Microwave‐accelerated Synthesis and Characterization of Potato Starch‐g‐poly(acrylamide)

Using a very low concentration of potassium persulfate as initiator, acrylamide could be efficiently grafted onto potato starch under microwave irradiation and for the grafting O₂ removal from the reaction vessel was not required. Under optimal conditions, grafting and efficiency observed were 160% and 89%, respectively. Grafted starch was characterized by using Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) and thermogravimetric analysis (TGA). It was observed that the microwave irradiation could significantly accelerate the synthesis of starch‐graft‐poly(acrylamide), because under identical conditions no grafting was observed in a conventional procedure. Viscosity, shear stability and water/saline solution retention of the microwave‐synthesized grafted starch were studied and compared with that of the parent starch.     

Response Surface Methodology for the Optimization and Characterization of Cassava Starch‐graft‐Poly(acrylamide)

Response surface methodology (RSM) was employed for the synthesis of cassava starch‐graft‐poly(acrylamide) using ceric ammonium nitrate as free radical initiator. Concentration of acrylamide, concentration of ceric ammonium nitrate, reaction temperature and duration of reaction were optimized using a 4‐factor 3‐level Box‐Behnken design. The dependent variables were percentage grafting (%G) and grafting efficiency (GE). Second order polynomial relationships were obtained for %G and GE, which explained the main, quadratic and interaction effects of factors. The highest%G and GE obtained were 174.8% and 90.7%, respectively. The optimum values of parameters predicted through RSM were 20 g acrylamide/10 g dry starch, 3.3 g/L ceric ammonium nitrate, 180 min reaction duration and 45ºC temperature with a %G of 190.0. For GE, the predicted levels of factors for the optimum value of 90.8% were 17.5 g acrylamide/10 g dry starch, 4.1 g/L ceric ammonium nitrate, 180 min reaction duration and 55ºC temperature. The graft reaction was confirmed by FTIR analysis, where the absorption bands corresponding to the C=O stretching and N‐H bending of the –CONH₂ group were observed. Scanning electron microscopic studies on grafted starches revealed that the granular structure of the starch was affected by the reaction. X‐ray diffraction analysis showed that the crystallinity of starch was decreased as a result of grafting and the reduction was higher for the grafted starches with higher percentage grafting.     

Study on Preparation and Thickening Efficiency of an Inverse Emulsion of Anionic Starch‐graft‐Polyacrylamide

A series of graft copolymers of starch with polyacrylamide was made by using a K₂S₂O₈ initiation system in inverse emulsion. The corresponding anionic graft copolymers, which have a different hydrolysis degree, are prepared by alkaline hydrolysis of the uncharged graft copolymers. Adequate hydrolytic conditions including type and amount of hydrolyzing agent, temperature, and time were studied. These graft copolymers have been tested for their temperature sensitivity, salt tolerance and shear stability, and a comparison has been made with ungrafted polyacrylamide (PAM). Experiments showed that a high hydrolysis degree can be obtained in a shorter time when NaOH and Na₂CO₃ were used together as hydrolyzing agents, and the highest solution viscosity was observed when the hydrolysis degree of the graft copolymers was approximately 30%, . In addition, the shear stability, temperature sensitivity and salt tolerance in the graft copolymers were also investigated.     

Preparation,characterization, and water resistance of cationic acetylated starch‐g‐poly(styrene‐butyl acrylate) surfactant‐free emulsion

Cationic acetylated starch‐g‐poly(styrene‐butyl acrylate) surfactant‐free emulsion (CAS‐g‐poly(St‐BA)) was synthesized by graft copolymerization of styrene (St) and butyl acrylate (BA) onto CAS using FeSO₄–H₂O₂ redox initiator. The maximum graft of 55.68% was derived when H₂O₂ concentration, monomer concentration, and St/BA ratio were 9%, 130%, and 1:1, respectively. The results obtained from FTIR, NMR (H¹ NMR and C¹³ NMR), XRD, SEM, and thermogravimetric analysis (TGA‐DTG) confirmed graft copolymerization of St and BA onto CAS. And it was demonstrated that film‐forming properties of starch were greatly improved via grafting St and BA onto starch. It was also found that paper sized with CAS‐g‐poly(St‐BA) exhibited higher ring crush index and bursting strength than paper sized with cationic potato starch (CS) and CAS, as well as much lower water absorption, which is further verified by contact angles results.     

Synergetically Acting new Flocculants on the Basis of Starch‐graft‐Poly(acrylamide)‐co‐Sodium Xanthate

A synergetically acting new flocculant on the basis of starch‐graft‐poly(acrylamide)‐co‐sodium xanthate (CSAX) was synthesized by grafting copolymerization of crosslinked corn starch, acrylamide (AM), and sodium xanthate, using epichlorohydrin (EPI) as cross‐linking agent and ceric ammonium nitrate (CAN) as polymerization initiator in aqueous solution. The effects of some factors, such as crosslinker, initiator, AM, NaOH, on the %Tr (turbidity removal rate), %Trd (turbidity removal rate of a water sample which has both turbidity and heavy metal ions %Hr (heavy metal ion removal rate) and %Hrd (heavy metal ions removal rate of water which has both heavy metal ions and turbidity), are investigated. As proven by FTIR and elemental analysis, the CSAX can be successfully synthesized and can remove both turbidity‐causing substances and heavy metal ions from aqueous solutions. Under optimum synthesis conditions CSAX exhibits excellent performance, i.e. %Tr = 98%, %Trd = 98.4%, %Hrd = 99% and %Hr = 91.6%, respectively.     

Evaluation of Novel Back‐flush Filtration for Removal of Homopolymer from Starch‐g‐PMMA

Starch‐g‐poly(methyl methacrylate) (PMMA) was prepared by emulsion photopolymerization without photoinitiator. Grafting efficiency was determined for two types of starch (high‐amylose and amylopectin) and at several illumination times. Since clogging of the graft copolymer prevented vacuum filtration and Soxhlet extraction was too time‐consuming, a new method to separate the PMMA homopolymer from the graft copolymer was developed. Back‐flush filtration uses an intermittent pressure pulse to clean the filter as the homopolymer is separated from the graft copolymer. Back‐flush filtration was shown to be more efficient by reducing the separation time and solvent use, and the grafting efficiencies obtained with back‐flush filtration compare favorably with those from Soxhlet extraction for the starch‐g‐PMMA copolymer systems studied. More accurate grafting efficiencies could be obtained by applying a nonstick coating to the inside chamber of the back‐flush filtration unit.     

Effects of starch alkenylsuccinylation on the grafting efficiency,paste viscosity,and film properties of alkenylsuccinylated starch‐g‐poly(acrylic acid)

Commercial cornstarch was alkenylsuccinylated with alkenylsuccinic anhydride to different degrees of substitution (DS) and then the products were graft‐copolymerized with acrylic acid for investigating the effects of starch alkenylsuccinylation on the graft copolymerization with vinyl monomer, as well as on paste viscosity and film properties of alkenylsuccinylated starch‐g‐poly(acrylic acid) (ASS‐g‐PAA). The number of carbon atom of alkenyl in alkenylsuccinates considered was 8 and 12, corresponding to octenylsuccinylation and dodecenylsuccinylation of starch, respectively. The graft copolymerization was accessed by grafting efficiency, grafting ratio, and conversion of monomer to polymer, and the film properties of ASS‐g‐PAA considered included tensile strength, breaking elongation, and work‐to‐break. Experimental results demonstrated that the alkenylsuccinylation showed marked effects on the copolymerization, paste viscosity, and film properties. It resulted in increased grafting efficiency, stable paste viscosity, and strong starch film. Carbon‐chain length of the alkenyl and DS value of the alkenylsuccinates also exhibited evident effects on the copolymerization and film properties. Octenylsuccinylation of starch before the copolymerization was superior to dodecenylsuccinylation in improving the efficiency and film properties. Low levels of octenylsuccinylation could be utilized to increase the efficiency of the copolymerization and improve the properties of starch film.     

Effects of starch acryloylation on the grafting efficiency,adhesion, and film properties of acryloylated starch‐g‐poly(acrylic acid) for warp sizing

In order to enhance the grafting efficiency of graft copolymerization of granular cornstarch with acrylic acid (AA) for improving the adhesion and film properties of starch‐g‐poly(acrylic acid) used as sizing agent, the esterification of hydrolyzed starch with acryloyl chloride was applied before graft copolymerization. The influence of three common initiators on the copolymerization were also studied. The initiators included ceric ammonium nitrate [Ce(NH₄)₂(NO₃)₆], hydrogen peroxide/ferrous ammonium sulfate [H₂O₂/FeSO₄ · (NH₄)₂SO₄], and potassium persulfate/sodium bisulfite [K₂S₂O₈/NaHSO₃]. It was found that acryloylation of starch before the copolymerization was an effective method for substantially enhancing the grafting efficiency and improving the performances such as adhesion‐to‐fibers and mechanical properties of grafted starch film. The acryloylation could increase the efficiency to 67–81% when the degree of substitution (DS) of acryloylated starch ranged from 0.010 to 0.036. The adhesion to polyester and cotton fibers reached their maximum at DS = 0.010 and 0.022, respectively. Strong and tough film was obtained when the DS value was in a range of 0.010–0.022. H₂O₂/FeSO₄ · (NH₄)₂SO₄ redox system was more appropriate for initiating the copolymerization of acryloylated starch with AA.     

Synthesis and Thermal Degradation of a Novel Starch Graft Copolymer Incorporating a Sulfobetaine Zwitterionic Monomer

A novel starch graft copolymer containing sulfobetaine moieties in the side chains was synthesized by grafting the sulfobetaine zwitterionic monomer 3‐dimethyl(methacryloyloxyethyl) ammonium propane sulfonate (DMAPS) onto potato starch in the presence of the ceric ammonium nitrate (CAN) / acid initiation system. The effects of the concentrations of CAN and DMAPS, the pH of the reaction medium and the polymerization temperature on the grafting reactions were investigated in terms of the grafting percentage (GP) and grafting efficiency (GE). When the CAN concentration, the pH of the reaction medium or the reaction temperature increased, GP and GE were found to first increase and then to decrease. The increase of DMAPS concentration resulted in a significant enhancement of GP and GE. Furthermore, the thermal degradation of such graft copolymer was studied under air atmosphere at various heating rates, and the corresponding activation energy of the degradation was determined by Ozawa's method.     

Isocyanate‐free Route to Starch‐graft‐Polycaprolactone via Carbonyldiimidazole (CDI)‐mediated End Group Conversion

This paper reports on the synthesis of biodegradable starch‐graft‐poly ϵ‐caprolactone (starch‐g‐PCL) in two steps. First, poly ϵ‐caprolactone (PCL) was modified on the terminal groups by using carbodiimidazole (CDI) as coupling agent. Then, the starch graft copolymers with PCL were prepared through a carbonate bond using carboimidazole function. Monofunctional and bifunctional reactive end‐group PCL terminated with carboimidazole groups were prepared and reacted with hydroxyl groups of starch. The resulting starch‐g‐PCL copolymers were characterized by FT‐IR, NMR, HR‐MAS‐NMR, DSC, MEB and XRD.     

Inverse Emulsion of Starch‐graft‐Polyacrylamide

An inverse emulsion of cationic starch‐graft‐polyacrylamide was prepared by inverse emulsion polymerization and a subsequent Mannich reaction. The copolymerization was carried out using potassium persulfate as initiator. The reaction conditions and factors affecting emulsion stability were studied. Experiments showed that a high solids content, a high cationic degree and a stable latex can be obtained under the following condition: A molar ratio starch/acrylamide/formaldehyde/dimethylamine of 0.11:1:1:1.2; a stable inverse emulsion system; graft copolymerization of starch and acrylamide for 2‐3 h at 50 °C; pre‐formation of an aldehyde‐amine adduct, which is subsequently dropped into an inverse emulsion of starch‐graft‐polyacrylamide. The reaction temperature was 45 °C, the reaction time was 3‐4 h, and the pH was 5.5.     

Characteristics of Novel Starch‐based Hydrogels Prepared by UV Photopolymerization of Acryloylated Starch and A Zwitterionic Monomer

New starch‐based hydrogels were prepared by the UV‐induced polymerization of acryloylated starch with the zwitterionic monomer 3‐dimethyl(methacryloyloxyethyl) ammonium propane sulfonate (DMAPS). The swelling kinetics of the resultant hydrogels in distilled water and their equilibrium swelling ratios in aqueous NaCl and CaCl₂ solutions were investigated. With increasing amount of incorporated DMAPS, the formed hydrogel had an enhanced swelling ability in distilled water and in aqueous salt solutions. In particular, antipolyelectrolyte swelling behavior of the hydrogel was observed in aqueous salt solutions.     

Microbial Starch‐Converting Enzymes: Recent Insights and Perspectives

Starch is an abundant, natural, renewable resource, and present as the major storage carbohydrate in the seeds, roots, or tubers of many important food crops, such as maize, wheat, rice, potato, and cassava. Uses of native starches in most industrial applications are limited by their inherent properties. Hence, they are often structurally modified after isolation to enhance desirable attributes, to minimize undesirable attributes, or to create new attributes. Enzymatic, rather than chemical, approaches are used in the production of starch syrups, maltodextrins, and cyclodextrins. However, the desire for starch‐active enzymes working optimally at high temperatures and low pH conditions with superior stability and activity is still not satisfied and this stimulates interest in developing novel and improved starch‐active enzymes through a variety of strategies. This review provides current information on enzymes belonging to GH13, 57, 70, and 77 that can be used in structural modifications of the starch polysaccharides or to produce starch‐derived products from them. The characteristics and catalytic mechanisms of microbial enzymes are discussed (including 4‐α‐glucanotransferase, branching enzyme, maltogenic amylase, cyclomaltodextrinase, amylosucrase, and glucansucrase). Product diversity after starch‐converting reaction and utilization in industrial applications are also dealt with.     

Rheology of Rice Starch‐Sucrose Composites

The effect of sucrose at different concentrations (0, 10, 20 and 30%) on rheological properties of rice starch pastes (5% w/w) was investigated in steady and dynamic shear. The steady shear properties of rice starch‐sucrose composites were determined from rheological parameters for power law and Casson flow models. At 25°C all the starch‐sucrose composites exhibited a shear‐thinning flow behavior (n=0.25–0.44). The presence of sucrose resulted in the decrease in consistency index (K), apparent viscosity (η_a,100) and yield stress (σ_oc). Dynamic frequency sweeps at 25°C indicated that starch‐sucrose composites exhibited weak gel‐like behavior with storage moduli (G′) higher than loss moduli (G′′). G′ and G′′ values decreased with the increase in sucrose concentration. The dynamic (η*) and steady‐shear (η_a) viscosities at various sucrose concentrations did not follow the Cox‐Merz superposition rule. G′ values as a function of aging time (10 h) at 4°C showed a pseudoplateau region at long aging times. In general, the values of G′ and G′′ in rice starch‐sucrose composites were reduced in the presence of sucrose and depended on sucrose concentration.     

Pasting Properties of Non‐waxy Rice Starch‐Hydrocolloid Mixtures

The swelling and pasting properties of non‐waxy rice starch‐hydrocolloid mixtures were investigated using commercial and laboratory‐generated hydrocolloids. The swelling power of the rice starch‐hydrocolloid mixtures was generally depressed at low concentration of hydrocolloids (0–0.05%), but increased directly with increasing hydrocolloid concentrations (0.05–0.1%). In gellan gum dispersion, the swelling power at 100°C was higher than that of control. The rice starch‐hydrocolloids mixtures showed shear‐thinning flow behavior (n = 0.26–0.49). Hydrocolloids except the exopolysaccharide from S. chungbukensis (EPS‐CB) increased apparent viscosity and consistency index (K) of rice starch dispersions, but decreased the n value. Hydrocolloids enhanced the trough and final viscosity of rice starch dispersions but EPS‐CB reduced the viscosity of rice starch pastes. Hydrocolloids lowered peak viscosity but addition of guar gum resulted in high peak viscosity, apparent viscosity, and consistency index of rice starch dispersions. Total setback viscosity appeared to be not affected by hydrocolloids at low concentration (0.05%). The hot and cold paste of the starch‐gellan gum mixture exhibited the highest viscosity values in the Brookfield viscometer.     

Developing Biodegradable Mulch Films from Starch‐Based Polymers

This paper examines the development of starch‐based plastics for use as biodegradable mulch film. A variety of starch‐based polymers are blended with high performance biodegradable polyester polymers in order to determine the applicability of films to be processed on a film blowing line and to perform well in mulch film field trials. The process of material formulation, film blowing processing and scale‐up and performance properties are highlighted for a successful material. Insights into future developments of starch‐derived biodegradable polymers are given.     

Preparation and Aqueous Properties of Starch‐grafted Polyacrylamide Copolymers

In the present work, starch‐grafted polyacrylamide copolymers were prepared and their rheological properties, either in water or in water‐based muds, were investigated. The advantages in using starches as substrates to prepare additives which are suited for improving stability and the rheological properties of water‐based muds, lie in their low cost, and their lower biodegradability than native starches. Thus, various copolymer series were prepared by free‐radically grafting acrylamide (AM) onto starch using ceric ammonium sulphate (CAS) as initiator. It is shown that the intrinsic viscosity and the molecular weight of the grafted starches are controlled by the initiator and monomer concentrations. Furthermore, to predict the behaviour of the samples under oil‐well conditions, the aqueous solution properties of the copolymers such as water solubility, viscosity, shear rate, were determined as function of temperature, salt concentration and type, and aging time. The knowledge of these properties is a prerequisite for the use of the copolymers in drilling fluids. The data indicate that starch‐grafted polyacrylamide copolymers as compared to the non‐modified starch, behave as shear‐thinning, are salt resistant, and their rheological properties are stable with time. The grafted starches as prepared above were also added to water‐based mud and the rheological properties of the resulting muds were determined under oil‐well conditions. Grafted starches, having high AM contents, are more efficient in decreasing the filtrate volume, and increasing the plastic viscosity of the muds, when compared to PAC‐L, a modified cellulosic polymer used in the filtration control of most water‐based muds. Such improvements in the rheological properties of the muds were found to result from the behaviour and/or properties of the grafted starches in water.     

新型淀粉基阳离子多元共聚物的合成

用自制的引发剂MT-1,通过溶液聚合反应,制备了淀粉、丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化胺(DAC)三元共聚物。最佳反应条件为:引发剂用量占反应物固含量的1.0‰,丙烯酰铵、丙烯酰氧乙基三甲基氯化铵与淀粉质量比为4.2∶2.8∶3,反应温度55℃,反应时间4 h,产物的接枝率可达142.3%,特性粘数[η]446.9 ml.g-1,阳离子度可以达到22.1%。通过红外光谱对接枝共聚产品进行了表征。