     

Grafting of acryloyl cyanoacetohydrazide onto chitosan

Chitosan was grafted with a novel monomer namely Acryloyl cyanoacetohydrazide (ACAH) which contains carbonyl and cyano groups. The graft copolymerization was conducted in heterogeneous phase using potassium persulfate (K₂S₂O₈) and sodium bisulfite (NaHSO₃) as redox initiators. The effect of monomer concentration, initiator concentration and ratio, time and temperature on the extent of grafting (G%) and the efficiency of grafting were studied. Homopolymer formation has not been observed under all the investigated conditions. The grafted samples were characterized by FTIR spectroscopy, X-ray diffraction and thermogravimetric analysis. The crystallinity of the used chitosan was reduced by grafting. Dye uptake of the grafted samples towards the different types of dyes (acidic, and basic) was investigated and was found to improve profoundly over the native chitosan with a higher uptake for the acidic dye. The grafted samples showed an increased swelling in water, which increased further upon quaternization of the graft copolymers. The extent of swelling is higher in acidic and basic media more than in neutral pH. The quaternized graft copolymer was found to be soluble in water. The fungicidal activity of the quaternized graft copolymers towards three soil-borne sugar beets pathogens was investigated in vitro. The effect on the micro organisms is proportional to the amount of ACAH in the graft copolymer.     

Surface functionalization of Si3N4 nanoparticles by graft polymerization of glycidyl methacrylate and styrene

To improve dispersibility and interfacial interaction of nano‐Si₃N₄ particles in epoxy‐based composites, graft of glycidyl methacrylate (GMA) and styrene (St)/GMA onto the nanoparticles' surface was carried out in terms of emulsion polymerization method. The grafting polymers proved to be chemically attached to the nanoparticles via the double bonds introduced during the coupling agent pretreatment. The factors affecting the graft parameters, such as monomer concentration, initiator consumption, reaction time, etc., were investigated. It was shown that higher concentrations of monomer and initiator are favorable for the graft polymerization. When St/GMA was employed as the grafting monomer, the nanoparticles were found to play the role of polymerization loci. The grafted nanoparticles exhibit greatly improved dispersibility in cured epoxy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 992–999, 2006     

Grafting of methyl methacrylate on EPR and EPDR: Impact properties of polyvinyl chloride grafted polymer blends

EPDM rubber can be brought into water suspension after swelling in n-heptane containing proper emulsifiers and in shear stress; particles reach dimensions as low as 150 Å. Methyl methacrylate in emulsion can be grafted easily with Bz₂O₂ on the rubber. Grafting yields depend particularly on the monomer/rubber ratio. The grafted polymer can be recovered by precipitating the emulsion with acetone, which eliminates the homopolymer. The grafting mechanism is discussed in terms of different initiators (AIBN and Bz₂O₂) and unsaturated (EPDM) and saturated rubber (EPR); AIBN and PMMA radicals were inactive in abstracting hydrogen atoms from rubber chains. Mechanical properties of the blends with PVC of the raw graft product are discussed on the basis of the grafted polymer composition and synthesis conditions. Very high impact strength can be reached at 15% rubber content in the blend for a grafted polymer obtained from a monomer/rubber ratio equal to 0.75.     

Sepiolite grafted polypyrrole: Influence of degree of grafting on structural,thermal, and impedance properties of nanohybrid

Conductive pyrrole monomer was grafted on vinyl modified sepiolite by surface initiated emulsion graft polymerization. Effect of process variables such as monomer, initiator, and surfactant on degree of grafting (%) were investigated. Maximum 745% degree of grafting was obtained at optimized grafting conditions. Structural changes in sepiolite by grafting of polypyrrole chains was confirmed by Fourier transform infrared spectroscopy and X-ray diffraction techniques. Surface morphology of the grafted nanohybrid was investigated by scanning electron microscopy (SEM). Thermal studies were carried out to acquire information concerning thermal stability of the synthesized materials and it was found increasing with the increase in grafting (%) of polypyrrole in sepiolite grafted polypyrrole (MS-g-PPy). Complex impedance spectroscopic analysis was carried out to study the effects of grafting of PPy on the ac electrical properties of synthesized nanohybrid composite at ambient temperature in the frequency range of 0.5–10⁷ Hz. The value of electrical conductivity was affected by degree of grafting (%) and maximum value of 0.85 × 10⁻⁴ S/cm was achieved. Both dielectric loss factor and permittivity increase with the decrease of frequency exhibiting strong interfacial polarization at low frequency.     

Microwave irradiation graft copolymerization of hydroxyethyl methacrylate onto wool fabrics

Hydroxyethyl methacrylate was grafted onto woolen fabrics by microwave irradiation in the presence of catalyst (NH₄)₂S₂O₈. Various parameters of the graft copolymerization reaction, namely, time, microwave intensity, catalyst, and monomer concentration, were optimized. The graft copolymerization was also compared with conventional heating graft copolymerization at the same condition. Microwave irradiation was shown to improve the reactivity of the monomer. The moisture regain decreased as graft add-on increased. The Max load and the strain at Max load increased as graft add-on increased. The infrared spectra showed an additional peak at 1700 cm⁻¹, confirming ester carbonyl groups of the monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2343–2347, 1998