Starch Cationization Research Articles

Scientific basis of technology for production of cationic starch

Starch derivatives containing ether cationic groups (amino-, ammonium, sulfonium, phosphonium, etc.) are vital commercial product. Cationic starches with tertiary amino- and quaternary ammonium ether groups have found the greatest use. The paper is devoted to sore problem - deep processing of vegetable starch-containing raw materials and in particular production of domestic chemically modified (substituted) cationic starch. Comparative studies of the kinetics of the reac­tion of obtaining cationic ethers of potato and corn starch using N-(3-chloro-2-hydroxypropyl)-N,N,N-trimethylammonium © Литвяк В. В., 2019 chloride depending on the molar ratio of reagents, temperature, concentration of starch suspension and the nature of na­tive starch. The effect of starch cationization process on the morphological peculiarities of starch granules, as well as de­gree of crystallinity, was studied. The effect of cationization of starch on the structural characteristics of granules (degree of crystallinity-and-amorphism) at the general preservation of starch granules and physical and chemical properties (rheolog­ical and thermogravimetric) has been determined. A scientifically based, highly efficient method for cationization of starch N-(3-chloro-2-hydroxypropyl)-N,N,N-trimethylammonium chloride in an alkaline medium with the use of gelatinization inhibitors was developed allowing to obtain cationic starch with substitution degree of 0.01-0.06 mol/mol. The obtained cationic starch can be used in the pulp and paper, textile and other industry. The developed technology for production of chemically modified cationic starch has been successfully implemented at local enterprises.

OBTAINING NEW FLOCCULANTS BASED ON HIGH-SUBSTITUTED CATIONIC STARCHES

In this work synthesis of the high-substituted cationic starches by reaction of starches of different botanical origin with 3-chloro-2-hydroxypropyltrimetylammonium chloride in the presence of the alkaline catalyst was carried out by semi-dry way. The assessment of their flocculating properties on the model systems of kaolinic dispersions was carried out. It was established that the efficiency of a starch cationization substantially depends on its nature. This is due to various initial supermlecular structure and morphology of starch granules. The largest rate and degree of a cationization was characteristic for potato starch, and the least – for corn. The offered heterogeneous method of synthesis allows to receive the high-substituted cationic starches with preservation their granular and minimum changes in supramolecular structure. At achievement of particular extent of high-substituted (DScat> 0.1) cationic starches form the transparent colloid dispersions in cold water. Cationization of starches to higher DScat. demands increase in a consumption of cationic reagent and the catalyst. Formation of cationic bonds in starch was confirmed with results of element and IR-spectroscopical analyses. When carrying out a cationization of starch in an alkaline condition there can be changes of the supramolecular structure of a polysaccharide depending on a temperature and type of starch. Unessential decrease in a degree of crystallinity of all types of starches after their cationization at ambient temperature was demonstrated by the diffractograms received in work. Despite slight amorphicity of starch after their cationization it should be noted that all cationic starches having DScat> 0.1, easily disperse in cold water with formation of the homogeneous transparent pastes. The kinetics and efficiency of a flocculation of model kaolinic suspensions with synthesized cationic starches was investigated. Kaolinic suspensions for lack of flocculant are rather stable for a long time. Introduction to the system of cationic starch leads to fast destabilization of kaolinic dispersions. At the same time for all cationic starches with increase in a dose in the range of 0.5 – 7.5 mg/g(kaolin) the flocculation rate of particles of kaolin dispersions increases. The most efficiently a flocculation of dispersions of kaolin happens to the largest rate in the presence of cationic potato starch. It was established that the efficiency of a flocculation of mineral kaolinic systems is defined not only by a molecular mass of polymer, but also the sizes of non-draining chains which in the strong degree depend on a charge of microions and a rigidity of a polymeric chain. It was shown that the synthesized flocculants are not inferior in efficiency to the polyacrylamide derivants which are applied now.Forcitation:Butrim S.M., Bildyukevich T.D., Butrim N.S., Yurkshtovich T.L., Kaputskiy F.N. Obtaining new flocculants based on high-substituted cationic starches. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 1. P. 89-95

Properties of Cellulosic Material after Cationization in Different Solvents

Fibers resulting from pulping of wood are negatively charged by nature. Both the cellulose and hemicelluloses contribute to the anionicity. The negative charge of cellulosic material can be reversed with the same reagent commonly used for the cationization of starch. In this study, a bleached Kraft pulp was cationized in systems with different water-miscible organic solvents. Replacing 90% of the water with isopropanol and particularly with tetrahydrofuran yielded higher degrees of substitution and increased reaction efficiency. The degree of substitution depends on the concentration of the cationization reagent in water; partially replacing water with tetrahydrofuran can simulate a higher concentration while maintaining supramolecular properties, such as crystallinity and polymer chain integrity.

Modification of potato peel waste with base hydrolysis and subsequent cationization

Potato peel waste (PW) is a starch containing biomaterial produced in large amounts by food processing industry. In this work, the treatment of PW by alkaline hydrolysis and cationization in the water phase is reported. In order to improve the cationization of starch, PW was hydrolyzed by heating with alkaline (NaOH) ethanol solution (80%) in a water bath. The impact of variable molar ratios of anhydroglucose unit (AGU):NaOH, heating temperatures and times was studied on the degradation of starch and the molecular size distribution of the product. The hydrolyzed PW was cationized subsequently in water by using glycidyltrimethylammonium chloride and catalyzed by NaOH under microwave irradiation or in an oil bath. The impact of the various reaction conditions on the cationization and degree of substitution of starch was studied. The degree of substitution of the cationized starch varied in the range of 0–0.35.

High Hydrostatic Pressure (HHP)-assisted Starch Modification: Acid Hydrolysis, Hydroxypropylation, Acetylation, Cross-linking and Cationization

High hydrostatic pressure (HHP) processing is an attractive non-thermal technique because of its potential to achieve interesting functional effects. In spite of the rapid expansion of HHP application to food systems, limited information is available on effects of HHP on modification of starch and their struc- tural and physicochemical properties. Therefore, functional roles of HHP in starch modification such as acid-hydrolysis, hydroxypropylation, acetylation, cross-linking and cationization of starch, as well as physicochemical properties of HHP-assisted modified starches were reviewed. HHP-assisted modified starches revealed similar or different physicochemical properties compared to conventionally modified starches, suggesting the consideration of HHP as a processing parameter for hydrolysis and modification of starch. Moreover, HHP-assisted starch modification would be an attractive technology and can be ef- fectively used in starch industry with relatively low cost and short reaction time.

반응표면분석법에 의한 양이온성 옥수수전분 생산의 최적화

Cationic starch is widely used in the paper-making process as a wet-end additive to improve sheet strength and to provide better retention of fines as well as fillers. Cationic corn starch is generally used in most grades of paper because of its cheapness and opulency. Low-substituted cationic starch which has a degree of substitution (DS) of below 0.03 is widely used but regulations pertaining to the total amount of lead present in anionic waste have made paper companies leery about its continued use. As a result, the need for a high-substituted cationic starch which has a DS above 0.04 has been growing. On the basis of the results of the alkali gelatinization initiation concentration (AGIC) of corn starch suspension, the optimization of corn starch cationization was performed by response surface methodology (RSM). When 8% (w/w) cationic reagent was added to the starch suspension with 1.89% (w/w) of Na2SO4 and NaOH, after which 6.75 meq/g-starch of AGIC was added at 38.48°C. It appears that cationic starch can be produced with a reaction yield of 67.28% (DS 0.0302) over the course of 18 h. If the cationic reagent is increased to 20% (w/w), more than 24 h was needed to reach the maximum reaction yield. Within 24 h, the optimized cationization process produced cationic corn starch which has a DS of 0.064.

Preparation of high‐substituted cationic starch in presence of organic bases

AbstractCross‐linked N‐(hydroxypropyl)–N,N,N–trimethylammonium starch chlorides (CQS) with preserved microgranules, degree of substitution (DS) from 0.18 to 1.05 are prepared by reaction of starch with glycidyltrimethylammonium chloride (GTAC) accelerated by benzyltrimethylammonium hydroxide (BTMAOH) or tertiary amines–triethylamine (TEA) and dimethylbenzylamine (DMBA). When BTMAOH instead of NaOH is used as a catalyst, the reaction of cross‐linked starch (CS) with GTAC proceeds slightly slower and with a lower efficiency (RE). DMBA unexpectedly showed similar catalyst efficiency as BTMAOH. It is suggested that the reason for such phenomena is the reaction of GTAC with tertiary amines and the formation of strong bases – quaternary ammonium hydroxides. They actually catalyse starch cationization. DMBA is more active in this reaction in comparison with TEA. It is shown that, due to a higher amount of quaternary ammonium hydroxides in the liquid phase of the reaction mixture, the yield of starch cationization decreases. Cationization in the presence of organic bases provides higher sorption capabilities to the modified polysaccharide.

Application of evolutionary algorithms to the definition of the optimal twin‐screw extruder configuration for starch cationization

AbstractThe twin‐screw configuration problem (TSCP) involves defining the location of a set of predefined screw elements of a corotating twin‐screw extruder configuration to optimize different, often conflicting, objectives. A multiobjective optimization methodology based on Evolutionary Algorithms was developed and applied to solve the TSCP. This methodology is used in starch cationization case studies, involving different screw elements and screw lengths. The results obtained, taking into consideration various conflicting objectives, such as minimizing the specific mechanical energy and maximizing output and reaction efficiency, have physical meaning and thus validate the methodology. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers

Preparation and characterization of cationic corn starch with a high degree of substitution in dioxane–THF–water media

Cationic corn starch derivatives with a high degree of substitution are prepared in alkaline solution or in mixed media of organic solvent and water with different levels of the cationic reagent, 2,3-epoxypropyltrimethylammonium chloride. The starch cationization yield is investigated, and the results indicate that the degree of substitution (DS) of the samples depends on the reaction conditions and reaction media. The maximum DS values are up to 1.37 in 1,4-dioxane alkaline–aqueous solution. Meanwhile, the structures of the cationic starch derivatives are characterized by elemental analyses, FTIR spectroscopy, X-ray diffraction, and 13C NMR spectroscopy, as well as by SEM techniques.

Synthesis and physicochemical properties of low-substituted cationic ethers of starch

The kinetics of the formation of cationic starch ethers under the action of 3-chloro-2-hydroxypropyltrimethylammonium chloride is studied in relation to the reactant molar ratio, temperature, and concentration of the starch suspension. Comparative data on how the content of the introduced catoinic groups depends on the origin of native starch are presented. The efficiency of starch cationization and the physicochemical properties of the synthesized samples are examined by chemical analysis, scanning electron microscopy, X-ray diffraction analysis, and thermal gravimetric analysis.

Factors influencing production of cationic starches

The main factors – the amount of catalyst NaOH, the temperature and composition of reaction mixture – influencing the effectiveness of starch cationization with glycidyltrimethylammonium chloride (GTAC) were investigated. It was found that cationic or cross-linked cationic starches with preserved microgranules, a degree of substitution from 0.2 to 0.85 and reaction efficiency from 82% to 93% could be obtained during etherification of starch or cross-linked starch with a mixture containing GTAC, “free” water and 0.04–0.08mol/AGU sodium hydroxide in heterogeneous condition. The activation energy of the GTAC main reaction is lower than that of the side reactions, thus starch cationization at a lower temperature proceeds with higher reaction efficiency.The amount of NaOH in the cationization mixture has a great influence on the rate of the main and side reactions of GTAC. Only the main reaction – cationization of starch – proceeds when all the NaOH present in the reaction mixture is adsorbed from the liquid phase by the starch. The duration of this “first reaction stage” decreases with increasing reaction temperature and the amount of NaOH in the reaction mixture. NaOH present in the liquid phase of the reaction mixture catalyzes the side reactions of GTAC and changes their character.

Optimization and scale‐up of starch cationization in a twin screw extruder

AbstractIn a previous work, a theoretical model for the cationization of wheat starch in a modular self‐wiping corotating twin screw extruder has been developed and experimentally validated. Our objective in the present article was to use this model in a first step to optimize the cationization reaction on a laboratory scale extruder, and, in a second step, to extrapolate the results to an industrial scale extruder. We will show that the use of a theoretical model of reactive extrusion allowed us to define screw profiles and processing conditions according to the end‐use properties of the desired product and the limits of the process. Based on the performances obtained at laboratory scale, it permitted also to predict the performances of an industrial production line. POLYM. ENG. SCI., 47:814–823, 2007. © 2007 Society of Plastics Engineers

Computation of starch cationization performances by twin‐screw extrusion

AbstractA theoretical model for the cationization of plasticized wheat starch in a modular seIf‐wiping co‐rotating twin screw extruder was developed. Our objective was to build a model which would be able to predict the evolution of the cationization reaction along the screws, in relation with the processing conditions and the geometry of the twin screw extruder. Based on previous studies on reactive extrusion modeling, the present model takes into account the interactions occurring between the flow conditions encountered in the extruder and the kinetics of the reaction. It allows one to predict the influence of operating parameters such as reagent concentrations, feed rate, screw speed, and barrel temperature on the reaction extent. Depending on conditions, degrees of substitution in the range 0.01–0.05 are obtained, with efficiencies between 30 and 90%. A good agreement is found between theoretical results and experimental measurements, allowing future use of the model for optimization and scale‐up purposes. POLYM. ENG. SCI., 47:112–119, 2007. © 2007 Society of Plastics Engineers

Peculiarities of Starch Cationization with Glycidyltrimethylammonium Chloride

AbstractCationic starch derivatives containing quaternary ammonium groups with high degree of substitution are prepared by reaction of starch with glycidyltrimethylammonium chloride (GTAC) in different reaction media. In aqueous solutions of GTAC along with conventional hydrolysis of epoxy groups, their interaction with chloride ions also takes place. This resulted in formation of hydroxyl ions which accelerate both the hydrolysis of GTAC epoxy groups and can act as the internal catalyst in the reaction of GTAC with starch. Therefore, even in the absence of the external catalyst, cationic starch with a high degree of substitution can be obtained. The autocatalytic reaction of GTAC with starch proceeds more rapidly at higher temperatures but with lower reaction efficiency. Both in the absence of the external catalyst and in the case when sodium alkali is used as a catalyst the reaction of starch with GTAC proceeds only when a particular quantity of “free” water is present in the system. When the NaOH as catalyst is used the reaction efficiency is about 90%. The yield of starch cationization reaction decreases when the quantity of “free” water is twice or thrice higher than required for starch modification to begin.

Cationic Starches of High Degree of Functionalization: 12. Modification of Cellulose Fibers toward High Filler Technology in Papermaking

Modification of cellulose fibers via adsorption of highly functionalized 2-hydroxy-3-trimethylammonium propyl chloride starch (HPMA starch) with a degree of substitution (DS) in the range from 0.25 to 1.54 was investigated by electrokinetic measurements and filler retention tests. It was found that the amount of cationic HPMA starch adsorbed at the isotherm plateaus depends on two parameters: the DS of the starch derivative and, more remarkably, the amylose/amylopectin ratio. All studied HPMA starches allow significant improvement of kaolin particle retention in comparison to untreated fibers and fibers modified with low-substituted commercial starch. We suggest that, because of the local overcharging of the cellulose surface through the adsorption of starch macromolecules, the filler retention capacity is enhanced even at low and moderate degrees of coverage when the surface has a net-negative charge. Taking into account the efficiency and cost of starch cationization, the optimum DS of the HPMA starch for cellulose modification in papermaking was found to be in the range 0.6−0.7, where a degree of filler loading of 500 mg/g can be reached at a level of HPMA starch addition of 0.5−0.6%.

An Aqueous Alcoholic‐Alkaline Process for Cationization of Corn and Pea Starches

AbstractTo develop a more efficient process for cationization of corn and pea starches, the effects of gelatinization inhibitor, type of solvent and solvent concentration, starch: water ratio, reaction temperature and 2‐chloro‐3‐hydroxypropyltrimethylammonium chloride (CHPTAC) concentration on rate and efficiency of cationization of corn und pea starches in an aqueous alcoholic‐alkaline solvent were studied during 24h of reaction time. The use of watermiscible organic solvents in the aqueous alkaline media eliminated the requirement for a gelatinization inhibitor to minimize starch swelling. The alcohol concentrations which produced high reaction efficiencies were 35‐75% ethanol or 2‐propanol. Optimum conditions for the reaction included 65% ethanol, 50°C and a starch:water ratio of 1:1 (w/w). The degree of substitution (DS) value increased linearly with CHPTAC concentration up to O,2M CHPTAC, but reaction efficiency (RE) decreased at the O,2M CHPTAC concentration. Cationization of starch in the aqueous alcohol solvent would be an alternative to aqueous processes because of the higher DS and reaction efficiencies that were achieved more rapidly and without the aid of other gelatinization inhibitors.

The Reactivity of Native and Autoclaved Starches from Different Origins Towards Acetylation and Cationization

AbstractNative potato, waxy corn, corn, wheat, filed pea and lentil starches were autoclaved at 15 psi, 121°C for 1min. Scanning electron micrographs of the native and autoclaved starches showed no changes in granular surfaces and shapes. In all starches, the X‐ray intensities at most of the d‐spacings between 3‐18 Å increased upon autoclaving, being more pronounced in potato. The X‐ray patterns of cereals and legumes remained unchanged, while that of tuber (potato) became more cereal‐like. Differential scanning calorimetry of the starch samples revealed that autoclaving increased the gelatinization transition temperatures of wheat but decreased that of potato; the changes observed in waxy corn, corn, field pea and lentil starches were very small. The gelatinization enthalpy of all native starches decreased upon autoclaving while the percentage decrease was highly marked in potato. Image analysis of the native and autoclaved starches revealed changes in the granule size distribution patterns. Also, the population mean area of all native starch granules considerably increased upon autoclaving. Acetyl binding capacity, measured at 5% and 10% acetic anhydride addition levels, was higher in autoclaved than in native starches. Furthermore, autoclaving had no influence on starch cationization, studied at 3% and 6% reagent addition levels. The results indicated that the changes in starch molecular organization caused by autoclaving enhanced its reactivity towards acetylation but not cationization.

Use of a Twin‐Screw Extruder as a Chemical Reactor for Starch Cationization

AbstractThe objective of this work was to study the obtaining of cationic starch by using a pilot scale twin‐screw extruder Clextral BC45 as a chemical reactor. The reagent was 3‐chloro 2‐hydroxypropyltrimethyl ammonium chloride (CHPTMA) and catalyst was sodium hydroxide (NaOH). In a first set of experiments extruded starch gave higher chemical efficiencies than native starch (+15%) both being fed at the same location of the barrel. Influence of extrusion conditions on reaction kinetics was studied starting from extruded starch in order to optimize the reaction without interfering with starch melting phenomenon. In a second set of experiments, a special screw design was implemented in order to obtain a homogeneous starch molten phase in a first stage, and to achieve starch modification in a second stage. Changes of reacting conditions were performed through the modification of reagent quantities and molar ratios related to starch and NaOH, location of reagent injection, temperature of reaction and Specific Mechanical Energy input. Samples were evaluated through their degree of substitution (final DS < 0,09); their homogeneity and rheological behavior were studied by ion exchange chromatography and Brabender viscoamylograph. resp., Reaction efficiency was computed to optimize the process, leading to values up to 82%. Extruded samples were then compared to commercial cationic starches.