Preparation and Characterization of Starch-g-Polymethacrylamide Copolymers

In this article, methacrylamide was successfully grafted onto starch using benzoyl peroxide as a radical initiator in aqueous medium. The extent of grafting was found to be affected by the initiator, monomer, starch concentration, and temperature. The optimum initiator concentration is 2.0×10⁻³ mol/L. The graft yield was observed to increase with the monomer concentration and temperature. No optimum values for the monomer concentration and temperature were found. The overall activation energy for graft copolymerization was obtained. The grafted starches were characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). TGA thermograms showed that the thermal stability of starch increased as a result of grafting. SEM micrographs showed that the granular structure of starch was not maintained after graft copolymerization. The water uptake and moisture retainment values of starch graft copolymers were investigated.     

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     

Polyacrylonitrile‐grafted Cassia pudibunda seed gum: A potential commercial gum from renewable source

Cassia pudibunda (CP) seed gum was grafted with poly(acrylonitrile) using persulphate/ascorbic acid redox initiator. Optimal grafting Conditions were determined and maximum % grafting and % efficiency observed were 294 and 85.3%, respectively. Grafted CP gum (gum‐g‐polyacrylonitrile; CP‐g‐PAN) was characterized using FTIR, XRD, and TGA analysis. The CP‐g‐PAN sample with maximum %G was observed to be water insoluble, however, 1% solution of the base‐hydrolyzed CP‐g‐PAN had a viscosity of 114.7 centipoises, which was observed to increase continuously for first 5 days and there upon became fixed and was shown to be stable even after 20 days when left at room temperature. Water and saline retention for CP‐g‐PAN after 10 min soaking were observed to be 47 and 30.15 g/g, respectively. Thus, base‐hydrolyzed CP‐g‐PAN samples may find use as water sorbents and their aqueous solutions may be used commercially where medium to low viscosity solutions with high shelf life is the requirement. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 619–627, 2006     

Effect of graft-copolymerization with poly(acrylamide) on rheological and thermal properties of cassava starch

Graft copolymers of different grafting levels were synthesised by the free radical initiated reaction of cassava starch with acrylamide in presence of ceric ammonium nitrate. The viscosity properties of the native granular starch and the grafted starches were determined using a Rapid visco analyzer (RVA) and rheological properties by frequency sweep test under different conditions using a rheometer. Some of the grafted starches exhibited significantly higher and some others exhibited drastically reduced peak viscosity values irrespective of the percentage grafting. All the grafted starches exhibited very good viscosity stability as evidenced from the highly reduced breakdown and higher final viscosity values in comparison to native cassava starch. Thermal analysis of the pure granular cassava starch and grafted starches was carried out using a differential scanning calorimetry (DSC) and thermogravimetry. DSC studies showed that in comparison to native starch, the grafted starches showed lower temperatures of transition. The thermal stability of cassava starch was enhanced by grafting as observed from the thermogravimetric data. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

Characterization of cationic polyacrylamide‐grafted starch flocculant synthesized by one‐step reaction

Cationic polyacrylamide‐grafted starch (St‐g‐CPAM) flocculant was prepared by using corn starch and acrylamide (AM) as monomers, dimethyl diallyl ammonium chloride (DMDAAC) as cationic monomer through solution polymerization. The effects of initiator, reaction temperature, and monomer concentration on flocculation, the efficiency of grafting, and the yield of grafting were investigated. The results show that the optimal conditions of the polymerization are as follows: the concentration of ceric ammonium nitrate is 0.5%, the reaction temperature is 60°C, the concentration of total monomer is 20%, and the monomer ratio between AM and DMDAAC is 7 : 3. The flocculation capability was characterized by turbidity reduction. The thermal behavior, chemical structure, and microstructure of St‐g‐CPAM were also investigated by thermal gravimetric, IR, and SEM analyses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Graft copolymerization of methyl methacrylate onto sago starch using ceric ammonium nitrate and potassium persulfate as redox initiator systems

The graft copolymerization of methyl methacrylate (MMA) onto sago starch was carried out in aqueous media by different initiators of ceric ammonium nitrate (CAN) and potassium persulfate (PPS) and under a nitrogen gas atmosphere. Using CAN as an initiator, the maximum percentage of grafting (%G) was ascertained to be 246% at the following optimum conditions: a 70°C reaction temperature, a 2‐h reaction period, 2.0 mmol of CAN, 0.4 mmol of nitric acid, and 141 mmol of MMA. The maximum %G achieved with PPS as the initiator was 90%. The optimum conditions were a 50°C reaction temperature, a 1.5‐h reaction period, 47 mmol of monomer, and 1.82 mmol of PPS. The grafting of MMA onto sago starch was confirmed by the IR spectra of pure sago starch, MMA, and MMA grafted sago starch. This material may have application as a biodegradable plastic. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1375–1381, 2001     

Preparation,characterization, and some physical properties of polypropylene/poly(methyl acrylate)‐grafted glass wool composites

Polypropylene/poly(methyl acrylate)‐grafted glass wool (PMA‐g‐GW) mixes were prepared. The polymerization process was carried out using potassium persulfate (PPS) and PPS/acetone sodium bisulfite (ASBS) as a redox‐pair initiation system at 60 and 70°C. The effect of using PPS or PPS/ASBS on the grafting percent and conversion percent reveals that the conversion percent values on using PPS as an initiator are higher than those of PPS/ASBS, while in the case of grafting, the inverse is true, that is, using PPS as an initiator gives grafting percent values lower than those that can be obtained using PPS/ASBS. The dielectric properties, thermal diffusivity, specific heat capacity, and thermal conductivity of PP loaded with modified glass wool as a function of different types and concentrations of initiators—used in the grafting polymerization process, namely, PPS and the redox initiating system—were also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 723–732, 2003     

Synthesis of controlled thermoresponsive PET track‐etched membranes by ATRP method

Controlled thermoresponsive PET track‐etched membranes were synthesized by grafting N‐isopropylacrylamide (NIPAAm) onto the membrane surface via atom transfer radical polymerization (ATRP). The initial measurements were made to determine the anchoring of ATRP initiator on PET membrane surface. Thereafter, polymerization was carried out to control the mass of polymer by controlling reaction time grafted from the membrane surface and, ATR‐FTIR, grafting degree measurements, water contact angle measurements, TGA, and SEM were used to characterize changes in the chemical functionality, surface and pore morphology of membranes as a result of modification. Water flux measurements were used to evaluate the thermoresponsive capacity of grafted membranes. The results show the grafted PET track‐etched membranes exhibit rapid and reversible response of permeability to environmental temperature, and its permeability could be controlled by controlling polymerization time using ATRP method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Pectin grafted poly(N‐vinylpyrrolidone): Optimization and in vitro controllable theophylline drug release

The present article describes preparation, optimization, and characterization of pectin grafted polyvinylpyrrolidone hydrogels followed by controllable theophylline drug release. The gels were prepared in the presence of N,N′–methylenebisacrylamide (MBAA) crosslinker and ceric ammonium nitrate (CAN) initiator under N₂ atmosphere. Optimum conditions, in terms of percent of grafting (%G), were determined as follows: Pectin = 1.0 g, [NVP] = 2.81 mM, [MBAA] = 0.65 mM, [CAN] = 0.073 mM, polymerization temperature = 30°C and time = 4.0 hrs. Hydrogels were characterized by FTIR, TGA, DSC, XRD, and SEM. In vitro controllable release of theophylline model drug was studied using different N‐vinylpyrrolidone monomer to MBAA crosslinker ratio (i.e., [NVP]/[MBAA] ratios) and different polymerization temperatures at two pH values, namely 5.5 and 7.4. The optimum conditions for colon‐targeted vehicles that could provide the least theophylline release at pH 5.5, and the most theophylline release at pH 7.4, were as follows: [NVP]/[MBAA] = 4.33, polymerization temperature = 10°C and %G = 62.2. Such promising hydrogel characteristics may play the key role in many future drug release implementations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Factors influencing absorbent properties of saponified starch‐g‐(acrylic acid‐co‐acrylamide)

Mixtures of acrylamide (AM) and acrylic acid (AA) were grafted onto gelatinized maize starch by using ceric ammonium nitrate (CAN) as an initiator. These graft copolymers were hydrolyzed with alkali to yield hydrogels. The effects of different reaction variables, such as the concentration of the initiator and crosslinker, initial dilution of monomers, gelatinization conditions of starch, and the ratio of AM and AA in the monomer feed, on the water absorption capacities of these hydrogels have been examined. Absorption increases on gelatinizing starch at a higher temperature for a longer time as smaller granules gelatinize only under these conditions. The higher proportion of AA in the monomer feed enhances absorption due to formation of polyelectrolyte. The optimum conditions for obtaining maximum water absorbency established in the present study are granular maize starch = 2.0 g; gelatinization temperature = 95°C; gelatinization time = 60 min; AM = 1.0 g; AA = 4.0 g; CAN = 0.008 mol/L; N,N′‐methylene bisacrylamide = 1%. The product so formed was saponified with NaOH and then precipitated in excess of methanol. The dried and finely powdered product showed the maximum water absorbency of 510 g/g. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2480–2485, 2000     

Thermal behavior and surface morphology studies on polystyrene grafted sago starch

Polystyrene grafting onto sago starch was carried out by using ceric ammonium nitrate as a redox initiator. The grafted copolymers were characterized by FTIR, thermogravimetry (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). FTIR spectra analysis of the grafted chain and commercial polystyrene was identical, indicating that styrene was successfully grafted onto sago starch. TGA thermograms and analysis of DSC curves showed that the thermal stability of starch increases as a result of grafting. SEM micrographs showed the deformed prolate ellipsoidal shape of sago starch particles and this shape disappeared in polystyrene grafted sago starch being replaced with a spongy surface with pores. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2053–2058, 2003     

The graft copolymerization of corn starch by microwave irradiation with rheological phase reaction

The corn starch was grafted by microwave irradiation with rheological phase reaction, to meet the sizing requirements of polyester/cotton blended yarn and avoid the disadvantages of corn starch size including brittle, hard, and size shedding. On the basis of the damping characteristics of corn starch film and the polarity of grafting monomer, the grafting effect of grafted corn starch was researched by using infrared spectroscopy, SEM, rotary viscometer, and thermomechanical analyzer. The results showed that both hydrophilic groups and hydrophobic groups were introduced in the molecular chains of grafted corn starch. The storage modulus of grafted corn starch film reached 285–315 MPa, being four times higher than that of nongrafted corn starch film. Compared with corn starch sizing, the viscosity of grafted corn starch sizing decreased 62.5%. Furthermore, through analyzing grafting law and establishing regression equation, it was indicated that the irradiation time and initiator content influenced the grafting ratio of grafted starch significantly. The grafting ratio could reach 19.57%, when the irradiation time and initiator content were selected with 3.5 min and 4.55%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Starch‐grafted polypropylene: Synthesis and characterization

Graft copolymerization of starch has been carried out onto preirradiated polypropylene (PP) in an aqueous medium using benzoyl peroxide (BPO) as the radical initiator. The maximum percentage of grafting (115%) of starch onto PP was obtained at optimum conditions of BPO concentration, 1.239 × 10⁻³ moles; temperature, 65°C; in 120 min. using 30 mL of water. Swelling studies were carried out in pure, binary, ternary and quaternary solvent systems comprising of water, ethanol (EtOH), dimethylsulphoxide (DMSO), and N,N‐dimethylformamide (DMF) in different ratios. Maximum swelling is observed in DMSO and DMF, followed by EtOH and least in water for true graft. Water retention studies of pristine PP and PP‐g‐Starch (both composite and true graft) were investigated at different time periods, temperature and pH. The composite contains grafted PP, unreacted starch and unreacted PP whereas true graft is the product from which both unreacted polymers have been removed. Maximum % water retention of PP‐g‐Starch (composite) (110%) was observed in 8 h at 50°C in neutral medium (pH = 7). The graft copolymers were characterized by FTIR, DTG, DTA, TGA, and SEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of cardanol‐grafted natural rubber—The solution technique

Cardanol, a by‐product of the cashew industry, has been recently proven to be a multifunctional additive (MFA) in rubbers. It is expected that grafting of cardanol onto natural rubber (NR) would impart inherent MFA characteristics to the rubber. Grafting has been carried out in solution using toluene as the solvent and a peroxide initiator. Optimized conditions of grafting reaction could be arrived at using a statistical tool namely orthogonal array testing strategy, keeping the maximum percentage of grafting as the selection criteria. Further studies were conducted to study the influence of monomer concentration and initiator concentrations. The effect of the reaction temperature and reaction time were also investigated. Characterization of grafted rubber was carried out with the help of infrared spectroscopy, nuclear magnetic resonance spectroscopy and thermal analysis. IR spectrum of cardanol exhibited the characteristic peak of cardanol at 3356 cm^?1. Percent grafting (PG) of cardanol onto NR was determined by residual weight method. PG increased with increasing cardanol quantity reached an optimum and then decreased. The increase in reaction time and reaction temperature also caused increasing levels of the grafted cardanol. However, PG continuously increased with increasing initiator concentrations. Differential scanning calorimetry studies of the grafted NR showed a lower glass transition temperature than that of the raw NR, which is indicative of the plasticization effect of cardanol. The thermogravimetric analysis showed a higher thermo oxidative stability for cardanol‐grafted NR. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Studies on preparation and properties of vinyltriethoxysilane‐grafted styrene‐butadiene rubber

Graft polymerization of vinyltriethoxysilane (VTES) onto styrene‐butadiene rubber (SBR) was carried out in latex using benzoic peroxide (BPO) as an initiator. The concentration of VTES effecting on vulcanization characteristics, mechanical properties and thermal properties of VTES‐grafted SBR (SBR‐g‐VTES) were investigated. The grafting of VTES onto SBR and its pre‐crosslinking were confirmed by attenuated total teflectance‐Fourier transform infrared reflectance and proton nuclear magnetic resonance. The mechanism of graft polymerization was studied. The results revealed that the minimum torque, optimum cure time, tensile strength, thermal decomposition temperature, and glass transition temperature (T_g) all increased with the increasing concentration of VTES. But the grafting efficiency of VTES, rate of vulcanization, and elongation at break of the SBR‐g‐VTES decreased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Solvothermal process for grafting dibutylmaleate onto poly(ethylene‐co‐1‐octene)

Solvothermal process was successfully developed to graft dibutylmaleate (DBM) onto poly(ethylene‐co‐1‐octene) (POE) with dicumyl peroxide (DCP) as free radical‐initiator. FTIR spectra demonstrate that DBM is successfully grafted onto the backbone of POE by this novel method. The influences of DBM content, DCP concentration, POE concentration, reaction temperature and reaction time on the grafting copolymerization have been investigated in detail through grafting degree (GD). It is worthy to indicate that high grafting degree (above 15%) can be achieved through the one‐pot way when the graft reaction is carried out in 40 mL toluene at 150°C for 5 h with 1.6 g DBM, 6–8 g POE and 0.35 g DCP. This developed solvothermal process is becoming an effective way to prepare POE‐g‐DBM graft copolymers, and can be extended to other systems. In addition, TGA results show that the thermal properties of POE are enhanced after the grafting reaction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of biodegradable polyethylene by graft copolymerization of starch using glucose–Ce(IV) redox system

Graft copolymerization of low‐density polyethylene (LDPE) onto starch was carried out with glucose–cerium(IV) redox initiator in an aqueous sulfuric acid medium under nitrogen atmosphere. The graft yield was influenced by various parameters like reaction time, temperature, and concentrations of acid, glucose, polyethylene (PE), starch, and initiator. A maximum graft yield of 85.66% was obtained at a temperature of 50°C and at higher concentration of starch. Effect of grafting on crystallinity, morphology, and thermal properties of modified PE has been evaluated using X‐ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA/DTA). Biodegradability of starch‐grafted PE has been tested applying soil‐burial test. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3229–3239, 2006     

Preparation and properties of bitumen modified with the maleic anhydride grafted styrene‐butadiene‐styrene triblock copolymer

A procedure to improve the properties of styrene‐butadiene‐styrene (SBS) copolymer modified bitumen by grafting of maleic anhydride (MAH) onto SBS in the presence of benzoyl peroxide (BPO) as initiator was proposed. The effects of the grafting degree (GD) on the properties of modified bitumen were investigated. FTIR spectroscopy was employed to verify the grafting of MAH onto SBS. The GD of MAH onto SBS was determined by a back titration procedure. To assess the effects of the GD of grafted SBS on properties of modified bitumen, the softening point, penetration, ductility, elastic recovery, penetration index, viscosity, storage stability, and dynamic shear properties were tested. Experimental results indicated that the SBS grafted with maleic anhydride (SBS‐g‐MAH) copolymer was successfully synthesized by solvothermal method, and different GD of the SBS‐g‐MAH was obtained by control the MAH concentration. The GD of the MAH onto SBS has great effect on the rheological properties of the modified bitumen, and the high temperature performance and storage stability of modified bitumen were improved with the GD of the MAH onto SBS increasing. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthesis and evaluation of fluorosilicone‐modified starch for protection of historic stone

Starch is sensitive to moisture and is weak to durability in the protection application to ancient relics. Therefore, two fluorosilicone‐modified starches are firstly prepared and evaluated for the protection of historic stones. The fluoro‐silicone copolymer grafted starch of P(VTMS/12FMA)‐g‐starch is synthesized by grafting copolymer of vinyltrimethoxysilane (VTMS) and dodecafluoroheptyl methacrylate (12FMA) onto starch. While the fluoro‐silicone starch latex of VTMS‐starch@P(MMA/BA/3FMA) is obtained by emulsion polymerization of VTMS primarily grafted‐starch (VTMS‐starch) with methyl methacrylate (MMA), butyl acrylate (BA) and 2,2,2‐trifluoroethyl methacrylate (3FMA). The grafting fluorosilicone copolymer onto starch improves obviously their hydrophobic and thermal properties. Comparatively, VTMS‐starch@P(MMA/BA/3FMA) film performs higher water contact angle (107°) and thermal stability (350–430°C) than p(VTMS/12FMA)‐g‐starch film (72°, 250–420°C) due to the migration of fluorine‐containing group onto the surface of film during the film formation. Therefore, VTMS‐starch@P(MMA/BA/3FMA) shows much better protective performance in water‐resistance, and salt/freeze‐thaw resistance for stone samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41650.