Modification of carbohydrate polymers via grafting of methacrylonitrile onto pregelled starch using potassium monopersulfate/Fe2+ redox pair

The graft copolymerization of reactive pregelled starch (PGS) with methacrylonitrile (MAN) was performed and the reaction conditions were optimized using potassium monopersulfate (PMPS) in the presence of ferrous ion redox pair as initiator. Emphasis was directed towards increasing the graft formation and decreasing homopolymerization. The grafting parameters were studied with respect to graft yield and graft reaction efficiency percent. In addition, the newly prepared polymethacrylonitrile (polyMAN)‐pregelled starch graft copolymers were applied to cotton textiles to see their suitability as a new sizing agent. Based on the results obtained, appropriate conditions for grafting MAN onto pregelled starch was established and the graft yield was higher under the following conditions: using 0.004 mol l^?1 potassium monopersulfate as initiator, 0.005 mol l^?1 ferrous ion concentration, 0.003 mol l^?1, sulfuric acid, 50 % MAN concentration (based on weight of substrate), material to liquor ratio 1:2.5, reaction time 60 min, and polymerization temperature 40 °C. Finally, fabric samples sized with polyMAN‐pregelled starch graft copolymers acquired higher tensile strength and abrasion resistance than that sized with original pregelled starch, while elongation at break was unaltered. Copyright © 2004 Society of Chemical Industry     

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     

Graft copolymers of starch–polyacrylonitrile prepared by ferrous ion–hydrogen peroxide initiation

The effect of concentration, reactant ratios, temperature, and starch pretreatment on grafting of acrylonitrile onto starch were studied. Grafting was efficient at high concentrations (8–12% starch) when granular starch was used. The molecular weights for grafted polyacrylonitrile (PAN) were higher when gelatinized starch was used, but grafting efficiencies (grafted PAN/total PAN) were much lower. The molecular weight of the grafted side chain increased with increased concentration of reactants. The grafting frequency was highest when the reaction mixture was kept at 5°C and decreased with increased swelling of the starch. The starch–polyacrylonitrile graft copolymers were saponified and dried to give products which absorbed 75–440 ml H₂O per gram and 20–70 ml synthetic urine per gram.     

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     

Reactive extrusion vs. batch preparation of starch–g–polyacrylonitrile

Acrylonitrile (AN) was graft polymerized onto unmodified cornstarch by a continuous reactive extrusion process and, for comparison, by a typical batch reaction process. The effect of AN/starch weight ratios, level of ceric ammonium nitrate (CAN) initiator, starch in water concentration, reaction temperature, reaction time, and extruder screw speed in the reactive extrusion process was studied. Add-on, reaction efficiency, grafting frequency, weight average molecular weight (MW) and MW distribution of polyacrylonitrile (PAN), and water absorbency of the saponified copolymers were determined. Processing times in the twin-screw extruder (ZSK) were 2–3 min, and total reaction time was about 7 min before reaction of the extruded material was terminated, compared to a reaction time of 2 h used in the typical batch procedure. The continuous reactive extrusion process was found to be a rapid and efficient means of preparing St-g-PAN with high add-on (% PAN of the grafted product). For example, 42% add-on was achieved within the 7-min reaction period using an AN/starch weight ratio of 1.0 (3.5% CAN, starch weight basis), as compared to 38–49% for the 2-h batch process (0.75–1.5 AN/starch ratio). Percentages of homopolymer of the copolymers were low for both extrusion and batch processes. Grafting frequencies were substantially higher while MWs were significantly lower for grafts from the extrusion process. Water absorbency of the saponified St–g–PAN products was somewhat greater for the products prepared by the batch process.     

Preparation and characterization of poly(methyl methacrylate) grafted sago starch using potassium persulfate as redox initiator

In this article, the graft copolymerization of methyl methacrylate (MMA) onto sago starch (AGU) was carried out in aqueous medium using potassium persulfate (PPS) under nitrogen gas atmosphere. The maximum percentage of grafting achieved was 90% under optimized conditions of reaction temperature, monomer, PPS, AGU, and reaction period corresponding to 50°C, 47 mmol, 1.82 mmol, 6.17 × 10^?3 mol L^?1, and 1.5 h, respectively. The grafting of MMA onto sago starch was confirmed by the differences in infrared spectroscopy. The viscosity measurement and the average molecular weight determination were estimated using Huggin's and Mark Houwink's equations, respectively. This material may have application as a biodegradable plastic. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1891–1897, 2004     

Synthesis and physicochemical properties of graft copolymer of corn starch and acrylamide

Graft copolymerization of corn starch with acrylamide using ceric ammonium sulphate/citric acid initiation system has been studied under nitrogen atmosphere in aqueous medium. The grafting parameters are favored by increasing monomer concentration and reaction time but are affected by higher concentration of initiator and high temperature. The optimum conditions established for grafting were as follows: the concentration of initiator, 0.003 mol/L; the concentration of citric acid, 0.03 mol/L; monomer/starch, 1:1 feed ratio (w/w); reaction time, 3.0 h; and temperature, 35°C. The extent of grafting was examined by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy. Both swelling power and solubility increased with the increase in temperature. Graft copolymerization increased swelling power and reduced solubility. Rapid visco‐analyzer pasting profile was studied. Graft copolymerization of corn starch results in high pasting temperature, high peak viscosity, and setback as compared with native starch. Breakdown was retarded at low percentage grafting (6.60%) but increased at high percentage grafting (60.27%). POLYM. COMPOS. 28:47–56, 2007. © 2007 Society of Plastics Engineers     

Preparation and characterization of ultra‐low molecular weight poly(vinyl alcohol) graft copolymer

Graft reaction of acrylamide (AM) and 4‐vinyl pyridine (4‐VP) onto ultra‐low molecular weight poly(vinyl alcohol) by ceric (IV) ion initiation had been systematically investigated; and the graft conditions were optimized by studying the effect of monomer/initiator concentration, solvents composition, reaction time and temperature. At optimized conditions, the maximum grafting efficiency and grafting ratio was ～ 50% and 51%, respectively with the presence of AM, whereas they decreased to 19% and 23%, respectively, without the presence of AM. Thermogravimetric analysis showed that as‐resulted graft copolymer had a lower thermal stability than homopolymer PVA. FTIR and ¹H‐NMR confirmed chemical structure of as‐synthesized graft copolymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal,mechanical, and surface characterization of starch–poly(vinyl alcohol) blends and borax‐crosslinked films

Starch–poly(vinyl alcohol) (PVA) blends with different compositions were prepared and crosslinked with borax by in situ and posttreatment methods. Various amounts of glycerol and poly(ethylene glycol) with a molecular weight of 400 were added to the formulations as plasticizers. The pure starch–PVA blends and the crosslinked blends were subjected to differential scanning calorimetry, thermogravimetry, and X‐ray photoelectron spectroscopic studies. Broido and Coats–Redfern equations were used to calculate the thermal decomposition kinetic parameters. The tensile strengths and elongation percentages of the films were also evaluated. The results suggested that the glass‐transition temperature (T_g) and the melting temperature strongly depended on the plasticizer concentration. The enthalpy relaxation phenomenon was dependent on the starch content in the pure blend. The crosslinked films showed higher stability and lower T_g's than pure PVA and starch–PVA blends, respectively. High‐resolution X‐ray photoelectron spectroscopy provided a method of differentiating the presence of various carbons associated with different environments in the films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1313–1322, 2005     

Graft Copolymerization onto Starch–I. Synthesis and Optimization of Starch Grafted with N-tert-Butylacrylamide Copolymer and its Hydrogels

Grafting of N-tert-butylacrylamide (BAM) onto starch in aqueous medium initiated by ceric ammonium nitrate ion has been studied under N₂ atmosphere. The optimum conditions with respect to monomer concentration, initiator concentration, polymerization temperature, polymerization time and material to liquor ratio were studied in terms of percent of grafting efficiency (%GE) and percent of grafting yield (%GY). The optimum conditions obtained for the grafting of BAM on 1.0 g starch were: [BAM]=0.020 mol/L, [CAN]=0.91×10^–3 mol/L, Temperature=30C, and Time=240 min. Starch-g-BAM copolymer was characterized by FTIR, TGA for thermal stability, X-ray diffraction (XRD) for the crystallinity and scanning electron microscope (SEM) for surface morphology of the copolymer. Acid hydrolysis and viscosity average molecular weight (M _v) of copolymer were evaluated for the copolymer. Hydrogels prepared by grafting of BAM onto gelatinized starch showed maximum water uptake and moisture retain of 162% and 63% respectively.     

Effect of graft copolymerization of 2-hydroxyethyl methacrylate on the properties of polyester fibers and fabric

Graft copolymerization of hydroxyethyl methacrylate (HEMA) onto poly(ethylene terephthalate) (PET) fibers using benzoyl peroxide (BP) as initiator was carried out in water and in water/organic solvent as a reaction medium. The effect of initiator concentration, reaction time, temperature, and reaction medium as well as addition of FeSO₄ to the polymerization medium was studied. Percent grafting was enhanced significantly by increasing BP concentration up to 0.016 mol/L and then decreased upon further increase in initiator concentration. Increasing the monomer (HEMA) concentration up to 0.48 mol/L improves significantly the graft yield. Raising the polymerization temperature up to 85°C causes a significant increase in grafting yield; further increase in temperature leads to decrease in graft yield. Incorporation of Fe⁺² ions in the polymerization system decrease the graft yield. The same situation is encountered when water/solvent mixture is used as reaction medium. Solvent employed were methanol, toluene, and benzene.     

Graft copolymerization of methyl methacrylate onto starch using a Ce(IV)–glucose initiator system

Graft copolymerization of methyl methacrylate onto starch was carried out in aqueous medium using Ce(IV)–glucose initiator in the temperature range 40–60°C. Effects of concentration of Ce(IV), glucose, H₂SO₄, monomer, and starch on grafting were investigated. Percentages of grafting were evaluated and compared. The overall energy of activation was calculated from the effects of time and temperature of polymerization. The reaction mechanism was also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 981–990, 2004     

Graft copolymerization of maleic anhydride onto low‐molecular‐weight polyisobutylene through solvothermal method

The free‐radical graft copolymerization of maleic anhydride (MAH) onto highly reactive low molecular weight polyisobutylene was conducted by the use of benzoyl peroxide as an initiator through the solvothermal method. Fourier transform infrared spectra and ¹H‐NMR spectra confirmed that maleic anhydride was successfully grafted onto highly reactive low molecular weight polyisobutylene backbone, and the grafting mechanism also was proposed. The effect of benzoyl peroxide content, MAH concentration, total reactant amount in the reaction vessels, reaction temperature and time, and different kinds and volumes of solvents on MAH's degree of grafting was investigated in detail. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melt grafting of glycidyl methacrylate onto polypropylene and reactive compatibilization of rubber toughened polypropylene

Free radical melt grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) was studied. The extent of GMA grafting and the molecular weight of the functionalized PP copolymers were controlled by carefully manipulating various reaction factors, such as monomer concentration, initiator concentration, reaction temperature, and molecular weight of the starting PP homopolymer. The use of a second monomer, styrene, in the grafting process helped to increase GMA grafting further and reduce chain scission. The GMA modified PP copolymer was found to be able to reactively compatibilize PP/acrylonitrile-co-butadiene-co-acrylic acid rubber (NBR) blends. Up to an eight-fold increase in the impact energy of the PP/NBR blend was obtained. The compatibilizing capacities of the reactive copolymers, in terms of impact energy improvement of the PP/NBR blend, were found not to be exclusively dependent on the total concentration of reactive functionalities in the matrix of the blend. The characteristics of the reactive copolymers, i.e., the extent of functionalization and the molecular weight, were found to have significant influences on the compatibilizing capacity. A large amount of moderately functionalized copolymer offers better compatibilization performance than a small amount of highly functionalized copolymer. A significant drop in impact energy was observed with declining molecular weight of the copolymer.     

Molecular control of polystyrene in the reverse iodine transfer polymerization (RITP) – Suspension process

The reverse iodine transfer polymerization (RITP)-suspension polymerization of styrene was carried out in the presence of molecular iodine (I₂) using AIBN as an initiator and polyvinylalcohol (PVA) as a stabilizer under argon atmospheres at 70 °C for 10 h in the absence of light. The effect of iodine and styrene contents on the molecular characteristics was investigated. The result was summarized into three categories; (1) the two different polymerizations, the emulsion and suspension, simultaneously occurred in the RITP-suspension polymerization. (2) The emulsion fraction decreased, whereas the suspension fraction increased with the I₂ content from 0 to 0.25 mmol, resulting in the decreased molecular weight of the resultant polymer from 320,000 to 59,000 g/mol, respectively. This was arisen from the higher reaction rate of the RITP-suspension polymerization due to the better solubility of AIBN in the monomer droplet in the suspension phase than in the micelle in the emulsion phase upon the increased I₂ content. (3) As the styrene content increased up to 40 wt% under fixed I₂ content, the suspension fraction dominated, resulting in the reduced molecular weight from 59,000 to 38,000 g/mol, respectively. This was rationalized that the temperature increment upon the relatively small amount of solvent, which means due to the large amount of monomer, induced the rapid polymerization in the monomer droplets where the suspension polymerization was favorable. Thus, the RITP-suspension process dramatically decreased the molecular weight of PS not only by the presence of I₂, but also by the dominated suspension fraction.     

Microwave irradiated synthesis of grafted cationic starch: Synthesis,characterization, application,and biodegradation

A biodegradable copolymer was synthesized by grafting copolymerization of acrylamide, β‐hydroxyethyl methacrylate, and n‐butyl acrylate onto corn cationic starch (CS) by microwave irradiation. The grafted cationic starch (GCS) was characterized by Fourier‐transform infrared spectroscopy, scanning electron microscopy, and X‐ray diffraction. The optimum conditions on graft copolymerization with respect to reaction temperature, exposure time, and initiator concentration were investigated. Physicochemical properties of GCS, such as swelling power, solubility, intrinsic viscosity, and apparent viscosity, were studied, and its application performances as textile sizing agent were tested. Results showed that compared with CS, physicochemical properties of GCS were significantly improved, including decreased crystallinity, weakened granular, increased hydration capacity, and rheological property. Polyester/cotton blended yarns sized with GCS obtained more reinforced mechanical properties than samples sized with CS and exhibited higher tensile strength and abrasion resistance than polyvinyl alcohol (PVA) sized yarns. The mechanisms that the starch physicochemical properties affected on the sizing performances were discussed as well. Biodegradation analysis on these sizing agents showed that BOD₅/COD_cr of GCS was 0.263, which outclasses that of PVA (BOD₅/COD_cr = 0.009). This novel biomaterial could be expected to have promising applications especially in textile industry and be an ideal substitute for PVA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1645–1652, 2013     

Optimized conditions for the grafting reaction of poly(methyl acrylate) onto rubberwood fiber

Graft copolymerization of poly(methyl acrylate) (PMA) onto rubberwood fiber (RWF) was carried out by free radical initiation. Hydrogen peroxide and ferrous ions were used as an initiator system. Effects of various parameters (reaction temperature and reaction time, as well as hydrogen peroxide, ferrous ammonium sulfate and monomer concentrations) on the grafting percentage were investigated. A high percentage of grafting was achieved when optimum reaction conditions were used. The optimum temperature of the reaction was determined to be about 55 °C and the reaction time was 120 min. The optimum concentration of H₂O₂ was 0.03 M and the amounts of Fe²⁺ and MA were 0.4 mmol and 0.05 mol, respectively. The PMA homopolymer was removed from the graft copolymer by Soxhlet extraction using acetone. The presence of PMA on the fiber was confirmed by FT-IR spectroscopy and gravimetry. The surface morphology of the poly(methyl acrylate)-graft-(rubberwood fiber) was studied by means of scanning electron microscopy. Copyright © 2004 Society of Chemical Industry     

淀粉接枝丙烯酰氧乙基三甲基氯化铵共聚物的合成

以玉米淀粉为原料,在水介质中通过硝酸铈铵引发淀粉与丙烯酰氧乙基三甲基氯化铵(DAC)接枝共聚,制备系列含阳离子季铵基团的淀粉-DAC接枝共聚物,系统考察了反应条件对接枝共聚物接枝率(PG)的影响。结果表明:在本实验体系内可制备较高接枝率的阳离子接枝共聚物。当硝酸铈铵的浓度为1.5×10-2mol/L,m(DAC)∶m(淀粉)=3,反应温度40℃,反应时间4 h时,接枝共聚物的接枝率最高可达118.67%。用FTIR、1HNMR、XRD对接枝共聚物结构进行了表征。     

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     

Grafting vinyl monomers onto silk fibers: Graft copolymerization of methyl methacrylate onto silk using acetylacetonate Mn(III) complex

The graft copolymerization of methyl methacrylate onto Mulberry silk fibers was studied in aqueous solution using Mn(acac)₃ as initiator. Perchloric acid was found to catalyze the reaction. The rate of grafting was investigated by varying the concentration of the monomer and the complex, acidity of the medium, the solvent composition of the reaction medium, the surfactants, and the inhibitors. The graft yield increases with increasing concentration of Mn(acac)₃ up to 0.01 mol/L, decreasing thereafter. Increase of MMA concentration up to 0.56 mol/L increases graft yield, and thereafter it decreases. Among the various vinyl monomers studied, MMA was found to be most suitable for grafting. Grafting increases up to 7.5 × 10^?3 mol/L of HClO₄ concentration, and thereafter it decreases. A suitable reaction scheme has been proposed and a rate equation has been derived. The energy of activation has been calculated from the Arrhenius plot. The chain transfer constants for various chain transfer solvents have been evaluated from the average molecular weight (M?) of grafted poly(methyl methacrylate).