Cassava starch‐graft‐polymethacrylamide copolymers as flocculants and textile sizing agents

Cassava starch‐graft‐polymethacrylamide (PMAM) copolymers were synthesized by a free‐radical‐initiated polymerization reaction, and the products were tested for their efficiency as flocculants and textile sizing agents. The highest percentages of grafting and monomer conversion were 79.9 and 78.0%, respectively. The grafted starches were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction analysis, scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The average molecular weight of PMAM chains in the grafted starches ranged from 15.9 to 30.8 × 10⁵ g/mol. The grafted starches exhibited a higher peak viscosity and paste stability in comparison to the native starch (NS). Dynamic mechanical analysis showed that grafting provided fairly shear‐stable hydrogels, and the highest storage modulus obtained was 17,900 Pa compared to 1879 Pa for NS. The flocculation studies demonstrated the superiority of starch‐g‐PMAM over cassava starch and PMAM as an efficient flocculant. The tensile strength of cotton yarns sized with the starch‐grafted copolymer was significantly higher (104 MPa) compared to that sized with NS (34 MPa). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39810.     

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     

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.     

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 and characterization of starch‐poly(methyl methacrylate) graft copolymers

The graft copolymerization was carried out by methyl methacrylate with starch in which azobisisobutyronitrile was used as an initiator. The grafting reactions were carried out within a 65–95°C temperature range, and the effect of the monomer, initiator concentrations, and the amount of starch on the graft yield were also investigated. The maximum graft yield was obtained at a azobisisobutyronitrile concentration of 2.0 × 10^?3 mol/L. The overall rate activation energy of the reaction was found to be 89.42 kJ/mol. The grafted starches were characterized with infrared spectroscopy, scanning electron microscopy, and thermogravimetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 53–57, 2002     

Removal of basic dyes from aqueous solutions using 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‐AA (St‐gr‐AA) copolymers were determined. When the AA molar concentrations were 0.3 and 0.5 mol/L, GP% of St‐gr‐AA copolymers were 10.5% (St‐gr‐AA‐1) and 14% (St‐gr‐AA‐2), respectively. St‐gr‐AA copolymers have been used for the adsorption of basic dye (Safranine T) from aqueous solutions. Effects of various parameters such as treatment time, initial pH of the solution (pH = 2–6), initial dye concentration (50– 500 mg/L), and GP% of starch graft copolymers were investigated.Basic dye removal capacities of the copolymers increase along with the augment of initial concentration of the adsorbate, GP% of the copolymers, and pH. The adsorption capacities for St‐gr‐AA‐1 and St‐gr‐AA‐2 reach 116.5 and 204 mg/g, respectively. Equilibrium adsorption data were obtained and fitted very well to Freundlich model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of poly(ether sulfone)‐graft‐polydimethylsiloxane copolymers

Novel poly(arylene ether sulfone) (PAES) polymers containing polydimethylsiloxane (PDMS) side chains were synthesized and characterized with NMR and Fourier transform infrared spectroscopy. The thermal properties of the copolymers were evaluated with differential scanning calorimetry and thermogravimetric analysis. The polymers showed perfect thermal stability, as the decomposition temperatures were all above 380°C, and exhibited glass‐transition temperatures in the range 130–188°C. Furthermore, the surface properties of the copolymers were evaluated by X‐ray photoelectron spectroscopy and contact angle analysis. The results show that the hydrophobic abilities of the graft copolymer surfaces were improved significantly compared to PAES through the introduction of the PDMS chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of superabsorbent starch‐graft‐poly(potassium acrylate‐co‐acrylamide) and its properties

The superabsorbent's ability to resist deformation and to resist deswelling under externally applied pressures is important in practical application. For instance, it is used in infant diapers, in soil for agriculture, and in forestry. In this article, we report on the synthesis of a superabsorbent/starch‐graft‐poly(potassium acrylate‐co‐acrylamide) by inverse suspension polymerization. The effects of reaction conditions, such as monomeric concentration, ratio of water to oil, reaction temperature, and obtaining spherical resin, were investigated. Experiments showed that the superabsorbent has a good compressive strength and keeps the shape of particles after absorbing water. After mixing with soil it does not become sticky, and the loose structure can better retain air. It is fit to retain water in soil. In addition, thermogravimetric analysis revealed the superior thermal stability of the grafted product and its large particle size also reduces risk of air pollution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1536–1542, 2003     

In‐depth characterization of granular starch‐graft‐polyester compositions as obtained by in situ polymerization of lactones from the starch surface

The synthesis of poly(ε‐caprolactone) (PCL)‐grafted granular starch was carried out either in bulk (without solvent) or in toluene suspension by a two‐step procedure. First step relied upon the activation of the hydroxyl groups available at the starch surface by alkylaluminum derivatives like AlEt₃ and removal of non‐surface‐grafted organo‐aluminum active species. The latter species were made free in solution by reaction with the remaining water molecules still contaminating the polymerization medium despite intensive drying of the starch granules. In the second step, ε‐caprolactone was polymerized via a coordination‐insertion ring‐opening polymerization as initiated by the surface‐grafted aluminum alkoxide species. The present contribution aims at investigating various parameters such as nature of the alkyl aluminum activator and monomer (δ‐valerolactone was studied as well), temperature, concentration, and addition of a solvent (polymerization in toluene suspension), reaction time, and also the experimental procedure used to recover the polyester chains and measure the grafting efficiency. It turns out that, under the studied conditions, dialkylaluminum alkoxides surface‐grafted onto the starch granules were more likely generated and promote a fast polymerization reaction with the formation of grafted PCL chains with a molecular weight that can be as high as 225 000 (M_n value) for polymerization carried out in toluene suspension. Copyright © 2004 Society of Chemical Industry     

Optimization of synthesis and characterization of cassava starch‐graft‐poly(acrylonitrile) using response surface methodology

Graft copolymerization of poly(acrylonitrile) onto cassava starch was carried out with potassium persulphate (PPS) as the free radical initiator using a response surface Box–Behnken design. Different levels of monomer concentration, initiator concentration, and temperature were used, and regression models were generated in terms of these factors, which can be used to predict the grafting level and efficiency at a given level of the factors. The grafted starches were characterized by FTIR, XRD, and SEM analyses and determination of %grafting (%G), N‐content, thermal properties, water and saline solution retention, and rheological properties. Under the conditions used, %G was found to depend only on the temperature used for the reaction. The maximum %G of 120.1 was obtained for the sample synthesized under the following conditions: weight of AN = 0.753 mol/10 g starch, weight of PPS = 0.284 g and temperature = 55°C, and the grafting efficiency was 30.03%. The absorption bands at 2243 cm^?1 for the nitrile group (? CN) in the FTIR spectra of the products confirmed the grafting reaction. There was a decrease in crystallinity and disappearance of the granular structure after grafting of the starch. The melting temperatures of the graft copolymers determined by differential scanning calorimetry analysis were higher than that of the native starch. The grafted starches exhibited very high thermal stability as observed from the thermogravimetric analysis. The superabsorbent polymer prepared from the grafted starch by alkali saponification exhibited a maximum water absorbency of 636 g/g. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of starch‐graft‐poly(acrylamide)/attapulgite superabsorbent composite

A novel starch‐graft‐poly(acrylamide)/attapulgite superabsorbent composite was synthesized by graft copolymerization reaction of starch, acrylamide (AM), and attapulgite micropowder using N.N‐methylene‐bisacrylamide (MBA) as a crosslinker and ammonium persulphate (APS) as an initiator in aqueous solution, followed by hydrolysis with sodium hydroxide. The effects on water absorbency, such as amount of crosslinker, initiator, attapulgite, weight ratio of acrylamide to starch in the feed, gelatinization conditions of starch and molar ratio of NaOH to acrylamide, and so forth, were investigated. These superabsorbent composites were characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The water absorbencies for these superabsorbent composites in water and saline solution were investigated, and water retention tests were carried out. Results obtained from this study showed that the water absorbency of superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% exhibit absorption of 1317 g H₂O/g sample and 68 g H₂O/g sample in distilled water and in 0.9 wt % NaCl solution, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1351–1357, 2005     

Synthesis of cassava starch‐g‐poly(methyl methacrylate) copolymers with benzoyl peroxide as an initiator

Graft copolymers of cassava starch and methyl methacrylate (MMA) were synthesized by free‐radical polymerization with benzoyl peroxide (BPO) as an initiator in an aqueous medium at 80°C. The formation of graft copolymers was confirmed by analysis of the obtained products with Fourier transform infrared spectroscopy and scanning electron microscopy. The effects of the amount of cassava starch, the amount of MMA monomer, the amount of BPO, and the reaction time on the grafting characteristics were studied. The optimum condition for grafting were obtained when 5 g of cassava starch, 5 g of MMA, 0.1 g of BPO, and a reaction time of 3 h were used. These condition provided a graft copolymer with 25.00% add‐on, 81.40% monomer conversion, 54.30% homopoly(methyl methacrylate) formed, 45.70% grafting efficiency, 37.20% grafting ratio, and 95.54% yield. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4083–4089, 2006     

Synthesis and surface properties of polystyrene‐graft‐poly(ethylene glycol) copolymers

Polystyrene‐graft‐poly(ethylene glycol) copolymers (PS‐g‐PEG) were successfully synthesized using the “grafting‐through” method. The graft copolymers and the surface properties of their coats were characterized by 1 H‐NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), static contact angle measurement, and atomic force microscopy (AFM). Both DSC and TEM indicated that the graft copolymers had a microphase separated structure. AFM showed the microphase separated structure also occurred at the coat surface, especially at high PEG content, which could also be indirectly confirmed by the XPS and contact angle results. The formation mechanism of the microphase separated structure was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1458–1465, 2007     

Synthesis and characterization of polyacrylamide grafted copolymers of Kundoor mucilage

In the present research, grafting of acrylamide monomer onto a water‐soluble food grade polysaccharide, Kundoor mucilage, initiated by ceric ion in aqueous medium has been studied under N₂ atmosphere. Ceric ion initiated solution polymerization was found to be satisfactory for the formation of copolymer. The effect of monomer concentration, initiator concentration, reaction time, and temperature, in terms of grafting efficiency (%GE) and percent of grafting (%PG), have been investigated. The graft copolymers were characterized by FTIR, differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and X‐ray diffraction (XRD). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1186–1191, 2005     

Synthesis and characterization of oligosalicylaldehyde‐graft‐oligoaniline and its beginning oligomers

Conjuge bonding oligosalicylaldehyde‐graft‐oligoaniline (OSA‐graft‐OA) was synthesized from the polycondensation reaction of oligosalicylaldehyde (OSA) with oligoaniline (OA). There were various functional groups such as ? OH, ? NH and ? CH?N in the structure of the graft cooligomer. The physical properties of graft‐co‐oligomers such as melting temperature and solubility were studied: number‐average molecular weight, mass‐average molecular weight, and a polydispersity index of OA, OSA, and fractions of the graft cooligomers [(OSA‐graft‐OA)‐I] and [(OSA‐graft‐OA)‐II] were found to be 740, 780 g mol^?1,1.05; 3700, 5990 g mol^?1, 1.62; 990, 2770 g mol^?1, 2.80 and 1300, 4100 g mol^?1, 3.15, respectively. The FTIR and UV‐Vis spectra of the graft cooligomer were compared with those of beginning oligomers. The spectral analyses results showed that the OSA‐graft‐OA synthesized from the polycondensation reaction of aromatic amine with aldehyde that have long oligophenol macromolecule bonded each other with an azomethine bridge through oligophenylamine side chains. The thermal stability of the graft cooligomer and oligomers were measured by thermogravimetric analysis (TG) under an air atmosphere. According to TG analyses, the carboneous residues of the [(OSA‐graft‐OA)‐I) (soluble in ethanol) and (OSA‐graft‐OA)‐II) (soluble in toluene)] were 23 and 40%, respectively, at 1000°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 218–226, 2002     

Polycarbonate-polystyrene block copolymers and their application as compatibilzing agents in polymer blends

The synthesis of a block copolymer with polystyrene (PS) and polycarbonate (PC) segments is described. It is produced by anionic polymerization of the styrene and endcapping with a hydroxyl group followed by subsequent reaction with phosgene and bisphenol-A. The polystyrene/polycarbonate block copolymer was used as a compatibilizing agent for blends of poly(ethylene terephthalate) (PET) and poly(p- phenylene oxide) (PPO). The block copolymer reduced the dimensions of the dispersed phase. The uniaxial mechanical properties of the compatibilized blends were improved by 5 to 10 wt% loadings of the copolymer.     

Synthesis and characterization of gelatin‐polydimethylsiloxane graft copolymers

Gelatin‐polydimethylsiloxane (PDMS) graft copolymers were prepared through the reaction between gelatin and α‐[3‐(2,3‐epoxypropoxy)propyl]‐ω‐butyl‐PDMSs. The copolymers were characterized by FTIR and ¹H‐NMR spectra. As proved by wide angle X‐ray analysis, a new characteristic crystalline peak appeared after the bonding of PDMS to gelatin chains. The microstructure and the elemental identification of gelatin and copolymers were followed through scanning electron microscope with energy dispersive spectrometer. The glass transition temperature of gelatin and copolymers were obtained by differential scanning calorimetry analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of hindered‐phenol‐containing amine moieties as antioxidants for polypropylene copolymers

(4‐Ethylphenyl)‐3,5‐ditertiarybutyl‐4‐hydroxybenzylamine, 1‐phenyl‐4‐(3,5‐ditertiarybutyl‐4‐hydroxybenzyl)piperazine, and 1‐(3,5‐ditertiarybutyl‐4‐hydroxybenzyl)piperidine were synthesized and characterized, and their performance in polypropylene copolymer (PPCP) was tested by multiple extrusions in a Brabender plasticorder. The thermooxidative stability of PPCP was assessed by the measurement of oxidative induction time at 200 ± 1°C, and the thermal stability was assessed by observation of the change in the melt flow rate. A comparative study of the synthesized antioxidants with the commercially available antioxidant 2,6‐ditertiarybutyl‐4‐methylphenol was made. The presence of phenolic and amino groups influenced the performance of the antioxidants. The performance of the antioxidants influenced the thermal stability of the PPCP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1097–1103, 2004     

Synthesis and characterization of temperature‐responsive copolymers based on N‐vinylcaprolactam and their grafting on fibres

BACKGROUND: Responsive materials are able to respond reversibly to an environmental stimulus. When the stimulus is temperature in the physiological range, the responsive material is particularly interesting for textile applications. We describe here the synthesis and characterization of reactive temperature‐responsive copolymers and their subsequent grafting on cotton fabrics. RESULTS: Copolymers of N‐vinylcaprolactam and various reactive monomers were synthesized via free radical polymerization in solution. The copolymers were characterized in terms of chemical structure, molecular weight and temperature‐responsive properties. The copolymer of N‐vinylcaprolactam and methacrylic acid (11 or 22 wt%) and the hydrolysed copolymer of N‐vinylcaprolactam and acryloyl chloride were found to be temperature responsive. They were subsequently grafted on cotton fabrics. The grafting was studied using X‐ray photoelectron spectroscopy and scanning electron microscopy measurements and was found to be effective. Finally, the modified cotton fabrics were found to exhibit temperature‐responsive water regain and water vapour transmission rates. CONCLUSION: Temperature‐responsive copolymers were synthesized, characterized and successfully grafted on cotton fabrics, yielding responsive fabrics. Such fabrics can hence be used to modulate the skin microclimate under textiles. Copyright © 2009 Society of Chemical Industry     

Synthesis of cyclodextrin‐based polymers and their use as debittering agents

Cyclodextrins (CDs) and their derivatives are used to suppress unpleasant tastes and odors or to achieve a controlled release of certain food constituents. This article describes the synthesis by nonconventional methods of (1) crosslinked, insoluble CD polymers and (2) water‐soluble, CD‐grafted carboxymethylchitosan and carboxymethylcellulose. The CD polymers were obtained by the reaction of β‐CD with one of the following crosslinking agents: epichlorohydrin, diphenyl carbonate, or hexamethylene diisocyanate. Their preparations were usually carried out under high‐intensity ultrasound, which resulted in much shorter reaction times and narrower distributions of particle size (as determined by scanning electron microscopy measurements). A novel, insoluble CD polymer was obtained by reticulation under microwaves of propargyl‐β‐CD with 1,3‐bis(azidomethyl)benzene through Huisgen 1,3‐dipolar cycloaddition. Short columns packed with the insoluble polymers were found to efficiently sequester naringin from aqueous solutions; successively, they could be easily regenerated by a counter‐current ethanol wash that also achieved an excellent recovery of the flavonoid. Differential scanning calorimetry thermograms showed that the crosslinked CD polymers formed inclusion complexes with naringin. The soluble polymers also interacted with bitter flavonoids of citrus fruits (naringin and limonin), as shown by the results of sensorial panel tests, in which they behaved as bitter‐masking agents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008