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     

Structure and properties of cellulose graft copolymers. I. Radiation-induced rayon–styrene graft copolymer

Rayon–styrene graft copolymers were prepared by the direct radiation method, with the use of the preswelling technique, by irradiation with γ-rays from ⁶⁰Co. The grafting was carried out in bulk styrene and in styrene–solvent mixtures, such as styrene–methanol and styrene–acetone, to study their effect on the graft copolymerization reaction and the structure of the resulting graft copolymer. The effects of carbon tetrachloride, a chain-transfer agent, was also investigated. Three different types of rayon yarn were used; Fortisan, a modifier-type high wet-modulus rayon, and a high-tenacity tire yarn, in order to study the effect of rayon microstructure on the grafting reaction. The molecular structure of the rayon–styrene graft copolymers was studied by hydrolyzing away the cellulose backbone and measuring the molecular weights of the grafted polystyrene branches. For grafting in bulk styrene, the molecular weights of the grafted polystyrene ranged from 400,000 to 1,000,000, while those of the polystyrene homopolymer formed in the outside solution were of the order of 30,000–50,000. The molecular weights of the grafted polystyrene branches tended to increase with per cent grafting in the graft copolymer. For grafting in styrene–methanol and styrene–acetone mixtures, the molecular weights of the polystyrene branches decreased with increasing solvent content. The addition of carbon tetrachloride to bulk styrene resulted in a sharp decrease in the molecular weights of the grafted branches. The grafting frequency or number of polystyrene branches per cellulose chain was calculated from the per cent grafting and the molecular weights of the polystyrene branches. The morphology of the rayon–styrene graft copolymers and some of their physical properties are discussed.     

Grafting of methyl methacrylate to nitrocellulose by ceric ions

Studies were carried out on grafting of various vinyl monomers to nitrocellulose by ceric ions. It was observed that graft copolymerization occurred only with methyl methacrylate (MMA) and methyl acrylate monomer. The variables such as initiator concentration, monomer concentration, time of grafting, and nitrocellulose content on grafting of MMA are discussed. By hydrolyzing away the nitrocellulose backbone, the grafted poly(methyl methacrylate) branches were isolated and the >c?o peak at 1740 cm^?1 in the infrared spectra of these isolated branches gave definite evidence of grafting. The molecular weight of isolated branches has been determined by viscometry. The probable mechanism of grafting may be at the α-carbon atom of primary alcohol or at a C₂-C₃ glycol group of the anhydro glucose unit or at the hemiacetal group of the end unit of nitrocellulose, as nitrocellulose is formed by the partial nitration of cotton cellulose.     

Graft copolymerization of acrylamide onto cellulose in presence of comonomer using ceric ammonium nitrate as initiator

The graft copolymerization of acrylamide (AAm) and ethylmethacrylate (EMA) monomers onto cellulose has been carried out using ceric ammonium nitrate (CAN) as initiator in presence of nitric acid at (25 ± 1)°C and varying feed molarity from 7.5 × 10^?2 mol dm^?3 to 60.0 × 10^?2 mol dm^?3 at fixed feed composition (f_AAm = 0.6). The graft yield (%G_Y) has shown a linear increasing trend upto a feed molarity of 37.5 × 10^?2 mol dm^?3. The composition of grafted copolymer chains was found to be constant (F_AAm = 0.56) during feed molarity variation but shown variations with feed composition (f_AAm) and reaction temperature. The grafting parameters have shown increasing trends up to 7.5 × 10^?3 mol dm^?3 concentration of ceric (IV) ions and decreased on further increasing the concentration of ceric (IV) ions beyond 7.5 × 10^?3 mol dm^?3. The IR and elemental analysis data were used to determine the composition of grafted chains (F_AAm) and reactivity ratio of acrylamide (r₁) and ethylmethacrylate (r₂) comonomers. The reactivity ratio for acrylamide (r₁) and ethylmethacrylate (r₂) has been found to be 0.7 and 1.0 respectively, which suggested for an alternate arrangement of average sequence length of acrylamide (mM?₁) and ethylmethacrylate (mM?₂) in grafted chains. The rate of graft copolymerization of comonomers onto cellulose was found to be proportional to square concentration of comonomers and square root to the concentration of ceric (IV) ions. The energy of activation (ΔEa) of graft copolymerization was found to be 9.57 kJ mol^?1 within the temperature range of 20–50°C. On the basis of experimental findings, suitable reaction steps have been proposed for graft copolymerization of selected comonomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2546–2558, 2006     

Preparation,characterization, and properties of cellulose–polyacrylamide graft copolymers

Graft copolymers of acrylamide on cellulose materials (α‐cellulose 55.8%, DP 287.3) obtained from Terminalia superba wood meal and its carboxymethylated derivative (DS 0.438) were prepared using a ceric ion initiator and batch polymerization and modified batch polymerization processes. The extent of graft polymer formation was measured in graft level, grafting efficiency, molecular weight of grafted polymer chains, frequency of grafting as a function of the polymerization medium, and initiator and monomer concentrations. It was found that the modified batch polymerization process yielded greater graft polymer formation and that graft copolymerization in aqueous alcohol medium resulted in enhanced levels of grafting and formation of many short grafted polymer chains. Viscosity measurements in aqueous solutions of carboxymethyl cellulose‐g‐polyacrylamide copolymer samples showed that interpositioning of polyacrylamide chains markedly increased the specific viscosity and resistance to biodegradation of the graft copolymers. The flocculation characteristics of the graft copolymers were determined with kaolin suspension. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 913–923, 2003     

Aminolysis reaction of poly(N-4-methylphenylitaconimide) and its graft copolymerization

Polyitaconimide and copolymers of itaconimide were transformed to macromolecules having diamido pendent groups via an aminolysis reaction. The polymers obtained were cast into films, which were then graft copolymerized with acrylamide (AAM) using ceric ion as an initiator. Radical homopolymerization and copolymerization of N-4-methylphenylitaconimide with methyl acrylate or ethyl acrylate were carried out at 60°C in benzene; high molecular weight polymer and copolymers (M?_n = 10⁴–10⁵) were obtained. The resulting polymer and copolymers were reacted with n-butylamine in order to produce polymers possessing a pendent 4-tolylcarbamoyl group (4-CH₃C₆H₄NHCO-), which can significantly promote the acrylamide (AAM) graft copolymerization initiated with ceric ion. Transparent films of the polymers were graft copolymerized with AAM in the presence of ceric ion at 45°C. The formation of graft polymers was verified by water absorption percentage, XPS and SEM.     

Radiation-induced graft copolymerization of styrene to cellulose

The radiation-induced graft copolymerization of styrene to cellulose has been studied in vacuo at 30°C and at dose rates from (0.37 to 8.73) × 10^?2 W/kg. Dioxan was used as solvent for monomer and polystyrene homopolymer, and water (2% total volume) was incorporated as swelling agent for cellulose. The concentration of styrene in the bulk medium was varied from 0.432 to 3.46 moles/l., and the rates of both grafting and homopolymerization were shown to be proportional to [monomer] · [intensity]^1/2. The value of 3.3 × 10^?4 l. mole^?1 sec^?1 derived for k_p²/k_t in homopolymerization is similar to that for normal free-radical polymerization of styrene. However, reduced termination during grafting yielded a much higher value (58 l. moles^?1 sec^?1). Degradation of cellulose in the absence of monomer was followed viscometrically, and values of 13.5 and 24.6 were derived for G (scission) in vacuo and in air, respectively.     

High temperature surface neutralization process with random copolymers for block copolymer self‐assembly

Hydroxyl terminated poly(styrene‐r ‐methyl methacrylate) (P(S‐r ‐MMA )) random copolymers (RCPs ), with molecular weight (M _n) spanning from 1700 to 69 000 g mol^?1 and equal styrene unit content, were grafted at different temperatures onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder forming polystyrene‐b ‐poly(methyl methacrylate) (PS ‐b ‐PMMA ) block copolymer thin films. When the grafting temperature increases from 250 to 310 °C, a substantial increase in the grafting rate is observed. In addition, an increase in the surface neutralization efficiency occurs thus resulting in an increase in the robustness of the surface neutralization step. These data revealed that the neutralization of the substrate is the result of a complex interplay between RCP film characteristics and underlying substrate properties that can be finely tuned by properly adjusting the temperature of the grafting process. © 2016 Society of Chemical Industry     

Flow injection analysis estimation of diffusion coefficients of pauci- and polydisperse polymers such as polystyrene sulfonates

Flow injection analysis, often used for determination of diffusion coefficients of nonpolymeric substances, has now been applied to the characterization of pauci- and polydisperse polymers in solution. A relative method was found useful for obtaining moderate quality evaluations of diffusion coefficients and related parameters of polymers. The width at half-height W_1/2 of the trace peak is found to be proportional to the number average molecular weight M?_n of pauci- and polydisperse polymers, allowing estimation of M?_r and diffusion coefficients. For sodium polystyrene sulfonates at substantially infinite dilution in 1.0 g L^?1 Na₂SO₄, a linear relation has been observed between the logarithms of the molecular weight M?_n and the mean diffusion coefficient D in the M?_n range of 1000–90,000 g mol^?1 or the D range of 30 × 10^?7 to 2 × 10^?7 cm² s^?1.     

Ceric ion‐induced graft copolymerization of acrylamide on cationic guar gum at low temperature

The solution polymerization of acrylamide (AM) on cationic guar gum (CGG) under nitrogen atmosphere using ceric ammonium sulfate (CAS) as the initiator has been realized. The effects of monomer concentration and reaction temperature on grafting conversion, grafting ratio, and grafting efficiency (GE) have been studied. The optimal conditions such as 1.3 mol of AM monomer and 2.2 × 10^?4 mol of CAS have been adopted to produce grafted copolymer (CGG1‐g‐PAM) of high GE of more than 95% at 10°C. The rates of polymerization (R_p) and rates of graft copolymerization (R_g) are enhanced with increase in temperature (<35°C).The R_p is enhanced from 0.43 × 10^?4 mol L^?1 s^?1 for GG‐g‐PAM to 2.53 × 10^?4 mol L^?1 s^?1 for CGG1‐g‐PAM (CGG1, degree of substitute (DS) = 0.007), and R_g from 0.42 × 10^?4 to 2.00 × 10^?4 mol L^?1 s^?1 at 10°C. The apparent activation energy is decreased from 32.27 kJ mol^?1 for GG‐g‐PAM to 8.09 kJ mol^?1 for CGG1‐g‐PAM, which indicates CGG has higher reactivity than unmodified GG ranging from 10 to 50°C. Increase of DS of CGG will lead to slow improvement of the polymerization rates and a hypothetical mechanism is put forward. The grafted copolymer has been characterized by infrared spectroscopy, thermal analysis, and scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3715–3722, 2007     

Thermal behavior of graft copolymers of cotton cellulose and acrylate monomers

Cotton cellulose yarn was grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate at various percentages of grafting. The effects of concentration of the initiator, concentration of the acid, and of temperature on grafting was studied and the mechanism discussed. The effect of reactivity of the monomer on the percentage graft-on is pointed out. Thermal behavior of natural and grafted cotton yarn was studied using dynamic thermogravimetry in air at a heating rate of 6°C/min up to a temperature of 500°C. The thermal stabilities of the samples grafted with various acrylate monomers to various percentages of grafting were computed from their primary thermograms by calculating the values of IDT, IPDT, and E^*. The results show that the thermal stability increases with increase in graft-on per cent, and the thermal stabilities of natural cotton and cotton grafted with different monomers are in the order ethyl > methyl > natural cellulose > methyl methacrylate > n-butyl acrylate.     

Grafting acrylonitrile on kenaf fibers using ceric ion–p-xylene redox pair

Polyacrylonitrile was grafted onto kenaf fibers in aqueous media by ceric ion–p-xylene redox system. The graft yield dependence on p-xylene concentration in the range 1.8–45.0 × 10⁻⁴M showed a minimum accompanied by an enhanced yield. This suggested the existence of two kinetically distinct grafting reactions associated with two precursor-initiating species, a p-xylyl radical and a diradical. The frequency of graft F_g and the average molecular weight of grafted polymer M_v were inversely related at varying concentrations of p-xylene with values for M_v of up to 5.18 × 10⁴. The effect of ceric ion concentration on M_v showed that the ion is nonterminating at low concentrations in the range 8.3–33.3 × 10⁻³M. The graft yield showed positive temperature dependence in the region of 30–40°C and a negative one at higher temperatures, resulting in a decrease in the initial rate of graft at 70°C by a factor of 8 compared to its value at 40°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1751–1755, 1999     

Separation and characterization of the vinyl side chains from grafted polyacrylonitrile–cotton copolymers

A method of separation of polyvinyl side chains from grafted polyacrylonitrile–cotton copolymers was developed in order to study the effect of length of side chain on copolymer properties. The method consists of dispersion of the copolymer (1 g.) containing 20% polyacrylonitrile in 75% aq. ZnCl₂ (100 ml.), addition of 6N HCl (100 ml.), heating for 1 hr. at 100°C., and precipitation and purification of the resulting vinyl polymer. The effect of hydrolysis on the intrinsic viscosity, the nitrogen content, and the infrared absorption spectra of the polyacrylonitrile polymers was investigated. It was concluded that this method of separation of the grafted polymers permitted a comparison of samples grafted by various techniques. A series of grafted copolymers was hydrolyzed, and the molecular weights of the isolated products were determined by measurements of intrinsic viscosity. Copolymer samples prepared by a post-irradiation grafting technique had the longest polyacrylonitrile side chains (molecular weight, 1 × 10⁶). Samples grafted by a simultaneous irradiation technique varied in side-chain length, depending upon the monomer-solvent system used in the preparation of the copolymer (molecular weight, 3 × 10⁴?5 × 10⁵). Chemically initiated grafting to cotton resulted in a copolymer containing relatively short side chains (molecular weight, 9 × 10⁴).     

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.     

Influence of starch granule swelling on graft copolymer composition. A comparison of monomers

Seven monomers, which varied widely in water solubility and ionic charge, were graft polymerized onto both unswollen starch and starch that had been swollen by heating in water to 60°C. Polymerizations were initiated with ferrous ammonium sulfate hexahydrate–hydrogen peroxide and, where applicable, with ceric ammonium nitrate. Graft copolymers were freed of ungrafted homopolymer by solvent extraction and were characterized by weight percentage of synthetic polymer incorporated in the graft copolymer, molecular weight of grafted branches, and grafting frequency. The influence of starch granule swelling on graft copolymer structure varied with the monomer used and could not be predicted on the basis of water solubility of monomer or its resulting polymer. With acrylonitrile and acrylamide, swollen starch gave higher molecular weight and less frequent grafts than unswollen starch. However, methyl methacrylate, N,N-dimethylaminoethyl methacrylate · HNO₃, N-t-butylaminoethyl methacrylate. HNO₃, and 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride produced less frequent graft of higher molecular weight when starch was unswollen. With acrylic acid, graft molecular weight was independent of starch granule swelling, although grafting was less frequent when swollen starch was used.     

Molecular weights of styrene–maleic anhydride copolymers

A dual-calibration method for the determination of molecular weights and molecular weight distribution of styrene–maleic anhydride copolymers (S/MA) by gel permeation chromatography (GPC) is introduced. It might be applicable to copolymers of other type. A linear relationship of intrinsic viscosity [η] and weight-average molecular weight (M?_w) for unfractionated S/MA in tetrahydrofuran (THF) at 25°C can be expressed by the equation The maleic anhydride content of the copolymers ranges from 5 to 50 mole-%, and the M?_w range is from 2 × 10⁴ to 7 × 10⁶. The plot of log [η] M?_w versus GPC elution volume of the S/MA copolymers falls on the same curve as that of the polystyrene standards in THF.     

Effect of acrylic acid neutralization on ‘livingness’ of poly[styrene‐ran‐(acrylic acid)] macro‐initiators for nitroxide‐mediated polymerization of styrene

BACKGROUND: The effect of acrylic acid neutralization on the degradation of alkoxyamine initiators for nitroxide‐mediated polymerization (NMP) was studied using styrene/acrylic acid and styrene/sodium acrylate random copolymers (20 mol% initial acrylate feed concentration) as macro‐initiators. The random copolymers were re‐initiated with fresh styrene in 1,4‐dioxane at 110 °C at SG1 mediator/BlocBuilder^® unimolecular initiator ratios of 5 and 10 mol%. RESULTS: The value of k_pK (k_p = propagation rate constant, K = equilibrium constant) was not significantly different for styrene/acrylic acid and styrene/sodium acrylate compositions at 110 °C (k_pK = 2.4 × 10^?6–4.6 × 10^?6 s^?1) and agreed closely with that for styrene homopolymerization at the same conditions (k_pK = 2.7 × 10^?6–3.0 × 10^?6 s^?1). All random copolymers had monomodal, narrow molecular weight distributions (polydispersity index M?_w/M?_n = 1.10–1.22) with similar number‐average molecular weights M?_n = 19.3–22.1 kg mol^?1. Re‐initiation of styrene/acrylic acid random copolymers with styrene resulted in block copolymers with broader molecular weight distributions (M?_w/M?_n = 1.37–2.04) compared to chains re‐initiated by styrene/sodium acrylate random copolymers (M?_w/M?_n = 1.33). CONCLUSIONS: Acrylic acid degradation of the alkoxyamines was prevented by neutralization of acrylic acid and allowed more SG1‐terminated chains to re‐initiate the polymerization of a second styrenic block by NMP. Copyright © 2008 Society of Chemical Industry     

Latexes of starch-based graft polymers containing polymerized acrylonitrile

The scope of graft reactions to produce starch-based latexes was extended by graft polymerization of acrylonitrile (AN) onto gelatinized cationic starch possessing quaternary amine functionality and by graft terpolymerization of AN and t-butylaminoethyl methacrylate (TBAEM) onto gelatinized starch by cerium (IV) initiation at 25°C. Grafting onto starches containing highly basic quaternary amines gave polyacrylonitrile [poly(AN)] grafts having about one fourth the number-average molecular weight (M?_n) (178,000–232,000) of those produced by grafting AN onto starches containing the less basic tertiary amine groups. Sonification at 20 KHz of graft polymerization reaction mixtures having up to 8% solids reduced viscosities from 400–3000 cP to 10–40 cP. Diameters of dried particles measured about 300–1500 Å. Shaker-type agitation during grafting onto starch having quaternary amine groups produced poly(AN) chains with lower M?_n values than those produced during blade stirrer-type agitation. M?_n values of grafted poly(AN) decreased with increasing reaction time, degree of substitution of amine in the starch, gelation time of cationic starch at 95°C, and cerium (IV) concentration. AN was copolymerized with TBAEM at molar ratios of 14–85:1 in grafting onto gelatinized starch to yield copolymer side-chain grafts analyzing 8–52:1 of polymerized AN to TBAEM moieties.     

Melting and crystallization behavior of poly(tetrafluoroethylene). New method for molecular weight measurement of poly(tetrafluoroethylene) using a differential scanning calorimeter

Melting and crystallization behavior of virgin polytetrafluoroethylene have been studied using a differential scanning calorimeter. Following quantitative relationship was found between number average molecular weight of polytetrafluoroethylene and the heat of crystallization in the molecular weight range of 5.2 × 10⁵ to 4.5 × 10⁷: M?_n = 2.1 × 10¹⁰ ΔH_c^?5.16, where M?_n is number average molecular weight and ΔH_c is the heat of crystallization in cal/g. The heat of crystallization is independent of cooling rate ranging from 4 to 32°C/min. This relationship provides a simple rapid and reliable method for measuring the molecular weight of polytetrafluoroethylene.     

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