CN1939932A - Synthesis of soluble amphoteric starch - Google Patents
Synthesis of soluble amphoteric starch Download PDFInfo
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- CN1939932A CN1939932A CN 200610021236 CN200610021236A CN1939932A CN 1939932 A CN1939932 A CN 1939932A CN 200610021236 CN200610021236 CN 200610021236 CN 200610021236 A CN200610021236 A CN 200610021236A CN 1939932 A CN1939932 A CN 1939932A
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Abstract
Synthesis of amphoteric soluble starch is carried out by taking starch as raw material, taking any kind from sodium chloroacetate, butanedioic anhydride and 3-chlorine-2-cysteic acid as anion reagent, taking any kind from 3-chlorine-2-hydroxypropyl trimethyl-ammonia chloride and N-(2,3-epoxide)trimethyl-ammonia chloride as cation reagent, catalyzing by composite catalyst, synthesizing the final product at 30-150 degree for 1-8hrs by semi-drying method. It' simple, cheap and efficient, has no after-treatment and waste ejection.
Description
Technical field
The present invention relates to a kind of synthetic method of soluble amphoteric starch.Relating in particular to starch is raw material, under the katalysis of composite catalyst, by the semidrying synthesis technique, starch is carried out the method for modification synthesizing water-solubility amphoteric starch with anionization reagent and cationic reagent.
Background technology
Amphoteric starch is meant in same starch molecule the modified starch that not only connects cation group but also connect anionic group.Amphoteric starch is the novel modified starch that grew up in recent years, integrated application the modification technology of yin, yang ionic starch, make its effect more outstanding.The character of amphoteric starch is difference with the difference of the technical recipe of making, application aims and effect are also made a world of difference, but with regard to its general character, contain positive and negative two kinds of electric charge groups on the starch molecule chain link of amphoteric starch simultaneously, it is ionic to be neutrality, little positive or little feminine gender, and gelatinization temperature is lower than ative starch.Because the mutual coordinative role of each group in the starch molecule, make its performance more excellent, effect is more outstanding, specificity is stronger, be competitively one of the products of development research of present various countries, its purposes relates to various fields such as papermaking, weaving, water treatment, oil, food, medicine and printing, and it still can be through composite or modification and develop more product innovations.Limit its application but, cost big because of complicated process of preparation, difficulty be high.
States such as day, moral, U.S. had carried out paractical research again to amphoteric starch in recent years, had delivered some articles and patent in succession.China starts late to the research and development of this class modified starch, and wet method is mainly used in production at present.Report that from present domestic and foreign literature the preparation method of amphoteric starch adopts water solvent method and organic solvent method mostly, in two steps anionic group and cation group received on the starch molecule that catalyzer adopts sodium hydroxide more.
US 4964953 has reported at first W-Gum suspension and etherifying agent behind 43 ℃ of reaction 24h, the gained cationic starch ether and the aqueous solution that contains tripoly phosphate sodium STPP are made into slurry, filter, being dried to humidity is 5%～7%, be warming up to 133 ℃, the reaction certain hour, synthetic quaternary ammonium starch ethers phosphate monoester.The clear 60-45693 of TOHKEMY is reported in the water solvent earlier with starch oxidation degraded carrying out again negatively charged ion, cationization reaction.US 5368690 once reported, in the water slurry of starch, was 9～12 with lime control pH value, added 3-chloro-2-sulphur propionic acid and cationic etherifying agent, at 20 ℃～45 ℃ reaction 6h～24h.The advantage of wet processing is the reaction conditions gentleness, and production unit is simple, and its drawback is that reaction conversion ratio is low, postprocessing working procedures many and problems such as contaminated wastewater and starch loss are arranged.US 4566910 has reported and has utilized vapo(u)r blasting equipment to prepare water-soluble phosphoric acid type quaternary ammonium group amphoteric starch in starch pasting state next step and two-step approach.The advantage of this method is to have avoided the water solvent method to carry out reaction needed under the starch granules state to add the gelatinization inhibitor, and the reaction efficiency height, and the reaction times is short, cost is low.But the shortcoming of this method is that by product and the intact reagent of unreacted in the reaction is difficult to remove the quality of some effects product.
US 827372 is an anionic monomer with the tripoly phosphate sodium STPP, and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is a cationic monomer, is solvent with ethanol, synthetic quaternary ammonium starch-phosphate under the sodium hydroxide katalysis.This method reaction efficiency height, constant product quality, reaction conditions gentleness, easy and simple to handle; But need to use a large amount of organic solvents, thereby conversion unit is huge, the cost height, dangerous.The synthetic method that yin, yang ion and starch is combined in the amphoteric starch in same site is also arranged, and this type of amphoteric starch is synthetic normally to be pre-mixed the yin, yang ionization reagent reaction and to generate amphiphilic ions, then with starch storage crop, forms the amphiphilic starch ether derivative.Reported as US 4243479 N-2-chloroethyl ethylamine hydrochloride has been joined in the phosphorous aqueous acid, slowly add concentrated hydrochloric acid, wait to reflux constant after, drip formaldehyde, backflow 3h is cooled to 24 ℃, gained solution is added in the water slurry that contains W-Gum, regulating the pH value is 11.8, reacts 6h down at 34 ℃, gets product.The advantage of this method is to connect the yin, yang ionic group at the same avtive spot of starch molecule, but has problems such as seriously corroded, environmental pollution be serious.
Just as described above, in the past exist complicated process of preparation in the method for synthetic amphoteric starch, the production cycle is long, cost is high, severe reaction conditions.Therefore the object of the present invention is to provide and do not use highly corrosive, virose material to be raw material, but and with simple production equipment and the program novel method with regard to the synthesizing water-solubility amphoteric starch.
Summary of the invention
The present invention aims to provide a kind of reaction raw materials cheapness, and reaction conditions gentleness, equipment requirements are not high, and environment and human body are not had injury, the method for the synthesizing water-solubility amphoteric starch that technology is simple and safe.
It innovates part: 1, on existing wet production basis, adopt semidrying synthesizing water-solubility amphoteric starch, shorten the reaction times, cut down the consumption of energy, improve monomeric transformation efficiency, reduce production costs; After reaction finished, product needn't separate, purifying.2, negatively charged ion, the cationization with starch carries out in a reactor, reduced operation link, and the basis is provided for reducing production costs.3, add composite catalyst and improve the alkalization degree of starch, the stability and the monomeric transformation efficiency of product, reduce the degraded of molecular chain, improve yield.
Advantage of the present invention: 1, the invention provides a reaction conditions gentleness, rapid, easy to operate, practical, reaction raw materials consumption is few, the transformation efficiency height, and the three wastes produce the synthetic method of few soluble amphoteric starch.2, effectively reduce production cost, make soluble amphoteric starch product purity height, modest viscosity, substitution value height, can be used for various fields such as papermaking, weaving, water treatment, oil, food, medicine and printing.3, soluble amphoteric starch is biodegradable, reduces environmental pollution.
Purpose of the present invention can realize by following measure:
In temperature is 30-120 ℃, with W-Gum, wheat starch, tapioca (flour), any or any phase mixture is a raw material in the yam starch, add in the reactor, add catalyzer while stirring, after starch is fully activated, with anionization reagent (sodium chloroacetate, Mono Chloro Acetic Acid, beta-propiolactone, Succinic anhydried, MALEIC ANHYDRIDE, the sulfonation MALEIC ANHYDRIDE, dithiocarbonic anhydride, 3-chloro-2-sulfo group propionic acid, Sodium phosphate dibasic/SODIUM PHOSPHATE, MONOBASIC, tripoly phosphate sodium STPP, sodium orthophosphate, Sodium hexametaphosphate 99, tetrasodium pyrophosphate, any in the clorox), cationic reagent (3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, N-(2,3-epoxy chloropropionate base) trimethyl ammonium chloride, N-(2, the 3-epoxypropyl) diethylamide, 1, any in the 2-epoxypropyl trimethylammonium chloride amine) add in the starch, after mixing, react under normal pressure, the reaction times is 1～8 hour.Reaction finishes, needn't be through washing, filters, is drying to obtain the soluble amphoteric starch powder, and its general formula is:
R wherein
1Be cationic substituent, R
2Be anion substituent.R
12-hydroxypropyl trimethyl ammonium chloride, wherein R specifically
2Represent C
2～C
4The alkyl that contains carboxylic acid, the substituting group of phosphorous, sulphur.R
2Specifically can be carboxymethyl (CH
2COOH), propyloic (CH
2CH
2COOH), carboxypropanoyl (COCH
2CH
2COOH), phosphate-based (PO
3 -) 2-sulfo group carboxypropanoyl (COCH
2CH (SO
3Na) 2-sulfocarboxylic ethyl (CH COOH),
2CH (SO
3Na) xanthogenic acid ester group (CS COOH),
2 -).
In above-mentioned reaction, the mass ratio of starch and anionization reagent 1: 0.02～0.5, the mass ratio of starch and cationic reagent 1: 0.02～0.8, the mass ratio of starch and catalyzer 1: 0.001～0.2, temperature of reaction is 30～150 ℃, and the reaction times, 1～8h got soluble amphoteric starch.
Used composite catalyst is sodium hydroxide/magnesium oxide in the semidrying synthesizing water-solubility amphoteric starch, sodium hydroxide-yellow soda ash/N, dinethylformamide, sodium hydroxide/calcium hydroxide, sodium hydroxide-calcium oxide/fatty alcohol-polyoxyethylene ether, sodium hydroxide/palmityl trimethyl ammonium chloride, potassium hydroxide/salt of wormwood, sodium hydroxide-phosphoric acid/urea, any in sodium hydroxide-aluminum oxide.
Co-catalyst magnesium oxide, calcium oxide, calcium hydroxide, yellow soda ash, salt of wormwood, aluminum oxide, phosphoric acid, urea, N in the just aforesaid composite catalyst, any quality is a starch quality 0.01～7% in dinethylformamide, palmityl trimethyl ammonium chloride, the fatty alcohol-polyoxyethylene ether.
The semidrying synthesis technique is: the starch of certain mass ratio, anionization reagent, cationic reagent and water, wherein, the consumption of water is 20%～40% of a reaction raw materials in reaction process, under the catalyst effect, in the dispersion system that starch-anionization reagent, cationic reagent-water-catalyzer constitute, carry out starch positively charged ion and anionic two-fold reaction and get certain substitution value, the soluble amphoteric starch of certain viscosity, its reaction formula is as follows:
Wherein, X represents cationic reagent; Y represents anionization reagent.X specifically can be 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, N-(2,3-epoxy chloropropionate base) trimethyl ammonium chloride, N-(2, the 3-epoxypropyl) diethylamide, 1, and is any in the 2-epoxypropyl dimethyl chlorination amine.Y specifically can be any in sodium chloroacetate, Mono Chloro Acetic Acid, beta-propiolactone, Succinic anhydried, MALEIC ANHYDRIDE, sulfonation MALEIC ANHYDRIDE, dithiocarbonic anhydride, 3-chloro-2-sulfo group propionic acid, Sodium phosphate dibasic/SODIUM PHOSPHATE, MONOBASIC, tripoly phosphate sodium STPP, sodium orthophosphate, Sodium hexametaphosphate 99, tetrasodium pyrophosphate, the clorox.
Embodiment:
[embodiment one]
Adding 1000g starch and 50g powdered sodium hydroxide fully stir 10min in special reactor, spray into 20% Virahol 200ml, fully stir 30min under 50 ℃ of temperature.Add 500g N-(2, the 3-epoxypropyl) trimethyl ammonium chloride (GTA) then, after fully stirring 30min under this temperature, be warming up to 80 ℃ of reaction 3h.Be cooled to 35 ℃, add 50ml dithiocarbonic anhydride and 25g magnesium oxide, 35 ℃ of sealed reaction 30min pulverize and promptly get finely powdered cationic starch sulphur ortho ester.
[embodiment two]
Spray into 100mlN after in special reactor 1000g starch and 50g powdered sodium hydroxide fully being stirred 10min, dinethylformamide is warming up to 50 ℃ and stirs 30min.Successively spray into 150ml sodium chloroacetate solution (the 50g Mono Chloro Acetic Acid is dissolved in 40% aqueous sodium hydroxide solution) then, 200mL quaternary ammonium salt solution (600g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride be dissolved in join in 10% aqueous sodium carbonate), fully stir 30min, be warming up to 80 ℃ of reaction 3h, pulverize and promptly get white fine powder shape carboxymethyl cationic starch.
[embodiment three]
In special reactor, add 1000g starch and 350mL quaternary ammonium salt solution (530g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride be dissolved in join in 40% aqueous sodium hydroxide solution) and 30ml fatty alcohol-polyoxyethylene ether, be warming up to 50 ℃ of stirring 30min after fully stirring 15min, be warming up to 80 ℃ of reaction 3h then, add 40g Succinic anhydried and 25g calcium oxide, after mixing, be warming up to 130 ℃ of reaction 1h, pulverize and promptly get finely powdered cationic starch succinate.
[embodiment four]
Add 1000g starch in special reactor, temperature remains on 50 ℃, with 250ml chlorine bleach liquor (active chlorine content is 5.5～5.7%).Abundant stirring reaction 1h under this temperature.Add 450g N-(2 then, 3-epoxy chloropropionate base) trimethyl ammonium chloride, 20g sodium chloroacetate and 10g palmityl trimethyl ammonium chloride, after fully stirring 30min under this temperature, be warming up to 80 ℃ of reaction 3h, pulverize and promptly get white fine powder shape oxidative cationic starch.
[embodiment five]
In special reactor, add 1000g starch and 300mL quaternary ammonium salt solution (550g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride be dissolved in join in 40% potassium hydroxide aqueous solution), in 50 ℃ stir 30min after, be warming up to 80 ℃ of reaction 2h.After adding 40g MALEIC ANHYDRIDE and 20g salt of wormwood mix, at 120 ℃ of reaction 2h.Add 30g sodium bisulfite reaction 30min then, pulverize and promptly get finely powdered cationic starch sulfonic group succinate.
[embodiment six]
In special reactor, add after 1000g starch and 300mL quaternary ammonium salt solution (550g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride be dissolved in join in 40% aqueous sodium hydroxide solution) fully stir 15min, in 50 ℃ stir 30min after, be warming up to 80 ℃ of reaction 3h.Be cooled to 30 ℃, add 10% phosphoric acid, fully stir.With 52.4gNaH
2PO
4/ Na
2HPO
4In a certain amount of water, be sprayed at the starch surface then equably as far as possible, add 40g urea, after mixing, be warming up to 120 ℃ of reaction 2h, pulverize and promptly get finely powdered cationic starch phosphoric acid ester.
[embodiment 7]
In special reactor, add 1000g starch and 50g powdered sodium hydroxide and 30g aluminum oxide, fully stir 10min, spray into 20% Virahol 200ml, under 50 ℃ of temperature, fully stir 30min.Add 100g3-chloro-2-sulfo group propionic acid and 500gN-(2, the 3-epoxypropyl) diethylamide then, after fully stirring 30min under this temperature, be warming up to 80 ℃ of reaction 3h.Pulverize and promptly get finely powdered 2-sulfo group propionic acid cationic starch.
Claims (8)
1. the synthetic method of a soluble amphoteric starch, it is characterized in that: with any in W-Gum, tapioca (flour), yam starch, the wheat starch or wherein any phase mixture is raw material, under the katalysis of composite catalyst, adopt semidry process, starch is carried out double modification with negatively charged ion and cationic reagent, the preparation soluble amphoteric starch, its general formula:
R wherein
1Be cationic substituent, R
2Be anion substituent.
2. the synthetic method of soluble amphoteric starch according to claim 1, it is characterized in that: cationic reagent specifically can be 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, N-(2,3-epoxy chloropropionate base) trimethyl ammonium chloride, N-(2, the 3-epoxypropyl) diethylamide, N, N-dimethyl-2-acetamido ethamine, 1, any in the 2-epoxypropyl dimethyl chlorination amine; Anionization reagent specifically can be any in sodium chloroacetate, Mono Chloro Acetic Acid, beta-propiolactone, Succinic anhydried, MALEIC ANHYDRIDE, sulfonation MALEIC ANHYDRIDE, dithiocarbonic anhydride, 3-chloro-2-sulfo group propionic acid, Sodium phosphate dibasic/SODIUM PHOSPHATE, MONOBASIC, tripoly phosphate sodium STPP, sodium orthophosphate, Sodium hexametaphosphate 99, tetrasodium pyrophosphate, the clorox.
3. according to claim 1 and 2, it is characterized in that: R
12-hydroxypropyl trimethyl ammonium chloride, N specifically, N-diethyl-N-2-hydroxypropyl, N, N-dimethyl-N-hydroxypropyl, N, N-dimethyl-N-ethyl; R
2Represent C
2～C
4The alkyl that contains carboxylic acid, the substituting group of phosphorous, sulphur, R
2Specifically can be carboxymethyl (CH
2COOH), 2-sulfocarboxylic ethyl (CH
2CH (SO
3Na) propyloic (CH COOH),
2CH
2COOH), carboxypropanoyl (COCH
2CH
2COOH), xanthogenic acid ester group (CS
2 -), 2-sulfo group carboxypropanoyl (COCH
2CH (SO
3Na) phosphate-based (PO COOH),
3 -).
4. the synthetic method of soluble amphoteric starch according to claim 1, it is characterized in that: the mass ratio 1: 0.02～0.5 of starch and anionization reagent, the mass ratio of starch and cationic reagent 1: 0.02～0.8, the mass ratio of starch and catalyzer 1: 0.001～0.2.
5. the synthetic method of soluble amphoteric starch according to claim 1, it is characterized in that: temperature of reaction is 30～150 ℃, reaction times 1～8h.
6. the synthetic method of soluble amphoteric starch according to claim 1, it is characterized in that: the semidrying synthesis technique is: in the dispersion system that starch-cationic reagent-anionization reagent-water-catalyzer constitutes, carry out the two-fold reaction of starch cationization and anionization, the consumption of water is 20%～40% of a reaction raw materials in reaction process.
7. soluble amphoteric starch synthetic method according to claim 1, it is characterized in that: used composite catalyst is for being sodium hydroxide/magnesium oxide, sodium hydroxide-yellow soda ash/N, dinethylformamide, sodium hydroxide-calcium oxide/fatty alcohol-polyoxyethylene ether, sodium hydroxide/calcium hydroxide, sodium hydroxide/palmityl trimethyl ammonium chloride, potassium hydroxide/salt of wormwood, sodium hydroxide-phosphoric acid/urea, sodium hydroxide/aluminum oxide in the semidrying synthesizing water-solubility amphoteric starch.
8. composite catalyst system according to claim 7, it is characterized in that: co-catalyst is magnesium oxide, calcium oxide, calcium hydroxide, yellow soda ash, salt of wormwood, aluminum oxide, phosphoric acid, urea, N, and any quality is 0.01～7% of a starch quality in dinethylformamide, palmityl trimethyl ammonium chloride, the fatty alcohol-polyoxyethylene ether.
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