CN101704897A - High-substitution carboxymethyl glutinous rice starch and preparation method thereof - Google Patents
High-substitution carboxymethyl glutinous rice starch and preparation method thereof Download PDFInfo
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- CN101704897A CN101704897A CN200910212559A CN200910212559A CN101704897A CN 101704897 A CN101704897 A CN 101704897A CN 200910212559 A CN200910212559 A CN 200910212559A CN 200910212559 A CN200910212559 A CN 200910212559A CN 101704897 A CN101704897 A CN 101704897A
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Abstract
The invention relates to high-substitution carboxymethyl glutinous rice starch and a preparation method thereof. The starch is prepared by the following steps of: (1) alkali treatment of glutinous rice starch; (2) etherification reaction; (3) subsequent treatment, i.e. adding acetic acid into products obtained from step (2) for neutralization till the products are neutral, washing by using methanol water solution with the volume faction of 80% till no chloride ion exists, filtering to obtain filter cakes, and then drying and pulverizing to obtain the carboxymethyl glutinous rice starch. The carboxymethyl group substitution of the carboxymethyl glutinous rice starch is not less than 0.88; and the carboxymethyl glutinous rice starch has the advantage of high substitution, and the preparation method of the carboxymethyl glutinous rice starch has simple process, high reaction efficiency and little environment pollution.
Description
Technical field
The present invention relates to a kind of high-substitution carboxymethyl glutinous rice starch and preparation method thereof.
Background technology
Carboxymethyl starch (CMS) is that starch plays a kind of polymer electrolyte (also being a kind of modified starch) that can be dissolved in cold water that etherification reaction generates with Mono Chloro Acetic Acid under alkaline condition.The chemical structure of carboxymethyl starch, character and function are all similar to carboxymethyl cellulose, and development prospect is wide.
The production of China's modified starch is extremely mostly based on wet processing.Wet processing is that starch is dispersed in water or the organic solvent, be made into the suspension that concentration is 35-45%, hydro-oxidation sodium and Monochloro Acetic Acid react with chemical reagent being lower than under the temperature condition of gelatinization in starch milk, then after filtration, cleaning, drying obtain product.For avoiding starch pasting, often need to add anti-gelation agent.Wet processing has many defectives: must increase chemical reagent (catalyzer, anti-gelation agent etc.); Reaction process is long, the aftertreatment difficulty, need a large amount of water washing and dry for a long time, and having a large amount of unreacted reagent and starch during aftertreatment runs off, not only reaction efficiency is lower, replacement is uneven, side reaction increases, and cause a large amount of alkaline waste waters to pollute, environment is done great damage, and the product caking is serious, the pulverizing difficulty.
Wet processing is owing to exist above-mentioned defective, so people work out dry process again.Existing dry process is directly starch to be mixed and reacts with reagent (only containing the less water about 20%), and reactant remains pulverulence.This technology is by the humidity of control reaction system, starch is remained on carry out solid state reaction under the ungelatinized state.Usually adopt Mono Chloro Acetic Acid in the existing dry process as etherifying agent.The subject matter that existing dry process exists is: when sodium hydroxide mixes with Mono Chloro Acetic Acid with powder or highly concentrated solution state, chemical reaction is violent, speed is difficult to control, and Mono Chloro Acetic Acid utilization ratio and reaction efficiency are low, and the substitution value of the carboxymethyl glutinous rice starch that makes is lower.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of high-substitution carboxymethyl glutinous rice starch.Another technical problem that the present invention will solve provides the preparation method of the high-substitution carboxymethyl glutinous rice starch that a kind of technology is simple, reaction efficiency is high, environmental pollution is little.
For solving the problems of the technologies described above, the invention provides a kind of high-substitution carboxymethyl glutinous rice starch, this starch is prepared by following method:
(1) alkaline purification glutinous rice starch: with mol ratio is that 1: 1.25 glutinous rice starch and sodium hydroxide powder thorough mixing is even, add concentration of volume percent then and be 60% aqueous isopropanol, stir, carrying out quaternization under 35 ℃ the temperature after 60 minutes, be cooled to room temperature, wherein: per 0.059 mole glutinous rice starch, the consumption of above-mentioned aqueous isopropanol are 4ml;
(2) etherification reaction: the mol ratio of adding and (1) middle glutinous rice starch is 1: 1 a sodium chloroacetate in the product that the processing of warp (1) step obtains, and fully stirring and evenly mixing carrying out etherification reaction under 70 ℃ the temperature after 150 minutes, is cooled to room temperature;
(3) subsequent disposal: in the product that obtains through the processing of (2) step, add acetate and neutralize, make described product to neutral, be that 80% methanol aqueous solution washs to there not being chlorion with volume fraction again, filter filter cake, dry after pulverizing obtains carboxymethyl glutinous rice starch, the carboxymethyl group substitution value of this glutinous rice starch is not less than 0.88.
For solving the problems of the technologies described above, the present invention also provides a kind of preparation method of high-substitution carboxymethyl glutinous rice starch, comprises following processing step:
(1) alkaline purification glutinous rice starch: with mol ratio is that 1: 1.25 glutinous rice starch and sodium hydroxide powder thorough mixing is even, add concentration of volume percent then and be 60% aqueous isopropanol, stir, carrying out quaternization under 35 ℃ the temperature after 60 minutes, be cooled to room temperature, wherein: per 0.059 mole glutinous rice starch, the consumption of above-mentioned aqueous isopropanol are 4ml;
(2) etherification reaction: the mol ratio of adding and (1) middle glutinous rice starch is 1: 1 a sodium chloroacetate in the product that the processing of warp (1) step obtains, and fully stirring and evenly mixing carrying out etherification reaction under 70 ℃ the temperature after 150 minutes, is cooled to room temperature;
(3) subsequent disposal: in the product that obtains through the processing of (2) step, add acetate and neutralize, make described product to neutral, be that 80% methanol aqueous solution washs to there not being chlorion with volume fraction again, filter filter cake, dry after pulverizing obtains carboxymethyl glutinous rice starch, the carboxymethyl group substitution value of this glutinous rice starch is not less than 0.88.
Among the preparation method of the present invention:
Concentration of volume percent is the adding of 60% aqueous isopropanol, make the microenvironment of reaction system be different from liquid phase reaction, caused the high local concentrations of reactive site, improved reaction efficiency greatly, utilize glutinous rice starch itself to have the molecular structure property of a lot of side chains, more carboxymethyl group is incorporated on the glutinous rice starch molecular chain, described aqueous isopropanol also has the effect of high dispersing, has eliminated water is disperseed and to cause the serious drawback of product caking;
Adopt sodium chloroacetate to substitute Mono Chloro Acetic Acid, react acutely when having solved the sodium hydroxide that exists in the existing dry process and mixing with Mono Chloro Acetic Acid, be difficult to control, Mono Chloro Acetic Acid utilization ratio and the low problem of reaction efficiency with powder or highly concentrated solution state as etherifying agent;
Adopt methanol aqueous solution to wash, and methanol aqueous solution can reclaim, reuse by the alcoholic solution recovery tower, so without sewage discharge, environment protecting is obvious;
The water content of whole reaction system is 17% only, makes the pulverizing of product become easy;
Owing to react completely, avoided the too much remnants of sodium hydroxide, make that the color and luster of carboxymethyl glutinous rice starch of the present invention is whiter than the color and luster of the glutinous rice starch of existing dry process preparation.
After tested:
The carboxymethyl group substitution value of carboxymethyl glutinous rice starch of the present invention reaches 0.88, the substitution value (only about 0.6) that is higher than the carboxymethyl starch that makes by existing wet processing, also being higher than the substitution value (only about 0.4) of the carboxymethyl starch that makes by existing dry process, is a kind of carboxymethyl glutinous rice starch of high substitution value;
The transparency of carboxymethyl glutinous rice starch of the present invention is 0.228 (is 1 to measure the transmittance under the 625nm with the transmittance of distilled water);
The viscosity of using No. 2 rotors of rotational viscosimeter to measure carboxymethyl glutinous rice starch solution of the present invention (weight percent concentration is 2%) in the time of 95 ℃ is 212.5mPa.s, and the viscosity of the existing glutinous rice starch solution of same concentration is 90mPa.s;
The viscosity of using No. 2 rotors of rotational viscosimeter to measure carboxymethyl glutinous rice starch solution of the present invention (weight percent concentration is 2%) in the time of 25 ℃ is 1593.3mPa.s, and the viscosity of the existing glutinous rice starch solution of same concentration is 117mPa.s.
As seen, carboxymethyl glutinous rice starch of the present invention has high stability at normal temperatures.
At first use the alkaline purification glutinous rice starch among the preparation method of the present invention, after alkalization finishes, add pulverous sodium chloroacetate again and carry out etherification reaction, then, adding acetate in the product that obtains neutralizes, make described product to neutral, last washing through routine, filter, dry, pulverizing makes carboxymethyl glutinous rice starch. as seen, preparation method of the present invention has adopted the alkaline purification glutinous rice starch, etherification reaction, these three processing steps of subsequent disposal, and existing dry process is directly starch and reagent mix to be reacted (for single stage method), therefore, preparation method of the present invention is different fully with existing dry process, has solved reagent effective consumption in the existing dry process, the problem that utilization ratio is low.
In sum, carboxymethyl glutinous rice starch of the present invention has the advantage of high substitution value; The preparation method of high-substitution carboxymethyl glutinous rice starch of the present invention, its technology is simple, reaction efficiency is high, environmental pollution is little.
In preparation method of the present invention: described aqueous isopropanol adds with spray pattern.Like this, it can mix more evenly with glutinous rice starch, sodium hydroxide powder, makes quaternization abundant.
Embodiment
The several embodiment of various details, but content of the present invention is not limited to this fully.
Embodiment 1
The preparation method of high-substitution carboxymethyl glutinous rice starch comprises following processing step:
(1) alkaline purification glutinous rice starch: 500 kilograms of glutinous rice starchs and 131.5 kilograms of sodium hydroxide powder thorough mixing are even, adding concentration of volume percent with spray pattern then is 210.5 liters of aqueous isopropanols of 60%, stir, carrying out quaternization under 35 ℃ the temperature after 60 minutes, be cooled to room temperature;
(2) etherification reaction: handling 306 kilograms of Powdered sodium chloroacetates of adding in the product that obtains through (1) step, fully stirring and evenly mixing carrying out etherification reaction under 70 ℃ the temperature after 150 minutes, is cooled to room temperature;
(3) subsequent disposal: in the product that obtains through the processing of (2) step, add acetate and neutralize, make described product to neutral, be that 80% methanol aqueous solution washs to there not being chlorion with volume fraction again, filter filter cake, the gained filter cake is dry after pulverizing obtains the white powder carboxymethyl glutinous rice starch in vacuum drying system, and the carboxymethyl group substitution value of this glutinous rice starch is not less than 0.88.
Embodiment 2
The preparation method of high-substitution carboxymethyl glutinous rice starch comprises following processing step:
(1) alkaline purification glutinous rice starch: 1000 kilograms of glutinous rice starchs and 263 kilograms of sodium hydroxide powder thorough mixing are even, adding concentration of volume percent with spray pattern then is 421 liters of aqueous isopropanols of 60%, stir, carrying out quaternization under 35 ℃ the temperature after 60 minutes, be cooled to room temperature;
(2) etherification reaction: handling 612 kilograms of Powdered sodium chloroacetates of adding in the product that obtains through (1) step, fully stirring and evenly mixing carrying out etherification reaction under 70 ℃ the temperature after 150 minutes, is cooled to room temperature;
(3) subsequent disposal: in the product that obtains through the processing of (2) step, add acetate and neutralize, make described product to neutral, be that 80% methanol aqueous solution washs to there not being chlorion with volume fraction again, filter filter cake, the gained filter cake is dry after pulverizing obtains the white powder carboxymethyl glutinous rice starch in vacuum drying system, and the carboxymethyl group substitution value of this glutinous rice starch is not less than 0.88.
Claims (3)
1. the preparation method of high-substitution carboxymethyl glutinous rice starch comprises following processing step:
(1) alkaline purification glutinous rice starch: with mol ratio is that 1: 1.25 glutinous rice starch and sodium hydroxide powder thorough mixing is even, add concentration of volume percent then and be 60% aqueous isopropanol, stir, carrying out quaternization under 35 ℃ the temperature after 60 minutes, be cooled to room temperature, wherein: per 0.059 mole glutinous rice starch, the consumption of above-mentioned aqueous isopropanol are 4ml;
(2) etherification reaction: the mol ratio of adding and (1) middle glutinous rice starch is 1: 1 a sodium chloroacetate in the product that the processing of warp (1) step obtains, and fully stirring and evenly mixing carrying out etherification reaction under 70 ℃ the temperature after 150 minutes, is cooled to room temperature;
(3) subsequent disposal: in the product that obtains through the processing of (2) step, add acetate and neutralize, make described product to neutral, be that 80% methanol aqueous solution washs to there not being chlorion with volume fraction again, filter filter cake, dry after pulverizing obtains carboxymethyl glutinous rice starch, the carboxymethyl group substitution value of this glutinous rice starch is not less than 0.88.
2. the preparation method of high-substitution carboxymethyl glutinous rice starch according to claim 1, it is characterized in that: described aqueous isopropanol adds with spray pattern.
3. the carboxymethyl glutinous rice starch that makes of the preparation method of high-substitution carboxymethyl glutinous rice starch according to claim 1 and 2, the carboxymethyl group substitution value of this glutinous rice starch is not less than 0.88.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229675A (en) * | 2011-05-19 | 2011-11-02 | 湖北达雅化工技术发展有限公司 | Preparation method of food grade high viscosity sodium carboxymethyl starch |
| CN103255677A (en) * | 2013-04-19 | 2013-08-21 | 西安富士得化学衍生物有限责任公司 | Papermaking dry strengthening agent and preparation and application methods thereof |
| CN103554282A (en) * | 2012-12-07 | 2014-02-05 | 新疆光大山河化工科技有限公司 | Highly substituted carboxymethyl starch sodium preparation method |
| CN104211822A (en) * | 2014-09-10 | 2014-12-17 | 江南大学 | Method for preparing carboxymethyl rice starch via intermittent feeding method |
| CN105330757A (en) * | 2015-12-14 | 2016-02-17 | 上海雅运纺织助剂有限公司 | Method for preparing high-substitution carboxymethyl starch |
| CN106749712A (en) * | 2017-01-16 | 2017-05-31 | 无锡市善源生物科技有限公司 | A kind of method that semidry method prepares CMS |
| CN108409874A (en) * | 2018-04-13 | 2018-08-17 | 齐鲁工业大学 | A kind of preparation method of high substituted degree etherificate cornstarch |
-
2009
- 2009-11-12 CN CN200910212559A patent/CN101704897A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229675A (en) * | 2011-05-19 | 2011-11-02 | 湖北达雅化工技术发展有限公司 | Preparation method of food grade high viscosity sodium carboxymethyl starch |
| CN102229675B (en) * | 2011-05-19 | 2012-11-28 | 湖北达雅化工技术发展有限公司 | Preparation method of food grade high viscosity sodium carboxymethyl starch |
| CN103554282A (en) * | 2012-12-07 | 2014-02-05 | 新疆光大山河化工科技有限公司 | Highly substituted carboxymethyl starch sodium preparation method |
| CN103554282B (en) * | 2012-12-07 | 2017-06-30 | 新疆光大山河化工科技有限公司 | The preparation method of substituted carboxymethyl starch sodium high |
| CN103255677A (en) * | 2013-04-19 | 2013-08-21 | 西安富士得化学衍生物有限责任公司 | Papermaking dry strengthening agent and preparation and application methods thereof |
| CN103255677B (en) * | 2013-04-19 | 2016-03-30 | 西安富士得化学衍生物有限责任公司 | A kind of papermaking dry-strengthening agent and methods for making and using same thereof |
| CN104211822A (en) * | 2014-09-10 | 2014-12-17 | 江南大学 | Method for preparing carboxymethyl rice starch via intermittent feeding method |
| CN105330757A (en) * | 2015-12-14 | 2016-02-17 | 上海雅运纺织助剂有限公司 | Method for preparing high-substitution carboxymethyl starch |
| CN106749712A (en) * | 2017-01-16 | 2017-05-31 | 无锡市善源生物科技有限公司 | A kind of method that semidry method prepares CMS |
| CN106749712B (en) * | 2017-01-16 | 2019-04-09 | 无锡市善源生物科技有限公司 | A kind of method of semidry method preparation carboxymethyl starch |
| CN108409874A (en) * | 2018-04-13 | 2018-08-17 | 齐鲁工业大学 | A kind of preparation method of high substituted degree etherificate cornstarch |
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Open date: 20100512 |