Graft copolymerizations of modified cellulose,grafting of acrylonitrile,and methyl methacrylate on carboxy methyl cellulose

Graft copolymers of acrylonitrile (ACN), methyl methacrylate (MMA), and their mixtures on carboxy methyl cellulose (d.S 0.4–0.5) were prepared by the use of ceric ion initiator in aqueous medium. The graft copolymers were characterized by IR spectroscopy. The extent of graft copolymerization of ACN and MMA was measured in terms of graft level, molecular weight of grafted polymer chains, and the frequency of grafting as functions of ceric ion concentration. It was found that at comparable reaction conditions, the molecular weight of the grafted polymer chains and the frequency of grafting were not of the same order of magnitude. For the monomer mixtures, the copolymer compositions obtained from the total nitrogen contents of the copolymer samples showed that a disproportionately low amount of ACN monomeric units were incorporated into the graft copolymer, even at high ACN content of the feed. © 1996 John Wiley & Sons, Inc.     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

Characterization and solution properties of a partially hydrolyzed graft copolymer of polyacrylamide and dextran

Graft copolymers of dextran (Dx) and polyacrylamide (PAM) were synthesized through the grafting of PAM chains onto a Dx backbone with a ceric‐ion‐induced solution polymerization technique. By the variation of the amount of the initiator (ceric ammonium nitrate), four different grades of graft copolymers were synthesized. The partial alkaline hydrolysis of Dx‐g‐PAM was carried out in an alkaline medium. Three grades of partially hydrolyzed products were synthesized through the variation of the amount of alkali. These hydrolyzed graft copolymers were characterized with elemental analysis, infrared spectroscopy, neutralization equivalent measurements, a rheological technique, scanning electron microscopy, thermal analysis, viscometry, and X‐ray diffraction. The flocculation efficiency and viscosifying characteristics of the graft copolymers were enhanced upon their alkaline hydrolysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

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     

Synthesis and properties of graft copolymer of cellulose diacetate with poly(caprolactone monoacrylate)

Cellulose diacetate grafting poly(caprolactone monoacrylate) copolymers (CDA‐g‐PCLA) were synthesized by a two‐step reaction of cellulose diacetate (CDA) with poly(caprolactone monoacrylate) (PCLA). The isocyanate‐terminated intermediate (NCOPCLA) was prepared and grafted onto cellulose diacetate chains. The results of the structure analysis indicated that PCLA was connected to CDA by chemical bonding. The flow temperature of graft copolymers was lower than that of the pure CDA and decreased with increasing the grafting percentage. Outdoor soil burial tests and active sludge tests indicated that the graft copolymers have good biodegradability in natural conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 85–90, 2003     

Synthesis and characterization of microcrystalline cellulose‐graft‐poly(methyl methacrylate) copolymers and their application as rubber reinforcements

In this study, redox‐initiated free radical graft copolymerization of microcrystalline cellulose (MCC) and methyl methacrylate (MMA) has been carried out in aqueous media to develop a novel cellulose‐based copolymer. Cerium ammonium nitrate was used as the initiator in the presence of nitric acid. Effects of monomer concentration, initiator concentration, polymerization time, and polymerization temperature on the graft parameters of copolymers were studied. The successful grafting copolymerization between MCC and MMA was validated through attenuated total reflection, wide‐angle X‐ray diffraction, field‐emission scanning electron microscopy, and thermal gravimetric analysis. In comparison to native MCC, the resultant copolymers exhibited enhanced thermal stability and better compatibility with natural rubber, suggesting its potential application as reinforcement material in rubber industry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42666.     

Graft copolymerization of vinyl monomers on cellulosic materials

Graft copolymers of acrylonitrile, ethyl acrylate, methyl acrylate, ethyl methacrylate and methyl methacrylate and of acrylonitrile/ethyl methacrylate and acrylonitrile/methyl methacrylate monomer mixtures on carboxymethylcellulose (degree of substitution 0.4–0.5) were prepared by use of ceric ion initiator in aqueous medium. The extent of graft polymer formation was measured in terms of graft level, molecular weight of grafted polymer chains and frequency of grafting as function of ceric ion concentration. It was found that at comparable reaction conditions, the molecular weight and frequency of grafting were not of the same order of magnitude. For the monomer mixtures, the copolymer compositions obtained from the total nitrogen content of the acrylonitrile/alkyl methacrylate copolymer samples showed that a relativity low amount of the acrylonitrile monomeric units were incorporated into the graft copolymer even at high acrylonitrile content of the feed.     

Preparation and characterization of grafting polyacrylamide from PET films by SI‐ATRP via water‐borne system

The grafted homopolymer and comb‐shaped copolymer of polyacrylamide were prepared by combining the self‐assembly of initiator and water‐borne surface‐initiated atom transfer radical polymerization (SI‐ATRP). The structures, composition, properties, and surface morphology of the modified PET films were characterized by FTIR/ATR, X‐ray photoelectron spectroscopy (XPS), contact angle measurement, and scanning electronic microscopy (SEM). The results show that the surface of PET films was covered by equable grafting polymer layer after grafted polyacrylamide (PAM). The amount of grafting polymer increased linearly with the polymerization time added. The GPC date show that the polymerization in the water‐borne medium at lower temperature (50°C) shows better “living” and control. After modified by comb‐shaped copolymer brushes, the modified PET film was completely covered with the second polymer layer (PAM) and water contact angle decreased to 13.6°. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of N‐vinyl pyrrolidone and cellulosics based functional graft copolymers for use as metal ions and iodine sorbents

To develop cost effective and eco friendly polymeric materials for enrichment and separation technologies, 1‐vinyl‐2‐pyrrolidone (N‐VP) was graft copolymerized onto cellulose, extracted from pine needles. Optimum conditions have been evaluated for the grafting of N‐VP onto cellulose and at these conditions it was also grafted onto cellulose phosphate, hydroxypropyl cellulose, cyanoethyl cellulose, and deoxyhydrazino cellulose. At the optimum grafting conditions for N‐VP, it was also cografted with maleic anhydride. Kinetics of radiochemical graft copolymerization has been studied and evaluation of the polymerization and grafting parameters as percent grafting, percent grafting efficiency, rate of polymerization, homopolymerization, and graft copolymerization have been evaluated. Graft copolymers have been characterized by elemental analysis, FTIR, and swelling studies. An attempt has been made to study sorption of some metal ions such as Fe²⁺ and Cu²⁺ and iodine on select graft copolymers to investigate selectivity in metal ion sorption and iodine sorption as a function of structural aspects of the functionalized graft copolymers to find their end uses in separation and enrichment technologies. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 373–382, 2005     

Graft copolymerization of methyl acrylate onto cellulose initiated by potassium ditelluratoargentate(III)

A novel redox system, potassium ditelluratoargentate(III) (DTA)–cellulose, was employed to initiate the graft copolymerization of methyl acrylate onto cellulose in alkali aqueous solution. Grafting parameters, such as total conversion, grafting efficiency and grafting yield, were evaluated comparatively. The dependence of these parameters on temperature, reaction time, initiator concentration and ratio of monomer to cellulose was also investigated. Graft copolymers with high grafting parameters were obtained, which indicated that the DTA–cellulose redox pair is an efficient initiator for cellulose grafting. The proof of grafting was obtained from gravimetric analysis and infrared spectra. A tentative mechanism involving a two‐step single‐electron‐transfer process of DTA is proposed to explain the generation of radicals and initiation. Thermogravimetry, X‐ray diffraction and scanning electron microscopy were also carried out to study the thermal stability, crystallinity and morphology of the grafted copolymers. Copyright © 2004 Society of Chemical Industry     

Grafting of polyelectrolytes onto polyacrylamide by reactive processing

Low‐molecular‐weight high‐charge‐density cationic poly diallydimethyl ammonium chloride (polyDADMAC) was grafted onto nonionic polyacrylamide (PAM) using organic peroxide initiators in the molten state carried out in a batch mixer. The graft copolymer can be used as a high performance flocculant. Glycerol was selected as a plasticizer. The grafting reaction was characterized in terms of composition, temperature, degree of grafting, and grafting efficiency. It was found that free radicals on polymer chains were induced by the decomposition of the initiator. Grafting was produced by free radical recombination termination. The degree of grafting increases with an increase of the polyDADMAC/PAM feed ratio. However, the grafting efficiency was lower than 10 wt % in this highly viscous polymer melt system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1412–1416, 1999     

Synthesis and characterization of grafted carboxymethyl guar gum

Graft copolymers of carboxymethyl guar gum (CMGG) and polyacrylamide (PAM) have been synthesized by grafting polyacrylamide chains onto carboxymethyl guar gum backbone using a ceric‐ion‐induced solution polymerization technique. By varying the amount of initiator, three different grades of graft copolymers are synthesized. The characterization of graft copolymer is carried out by FTIR, NMR, intrinsic viscosity measurement, SEM, SLS, DTG, and rheology. A comparison of flocculation efficiency of CMGG and its graft copolymer shows that the graft copolymer exhibits better flocculation performance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Initiation of surface graft polymerization by ceric ions on polymer microspheres

The surface graft polymerization of acrylamide on poly(styrene‐co‐acrylonitrile) copolymer microspheres by the initiation of ceric ions was studied. The grafting was verified by IR spectra and X‐ray photoelectron spectroscopy measurements. The resultant microspheres with surface‐grafted polymer chains were employed in the preparation of polymer‐microsphere‐supported palladium composite particles. The composite particles were then studied by transmission electron microscopy and X‐ray diffraction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 936–940, 2003     

Chemical Functionalization of Graphene Oxide by Poly(styrene sulfonate) Using Atom Transfer Radical and Free Radical Polymerization: A Comparative Study

Poly(sodium styrenesulfonate)-functionalized graphene was prepared from graphene oxide, using atom transfer radical polymerization and free radical polymerization. In atom transfer radical polymerization route, the amine-functionalized GO was synthesized through hydroxyl group reaction of GO with 3-amino propyltriethoxysilane. Atom transfer radical polymerization initiator was grafted onto modified GO (GO-NH₂) by reaction of 2-bromo-2-methylpropionyl bromide with amine groups, then styrene sulfonate monomers were polymerized on the surface of GO sheets by in situ atom transfer radical polymerization. In free radical polymerization route, the poly(sodium 4-styrenesulfonate) chains were grafted on GO sheets in presence of Azobis-Isobutyronitrile as an initiator and styrene sulfonate monomer in water medium. The resulting modified GO was characterized using range of techniques. Thermal gravimetric analysis, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy results indicated the successful graft of polymer chains on GO sheets. Thermogravimetric analysis showed that the amount of grafted polymer was 22.5 and 31?wt% in the free radical polymerization and atom transfer radical polymerization methods, respectively. The thickness of polymer grafted on GO sheets was 2.1?nm (free radical polymerization method) and 6?nm (atom transfer radical polymerization method) that was measured by atomic force microscopy analysis. X-ray diffractometer and transmission electron microscopy indicated that after grafting of poly(sodium 4-styrenesulfonate), the modified GO sheets still retained isolated and exfoliated, and also the dispersibility was enhanced.     

Competitive removal of heavy metal ions by cellulose graft copolymers

The effect of composition of graft chains of four types cellulose graft copolymers on the competitive removal of Pb²⁺, Cu²⁺, and Cd²⁺ ions from aqueous solution was investigated. The copolymers used were (1) cellulose‐g‐polyacrylic acid (cellulose‐g‐pAA) with grafting percentages of 7, 18, and 30%; (2) cellulose‐g‐p(AA–NMBA) prepared by grafting of AA onto cellulose in the presence of crosslinking agent of N,N′‐methylene bisacrylamide (NMBA); (3) cellulose‐g‐p(AA–AASO₃H) prepared by grafting of a monomer mixture of acrylic acid (AA) and 2‐acrylamido‐2‐methyl propane sulphonic acid (AASO₃H) containing 10% (in mole) AASO₃H; and (4) cellulose‐g‐pAASO₃H obtained by grafting of AASO₃H onto cellulose. The concentrations of ions which were kept constant at 4 mmol/L in an aqueous solution of pH 4.5 were equal. Metal ion removal capacities and removal percentages of the copolymers was determined. Metal ion removal capacity of cellulose‐g‐pAA did not change with the increase in grafting percentages of the copolymer and determined to be 0.27 mmol metal ion/g_copolymer. Although the metal removal rate of cellulose‐g‐p(AA–NMBA) copolymer was lower than that of cellulose‐g‐pAA, removal capacities of both copolymers were the same which was equal to 0.24 mmol metal ion/g_copolymer. Cellulose did not remove any ion under the same conditions. In addition, cellulose‐g‐pAASO₃H removed practically no ion from the aqueous solution (0.02 mmol metal ion/g_copolymer). The presence of AASO₃H in the graft chains of cellulose‐g‐p(AA–AASO₃H) created a synergistic effect with respect to metal removal and led to a slight increase in metal ion adsorption capability in comparison to that of cellulose‐g‐pAA. All types of cellulose copolymers were found to be selective for the removal of Pb²⁺ over Cu²⁺ and Cd²⁺. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2034–2039, 2003     

Synthesis and characterization of starch‐graft‐polyacrylamide copolymers and their application as filtration control agents in drilling fluid

Some starch‐graft‐polyacrylamide copolymers were prepared by the polymerization of corn starch with acrylamide in aqueous medium using a complex initiation system consisting of ceric ammonium sulphate and ammonium persulphate. The copolymers were applied to water‐based drilling fluid as filtration control agents. Their grafting parameters such as percentage of grafting, grafting efficiency, and solution viscosity (η) were investigated by using elemental analyzer and rotational viscometer. The results showed that increases in initiator concentration and reaction temperature first favored and then impeded the grafting reaction. Grafting of acrylamide onto starch increased with the increase of monomer concentration. It also increased with increasing reaction time up to a certain degree and then leveled off. For the graft copolymers, a higher percentage of grafting and higher η were beneficial in decreasing the filtrate volume of water‐based drilling fluid, even under an operating environments of 147°C and saturated salinity. A possible mechanism is proposed to interpret the improvement of fluid loss properties. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Ceric‐initiated free radical graft copolymerization of acrylonitrile onto kappa carrageenan

The polysaccharide, kappa carrageenan (kC), was modified using ceric‐initiated graft copolymerization of acrylonitrile (AN) under inert atmosphere in a homogeneous aqueous medium. Grafting was confirmed using FTIR spectroscopy, solubility test, elemental analysis, acid hydrolysis, and thermogravimetric analysis (TGA). kC‐graft‐poly(AN) products had a higher thermal stability than kC as revealed by TGA analysis. The polyacrylonitrile branches were isolated by acidic degradation of the carrageenan main chains and characterized by size exclusion chromatography (SEC). Residual monomers were not found by HPLC in graft copolymers stored even for longer periods. The effect of various factors affecting on grafting, i.e., concentration of the initiator, monomer, and polysaccharide as well as the reaction time and temperature were studied by conventional methods to achieve the optimum grafting parameters. The graft copolymerization reactions were kinetically investigated using semi‐empirical expressions and a suitable rate expression has been derived. According to the empirical rates of the polymerization and the graft copolymerization of AN onto kC backbone, the overall activation energy of the graft copolymerization reaction was estimated to be 20.96 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization, and flocculation characteristics of polyacrylamide‐grafted glycogen

The synthesis of glycogen‐g‐polyacrylamide (Gly‐g‐PAM) was carried out by a ceric ion‐induced solution polymerization technique. Six grades of graft copolymers were synthesized by the variation of catalyst and monomer concentrations. These graft copolymers were characterized by intrinsic viscosity measurements, FTIR spectroscopy, and X‐ray diffraction techniques. Flocculation performance of these graft copolymers were done in kaolin suspension. Of the above grades, the graft copolymer Gly‐g‐PAM 5, which has longer PAM chains, showed best flocculation performance. The flocculation performance of the graft copolymer was compared with commercial flocculants and other PAM‐grafted flocculants developed so far in the authors' laboratory. In all the cases, it was found that the graft copolymer performed the best. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 773–778, 2007     

Graft copolymers of starch. I. Copolymerization of gelatinized wheat starch with acrylonitrile. Fractionation of copolymer and effect of solvent on copolymer composition

The starch–polyacrylonitrile graft copolymer prepared from gelatinized wheat starch with ceric ammoninm nitrate as the initiator has been freed of ungrafted polyacrylonitrile and separated into fractions by extraction with dimethylformamide, γ-butyrolactone, and dimethyl sulfoxide. The copolymer fractions obtained differed appreciably in level of add-on, molecular weights of grafted chains, and grafting frequency. To determiue the molecular weights of grafted chains, the starch part of the copolymer was effectively removed by hydrolysis with α-amylase. It was necessary to dissolve or swell the polymer in dimethyl sulfoxide and freshly precipitate it by addition to water before enzymatic hydrolysis. In studying the effect of reaction medium on copolymer composition, there was less ungrafted homopolymer formed and a higher yield of graft copolymer possessing more frequent grafts with water than with aqueous dimethylformamide or aqueous ethylene glycol. Polymer solubility, the results of control polymerizations of acrylonitrile in the absence of starch, and the detection of glucose endgroups on the polyacrylonitrile liberated from the fractionated polymer by hydrolysis are presented as evidence that the copolymers obtained are true grafts rather thau intimate mixtures.     

Graft copolymers prepared by atom transfer radical polymerization (ATRP) from cellulose

A cellulose-based macro-initiator, cellulose 2-bromoisobutyrylate, for atom transfer radical polymerization (ATRP) was successfully synthesized by direct homogeneous acylation of cellulose in a room temperature ionic liquid, 1-allyl-3-methylimidazolium chloride, without using any catalysts and protecting group chemistry. ATRP of methyl methacrylate and styrene from the macro-initiator was then carried out. The synthesized cellulose graft copolymers were characterized by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The grafted PMMA and PS chains were obtained by the hydrolysis of the cellulose backbone and analyzed by GPC. The results obtained from these analytical techniques confirm that the graft polymerization occurred from the cellulose backbone and the obtained copolymers had grafted polymer chains with well-controlled molecular weight and polydispersity. Through static and dynamic laser light scattering and TEM measurements, it was found that the cellulose graft copolymer in solution could aggregate and self-assembly into sphere-like polymeric structure.