Grafted polysaccharides based on acrylamide and N,N‐dimethylacrylamide: Preparation and investigation of their flocculation performances

The graft copolymerization of N,N‐dimethylacrylamide (DMA) and acrylamide (AM) were carried out onto different polysaccharide backbones separately. The graft copolymers were synthesized by ceric ion induced redox polymerization technique. Three polysaccharides were used, namely hydroxyethyl starch (HES), hydroxyethyl cellulose (HEC) and Amylopectin (AP), for the grafting reactions. Among the three polysaccharides, HEC has linear structure, while HES and AP have a branch one. The graft copolymers were characterized by intrinsic viscosity measurements, FTIR spectroscopy, NMR (both ¹H and ¹³C) spectroscopy, and thermal analysis. Flocculation performances of the graft copolymers were evaluated in 1 wt % kaolin and in 0.25 wt % iron ore suspensions. A detailed comparative study of the flocculation properties of the synthetic graft copolymers was also made. It showed that graft copolymers based on DMA were better flocculants than those based on AM. Among the synthetic graft copolymers, HES‐g‐Poly (DMA) performed best when compared with the other synthetic graft copolymers as well as to the commercial flocculants in the same suspensions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

1,2‐propanediol–cellulose–acrylamide graft copolymers

1,2‐Propanediol–cellulose–acrylamide graft copolymers (PCACs) were developed for enhanced oil recovery. They were prepared with acrylamide and 1,2‐propanediol (PDO)–cellulose, which was formed through the addition of glycols to cellulose by the Shotten–Baumann reaction between 3‐chloro‐1,2‐propanediol and cellulose. The graft copolymerization was initiated with a redox system between Ce⁴⁺ and glycols in cellulose. The infrared spectrum of PDO–cellulose had some characteristic absorption bands around 2960 (νC? H) and 1050 cm^?1 (νC? O) that also appeared for the PDO group and pyranose ring of cellulose, respectively. The rate of Ce⁴⁺ consumption by PDO–cellulose was investigated through the calculation of the overall kinetic constant from the slopes of ln(D ? D_R) versus time (where D is the absorbance and D_R is the absorbance of the original polysaccharide solution) The results showed that PDO–cellulose had high reactivity and that there were two mechanisms of oxidation by Ce⁴⁺ with PDO–cellulose. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3022–3029, 2004     

Competitive removal of nickel (II), cobalt (II), and zinc (II) ions from aqueous solutions by starch‐graft‐acrylic acid copolymers

Graft copolymerization of acrylic acid (AA) onto starch was carried out with ceric ammonium nitrate as initiator under nitrogen atmosphere. The grafting percentages (GP%) of starch‐graft‐acrylic acid (St‐g‐AA) copolymers were determined. The effect of GP% of St‐g‐AA copolymers on the competitive removal of Co²⁺, Ni²⁺, Zn²⁺ ions from aqueous solution was investigated at different pH (2, 4, 6). The concentrations of each ion in aqueous solution 5 mmol/L. Effects of various parameters such as treatment time, initial pH of the solution and grafting percentage of starch graft copolymers were investigated. Metal ion removal capacities of St‐g‐AA copolymers increased with GP% of the copolymers and pH. The results show that the removal of metal ions followed as given in the order Co²⁺ > Ni²⁺ > Zn²⁺. In this study, metal ion removal capacities were determined by atomic absorption spectrophotometer (AAS). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

Rheological and thermal properties of saponified cassava starch‐g‐poly(acrylamide) superabsorbent polymers varying in grafting parameters and absorbency

Cassava starch‐graft‐poly(acrylamide) superabsorbent polymers (SAPs) with varying absorbencies were synthesized. Weight average molecular weight (M_w) of the hydrolyzed starch‐graft‐copolymers ranged from 1.6 × 10⁶ to 2.8 × 10⁶ g/mol, the largest being shown by the sample with highest percentage grafting. The storage (G′) and loss modulus (G″) of hydrogels were determined as a function of frequency. G″ was larger than G′ for the hydrogels with higher absorbencies and exhibited a liquid‐like behavior. However, hydrogels with lower absorbencies showed a reverse viscoelastic behavior. The viscosity of hydrogels determined using a Brookfield viscometer at different shear rates was found to be larger for the hydrogels with higher absorbencies. The melting temperature (T_m) and enthalpy change of fusion (ΔH_f) of the SAPs ranged from 149.7 to 177.7°C and 65 to 494.9 J/g, respectively and showed a positive correlation with grafting parameters and M_w. Heavy metal ion removal capacity of hydrogel followed the order Cu²⁺ > Pb²⁺ > Zn²⁺. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40368.     

Starch‐poly(acrylamide‐co‐2‐acrylamido‐2‐methylpropanesulfonic acid) graft copolymers prepared by reactive extrusion

Graft copolymers of starch with acrylamide and 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) were prepared by reactive extrusion in a twin‐screw extruder. The weight ratio of total monomer to starch was fixed at 1 : 3, while the molar fraction of AMPS in the monomer feed ranged from 0 to 0.119. Monomer to polymer conversions were 85% or greater, with grafting efficiencies of 68% (highest AMPS content) to 85% (no AMPS). Absorbency in distilled water at pH 7 increased linearly with the mole fraction AMPS in the grafted polymer, while absorbencies in 0.9% NaCl were independent of AMPS content. When swollen in water/ethanol mixtures, swelling decreased gradually with increasing ethanol volume fraction, followed by a large decrease over a narrow ethanol concentration. This behavior is similar to that observed for AMPS‐acrylamide gels. The swelling properties suggest these graft copolymers may have applications as responsive materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42405.     

Synthesis of starch‐graft‐polyacrylonitrile hydrolyzate and its characterization

The graft copolymerization of three vinyl monomer species, acrylonitrile (AN), acrylamide (AAm), and acrylic acid (AA), onto starch was carried out with ceric salt (Ce salt) as an initiator. With 3 mmol/L Ce salt, the monomer activity onto starch decreased in the following order: AN > AAm > AA. Grafting efficiency with AN as the grafting monomer was greater than 90%, but with AA and AAm, it was less than 50%. Starch‐graft‐polyacrylonitrile was hydrolyzed to introduce amide and carboxyl groups into starch. The hydrolyzates were analyzed with infrared spectroscopy. The hydrolysis reaction was accelerated with increasing alkali concentration, reaction temperature, and time. The water absorbancy of the hydrolyzate increased with an increasing carboxyl molar fraction in the polymer, and it dissolved in water above a 0.6 molar fraction. The absorbancy of water was 2 times higher than that of a NaCl aqueous solution. The copper‐ion‐exchange capacity of the sample was greater in graft copolymers with higher carboxyl group contents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1437–1443, 2001     

Tailoring of water‐soluble cellulose‐g‐ copolymers in homogeneous medium using single‐electron‐transfer living radical polymerization

Cellulose‐graft‐polyacrylamide and cellulose‐graft‐poly(N,N‐dimethylacrylamide) copolymers were prepared by single‐electron‐transfer living radical polymerization (SET‐LRP) in homogeneous medium. Cellulose macroinitiators for SET‐LRP, with different numbers of initiating sites along the cellulose backbone, were successfully synthesized by direct acylation of cellulose with 2‐bromoisobutyryl bromide in LiCl/dimethylacetamide. Dynamic light scattering revealed that cellulose macroinitiator molecules in dimethylsulfoxide (DMSO) exist primarily as individual chains with a certain amount of intermolecular aggregates. SET‐LRP of acrylamide and N,N‐dimethylacrylamide with the cellulose macroinitiators was carried out in DMSO solution. Formation of cellulose‐graft‐copolymers was confirmed using attenuated total reflectance Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy, and the products were water‐soluble. High content of poly(N,N‐dimethylacrylamide) in the copolymers enhanced the thermal stability relative to that of cellulose. Scanning electron microscopy studies of cellulose‐based particles formed from the copolymers using the aerosol flow reactor method revealed spherical nanoscale structures. Copyright © 2011 Society of Chemical Industry     

Starch‐g‐polycaprolactone copolymerization using diisocyanate intermediates and thermal characteristics of the copolymers

Starch‐g‐polycaprolactone copolymers were prepared by two‐step reactions. The diisocyanate‐terminated polycaprolactone (NCO–PCL) was prepared by introducing NCO on both hydroxyl ends of PCL using diisocyanates (DI) at a molar ratio between PCL and DI of 2:3. Then, the NCO–PCL was grafted onto corn starch at a weight ratio between starch and NCO–PCL of 2:1. The chemical structure of NCO–PCL and the starch‐g‐PCL copolymers were confirmed by using FTIR and ¹³C‐NMR spectrometers, and then the thermal characteristics of the copolymers were investigated by DSC and TGA. By introducing NCO to PCL (M_n : 1250), the melting temperature (T_m ) was reduced from 58 to 45°C. In addition, by grafting the NCO–PCL (35–38%) prepared with 2,4‐tolylene diisocyanate (TDI) or 4,4‐diphenylmethane diisocyanate (MDI) onto starch, the glass transition temperatures (T_g 's) of the copolymers were both 238°C. With hexamethylene diisocyanate (HDI), however, T_g was found to be 195°C. The initial thermal degradation temperature of the starch‐g‐PCL copolymers were higher than that of unreacted starch (320 versus 290°C) when MDI was used, whereas the copolymers prepared with TDI or HDI underwent little change. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 986–993, 2000     

Preparation of poly (MAA)‐crosslinked pregelled starch graft copolymer and its application in waste water treatments

Propelled starch (PG) was first crosslinked with epichlorohydrin to obtain insoluble crosslinked pregelled starch (CPS). The latter was graft copolymerized with different amounts of Methacrylic acid using potassium persulphate as initiator. This was done to obtain six levels of poly (MAA)‐crosslinked pregelled starch graft copolymers (PMCPS) having different graft yields (expressed as meq COOH/100 g starch) with increasing order and designated as (PMCPS 1 to PMCPS 6). The latter copolymers were dispersed in aqueous solution of heavy metal ions (Cu²⁺, Pb²⁺, Cd²⁺, and Hg²⁺) and filtered to form polymer‐metal ions complex. Different factors affecting the heavy metal ions removal such as pH, extent of grafting, treatment time and starch dose were studied in detail. It was found from the obtained results that; the residual metal ions removal from their aqueous solutions increased with (a) increasing the extent of grafting of PMCPS i.e., from PMCPS 1 to PMCPS 6; (b) Increasing the pH of the metal ions solution complex from 1 to 8; (c) increasing the starch dosage from 0.25 to 2.0% (W/V), then leveled off thereafter, (d) increasing the time of the reaction up to 20 min then leveled off after that. On the other hand, Pb, Cd and Hg ions were also removed from their solutions with different extent. Furthermore, the prepared copolymer could be recovered by washing the metal ions from the complex with weak acid 1N HNO₃ (pH 2) and the metal‐binding activity of the starch was slightly reduced by this process. Finally, the ability of PMCPS to remove three types of basic dyes from their solutions was also reported. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Formation of thermosensitive water‐soluble copolymers with phosphinic acid groups and the thermosensitivity of the copolymers and copolymer/metal complexes

Thermosensitive and water‐soluble copolymers were prepared through the copolymerization of acryloyloxypropyl phosphinic acid (APPA) and N‐isopropyl acrylamide (NIPAAm). The thermosensitivity of the copolymers and copolymer/metal complexes was studied. The APPA–NIPAAm copolymers with less than 11 mol % APPA moiety had a lower critical solution temperature (LCST) of approximately 45°C, but the APPA–NIPAAm copolymers with greater than 21 mol % APPA moiety had no LCST from 25 to 55°C. The APPA–NIPAAm copolymers had a higher adsorption capacity for Sm³⁺, Nd³⁺, and La³⁺ than for Cu²⁺, Ni²⁺ and Co²⁺. The APPA–NIPAAm (10:90) copolymer/metal (Sm³⁺, Nd³⁺, or La³⁺) complexes became water‐insoluble above 45°C at pH 6–7, but the APPA–NIPAAm (10:90) copolymer/metal (Cu²⁺,Ni²⁺, or Co²⁺) complexes were water‐soluble from 25 to 55°C at pH 6–7. The temperature at which both the APPA–NIPAAm copolymers and the copolymer/metal complexes became water‐insoluble increased as the pH values of the solutions increased. The APPA–NIPAAm copolymers were able to separate metal ions from their mixed solutions when the temperature of the solutions was changed; this was followed by centrifugation of the copolymer/metal complexes after the copolymers were added to the metal solutions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 116–125, 2004     

Graft copolymerization of methylmethacrylate with N‐substituted maleimide‐styrene copolymer by ATRP

Atom transfer radical polymerization (ATRP) was employed to prepare graft copolymers having poly(MBr)‐alt‐poly(St) copolymer as backbone and poly(methyl methacrylate) (PMMA) as branches to obtain heat resistant graft copolymers. The macroinitiator was prepared by copolymerization of bromine functionalized maleimide (MBr) with styrene (St). The polymerization of MMA was initiated by poly(MBr)‐alt‐poly(St) carrying bromine groups as macroinitiator in the presence of copper bromide (CuBr) and bipyridine (bpy) at 110°C. Both macroinitiator and graft copolymers were characterized by ¹H NMR, GPC, DSC, and TGA. The ATRP graft copolymerization was supported by an increase in the molecular weight (MW) of the graft copolymers as compared to that of the macroinitiator and also by their monomodal MW distribution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis of water‐soluble polyphenol‐graft‐poly(ethylene oxide) copolymers via enzymatic polymerization and anionic polymerization

Water‐soluble polyphenol‐graft‐poly(ethylene oxide) (PPH‐g‐PEO) copolymers were prepared using grafting‐through methodology. Polyphenol chains were synthesized via enzymatic polymerization of phenols, and the graft chains were synthesized via living anionic polymerization of ethylene oxides. The polymers were characterized using gel permeation chromatography, static light scattering and ¹H NMR, infrared and ultraviolet spectroscopies. The PPH‐g‐PEO graft copolymers are soluble in several common solvents, such as water, ethanol, N,N‐dimethylformamide, tetrahydrofuran and methylene dichloride. The solubility of the PPH‐g‐PEO graft copolymers is improved significantly compared with that of polyphenol. Copyright © 2009 Society of Chemical Industry     

Utilization of some starch derivatives in heavy metal ions removal

Three types of starch derivatives containing amide groups were used in removal of heavy metal ions from their solutions. These starch derivatives were poly(acrylamide)–starch graft copolymer, carbamoylethylated starch, and starch carbamate. The different factors affecting metal ion adsorption on these substrates, such as pH, metal ion concentration, type of starch derivatives, treatment time, and temperature, were studied. Results obtained indicate that the poly(acrylamide)–starch graft copolymer was a selective adsorbant for Hg²⁺ at pH 0.5–1. The adsorption values ofdifferent metal ions on these starch derivatives follow the order of Hg²⁺ > Cu²⁺ > Zn²⁺ > Ni²⁺ > Co²⁺ > Cd²⁺ > Pb²⁺. The adsorption values depend upon pH, type of starch derivative, treatment duration, and temperature. The adsorption efficiency percentage of metal ions on the three substrates follows the order of carbamoylethylated starch > poly(acrylamide) − starch graft copolymer > starch carbamate. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 69: 45–50, 1998     

Homogeneous graft copolymerization of chitosan with butyl acrylate by γ‐irradiation via a 6‐O‐maleoyl‐N‐phthaloyl‐chitosan intermediate

The graft copolymerization of butyl acrylate (BA) onto chitosan was tried via a new protection‐graft‐deprotection procedure. About 6‐O‐maleoyl‐N‐phthaloyl‐chitosan was synthesized and characterized by Fourier transform infrared spectra analysis (FT‐IR) and ¹H‐NMR. Because the intermediate 6‐O‐maleoyl‐N‐phthaloyl‐chitosan was soluble in organic solvents, the graft copolymerization was carried out in a homogeneous system. Grafting was initiated by γ‐irradiation. The graft extent was dependent on the irradiation dose and the concentration of BA monomer, and copolymers with grafting above 100% were readily prepared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 489–493, 2006     

Thermoresponsive poly(ϵ‐caprolactone)‐graft‐poly(N‐isopropylacrylamide) graft copolymers prepared by a combination of ring‐opening polymerization and sequential azide–alkyne click chemistry

A straightforward strategy is described to synthesize poly(?‐caprolactone)‐graft‐poly(N‐isopropylacrylamide) (PCL‐g‐PNIPAAm) amphiphilic graft copolymers consisting of potentially biodegradable polyester backbones and thermoresponsive grafting chains. PCL with pendent chlorides was prepared by ring‐opening polymerization, followed by conversion of the pendent chlorides to azides. Alkyne‐terminated PNIPAAm was synthesized by atom transfer radial polymerization. Then, the alkyne end‐functionalized PNIPAAm was grafted onto the PCL backbone by a copper‐catalyzed azide–alkyne cycloaddition. PCL‐g‐PNIPAAm graft copolymers self‐assembled into spherical micelles comprised of PCL cores and PNIPAAm coronas. The critical micelle concentrations of the graft copolymers were in the range 7.8–18.2 mg L^?1, depending on copolymer composition. Mean hydrodynamic diameters of micelles were in the range 65–135 nm, which increased as the length of grafting chains grew. PCL‐g‐PNIPAAm micelles were thermosensitive and aggregated upon heating. © 2014 Society of Chemical Industry     

Poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene by combination of ATRP and aminolysis processes

Block copolymers of very hydrophilic poly(N‐hydroxyethyl acrylamide) (PHEAA) with polystyrene (PS) were successfully synthesized by sequential atom transfer radical polymerization of ethyl acrylate (EA) and styrene monomers and subsequent aminolysis of the acrylic block with ethanolamine. Quantitative aminolysis of poly(ethyl acrylate) (PEA) block yielded poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene in well‐defined structures, as evidenced by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy techniques. Three copolymers with constant chain length of PHEAA (degree of polymerization: 80) and PS blocks with 21, 74, and 121 repeating units were prepared by this method. Among those, the block copolymer with 21 styrene repeating units showed excellent micellation behavior in water without phase inversion below 100°C, as inferred from dynamical light scattering, environmental scanning electron microscopy, and fluorescence measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of strach‐graft‐polyacrylamide copolymers by reactive extrusion

Graft copolymers of starch and polyacrylamide (PAAm) were prepared by reactive extrusion using a co‐rotating twin‐screw extruder and ammonium presulfate initiator. Feed rates were 109 g/min to 325 g/min (all components) at a moisture content of 50%, with screw speeds in the range 100 rpm to 300 rpm. Starch/acrylamide weight ratios ranged from 5:1 to 1.3:1. Conversions of acrylamide to PAAm were generally 80% or greater with residence times of 400 seconds or less. Conversion increased with feed rate, suggesting that reaction efficiency was proportional to the degree of fill in the extruder. Grafting efficiencies were in the range of 50% to 80%. PAAm molecular weight increased with increasing acrylamide content, consistent with free radical polymerization kinetics. Extrusion temperature had no significant impact on acrylamide conversion. Graft frequency, as measured by the number of anhydroglucose units per graft, was essentially constant over the starch: acrylamide ratio and temperature range studied. These results show that reactive extrusion offers the potential for rapid production of starch graft copolymers with unsaturated monomers.     

Synthesis of amine‐functionalized block copolymers for nanopollutant removal from water

Polyamines are rare in literature owing to increased reactivity, sensitivity to air and moisture, low stability, and processing difficulties. Here, we report the synthesis and characterization of highly processable polyamines and use them for the removal of dissolved metallic nanoparticles from water. Three amphiphilic block polyamines such as poly(N‐aminoethyl acrylamide‐b‐styrene), poly(N‐aminopropyl acrylamide‐b‐styrene), and poly(N‐aminoxylyl acrylamide‐b‐styrene) have been synthesized using atom transfer radical polymerization of ethyl acrylate and styrene followed by aminolysis of the acrylic block. The polymerization and properties of the polymers are studied using different physicochemical techniques. Surface morphology of films prepared from these block copolymers by dissolving in different solvents such as chloroform, tetrahydrofuran and N,N‐dimethylformamide, and drop‐casting polymers on a glass substrate show interesting porous films and spherical nanostructures. In addition, the amine‐functionalized block copolymers have been used for the removal of nanoparticles from water and show high extraction efficiency toward silver (Ag) and gold (Au) nanoparticles. All three amine‐functionalized block copolymers show higher extraction capacities (Q_e) toward Au NPs (50–109 mg g^?1) and Ag NPs (99–117 mg g^?1). Our approach allows us to make amine‐functionalized block copolymers which are stable in air and can be easily processed in nonpolar solvents. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40943.     

Graft copolymerization onto starch. I. Complexes of Mn3+ as initiators

Advantages in using the pyrophosphate complex of trivalent managanese over the sulfate complex as initiator for graft copolymerization onto starch are discussed. The first successful attempts to graft copolymerize acrylonitrile, methyl methacrylate, and acrylamide to starch and starch derivatives are described using managanic pyrophosphate as initiator. Selective solvent extraction of the reaction products and very low conversions of monomer to homopolymer in absence of starch substrates provide evidence for high grafting efficiencies obtained with acrylonitrile and methyl methacrylate. With acrylamide as monomer, however, low grafting efficiencies and considerable amounts of homopolymer are obtained under the experimental conditions investigated. Reaction mechanisms responsible for initiation of graft copolymerization are discussed. These are (a) glycol cleavage in the anhydroglucose units by Mn³⁺ ions leading to formation of a radical, and (b) enolization and further oxidation of oxidized starch by Mn³⁺ ions also leading to radical species. Mechanisms are also proposed for homopolymerization through Mn³⁺ oxidation of enols which probably are formed by “vinylogous” addition of water molecules to acrylamide and methyl methacrylate.