CN1563097A - Double modified starch and preparation method - Google Patents
Double modified starch and preparation method Download PDFInfo
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- CN1563097A CN1563097A CN 200410030778 CN200410030778A CN1563097A CN 1563097 A CN1563097 A CN 1563097A CN 200410030778 CN200410030778 CN 200410030778 CN 200410030778 A CN200410030778 A CN 200410030778A CN 1563097 A CN1563097 A CN 1563097A
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Abstract
The invention relates to a double modified starch and its production process. According to the production principle a compound modification method can be adopted to make carboxymethyl and alkenyl succinic acid radical be combined on starch molecule to simultaneously add the hydrophilic carboxyl group and lipophilic alkenyl group on the starch molecular so as to produce the modified starch simultaneously having hydrophilic property and lipophilic property-carboxymethyl alkenyl succinic acid starch ester, its product solubility in cold water (said product can be dissolved in cold water with 15 deg.C) and lipophilic property can be raised, and the application range of said modified starch can be broadened.
Description
Technical field
The present invention relates to food processing technology field, specifically a kind of carboxymethyl and octenyl succinic base are combined in double-modified starch and production method thereof on the starch molecule.
Background technology
Carboxymethyl starch (CMS) be a kind of be raw material with starch, the modified starch of making through etherification reaction.Carboxymethyl starch can partly substitute carboxymethyl cellulose (CMC) and use, and it is the polymeric dielectrics that can be dissolved in cold water, and is designated as foodstuff additive in Japan, at present it is called over-expense chain starch in Germany.It all has new application in fields such as papermaking, textile printing and dyeing, medicine, wastewater treatment, ore dressing, casting, tackiness agent, makeup, building materials, food, leather, oil-field development and daily chemical industries, and market outlook are boundless.Abroad had the scale production equipment of sodium starch glycolate, and be applied to every field as far back as the sixties.China starts from the mid-80 to the development of sodium starch glycolate, at present, domestic carboxymethyl starch industrial scale is little, kind is few, also do not form series product, especially the production of high viscosity carboxymethyl starch and derivative thereof is almost still blank, has restricted the development of carboxymethyl starch Application Areas.Though carboxymethyl starch has very high wetting ability, do not have lipotropy, restricted its application in containing oil production.
Starch octenyl succinate anhydride has many good performances such as lipotropy and wetting ability owing to introduced the octenyl succinic group on starch molecule, can be widely used in fields such as food, medicine, makeup, textile and paper.The research to this class modified starch abroad has very long history with application.The patent of having applied for starch octenyl succinate anhydride as far back as nineteen fifty-three Caldwell and O.B.Wurzburg; This product was listed the category of U.S. food additive in 1972, and in the foodstuff additive handbook is just listed it in recent years by China.At present, domestic because of being subjected to many effects limit such as starting material, the main dependence on import of this starch ester product.Starch octenyl succinate anhydride is different from other traditional modified food starch, in oil-in-water emulsion, play an important role especially, and be widely used in the varieties of food items, as Emulsion flavour, microscapsule powder goods, soft drink, salad dresser, yogurt and cheese, tinned pre-, candy.In this external weaving, papermaking and medicine, the latex coating use is arranged also.Another attracting purposes of starch octenyl succinate anhydride is to utilize its encapsulate to be used as the wall material of microcapsule, only needs during use to get final product with core with as the direct spraying drying of milk sap of the esterification starch of wall material.Starch octenyl succinate anhydride can be used in the higher system of oil-contg that traditional material can't use the wall material as microcapsule.From embedding rate, shelf-stable and the microscapsule powder performance such as redispersion water of rate of drying, oil, starch octenyl succinate anhydride is more effective than conventional wall materials such as gum arabic, maltodextrins.But starch octenyl succinate anhydride needs could dissolve in the water more than 50 ℃, uses for its commercialization and makes troubles, and has particularly limited at some and has needed the application in the dissolved microcapsule product under the cold water condition.
Summary of the invention
The object of the present invention is to provide and a kind of carboxymethyl and octenyl succinic base are combined in double-modified starch and production method thereof on the same starch molecule.This invention is according to the modified starch production principle, adopt the method for complex denaturation that carboxymethyl and octenyl succinic base are combined on the starch molecule, produce and have high-hydrophilic and lipophilic modified starch simultaneously, for industries such as food, medicine, weaving, daily-use chemical industry provide the starch material with special applications performance.
The double-modified starch chemistry carboxymethyl starch alkenyl succinate ester by name of this invention, the structural formula general formula is:
R is the thiazolinyl of 8～12 carbon atoms in the formula.
The physicochemical property of carboxymethyl starch alkenyl succinate ester is: white powder, nontoxic, free from extraneous odour, can dissolve in cold water.Have thickening, emulsification, dispersion, premium properties such as bonding.
Purposes: because the specific function that it has, and be widely used in the varieties of food items, as Emulsion flavour, microscapsule powder goods, soft drink, salad dresser, yogurt and cheese, tinned pre-, candy.In this external weaving, papermaking and medicine, the latex coating use is arranged also.
The double-modified starch of this invention can be produced by one of following two kinds of methods and obtain:
Method one:
Add starch and water in retort, the furnishing quality is 30～60% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 30～60 ℃, with NaOH or Na
2CO
2Regulate starch milk pH value to 8～10, in starch milk, add the alkenyl succinic anhydride of starch quality 1～10%, use the pH value of the alkali hierarchy of control simultaneously 7.5～10; React after 1～3 hour,, filter with sour adjust pH to 6～7, wash 2～3 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly; Adding concentration is 90～99% ethanol in retort, the starch alkenyl succinate ester that makes is added in the retort, the furnishing quality is 25～55% starch slurry than concentration, under the stirring action, adding concentration is 40% NaOH, regulate starch slurry pH value 10～14, stirring is warmed up to 40～50 ℃, and alkalization 0.5～2h adds the Mono Chloro Acetic Acid of starch quality 50～85% then, stirring down keeps slurry temperature at 55～65 ℃, reaction 4～8h with extremely neutral with slurry among the dense HCL, carries out centrifugation with the slurry after the neutralization, starch is used centrifugation after 80% the washing with alcohol again, after the oven dry carboxymethyl starch alkenyl succinate ester finished product.
The carboxymethyl starch alkenyl succinate ester purity height that this method is produced can be used as foodstuff additive.
Method two:
Add starch and water in retort, the furnishing quality is 30～60% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 30～60 ℃, with NaOH or Na
2CO
2Regulate starch milk pH value to 8～10, in starch milk, add the alkenyl succinic anhydride of starch quality 1～10%, use the pH value of the alkali hierarchy of control simultaneously 7.5～10; React after 1～3 hour,, filter with sour adjust pH to 6～7, wash 2～3 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly, drying; With concentration is that 30～50%NaOH liquid sprays in the starch alkenyl succinate ester of doing, and the sprinkling amount is controlled at 5～15% of starch quality, mixes powerful the stirring after 1～3 hour, and starch is pulverized, and crosses 80～200 mesh sieves, and starch must alkalize; With the starch after pulverizing and Mono Chloro Acetic Acid by in 5～10: 1 the mass ratio input mixer, after mixing, it is sent in the dry type reaction machine, and temperature remains on 50～90 ℃ of reactions 1～3 hour, dries then, pulverizes promptly to get carboxymethyl starch alkenyl succinate ester finished product.
This method advantage is that the product water content is lower, and it is low to consume energy, and drying rate is fast, non-wastewater discharge and help environmental protection, and the requirement of product conformance with standard, production cost is low.But product purity is low than method one, is not suitable for doing foodstuff additive.
The invention has the advantages that: starch is carried out etherificate and the two modifications processing of esterification, make and increased hydrophilic carboxylic group and lipophilic alkenyl group on the starch molecule simultaneously, improve product cold water-soluble (15 ℃ of cold water are also solvable) and lipotropy, improve the application performance of product, enlarged the range of application of this modified starch.
Found through experiments: product of the present invention is just swelling, dissolving rapidly in 2 minutes in 10～15 ℃ cold water, form transparent solution with viscosity, and product concentration of the present invention can be with the emulsification oleaginousness greater than 40% oil-water mixture at 3% o'clock solution, and carboxymethyl starch only can emulsification oil-containing 10% following oil-water mixture.Therefore, this product has good result to emulsification, the embedding that height contains oil production.
Embodiment:
Embodiment 1:
In retort, add starch and water, the furnishing quality is 30% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 30 ℃, regulate starch milk pH value to 8 with NaOH, the alkenyl succinic anhydride that adds starch quality 1% in starch milk uses the pH value of the alkali hierarchy of control 7.5 simultaneously; React after 1 hour,, filter with sour adjust pH to 6, wash 2 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly; Adding concentration is 90% ethanol in retort, the starch alkenyl succinate ester that makes is added in the retort, the furnishing quality is 25% starch slurry than concentration, under the stirring action, adding concentration is 40% NaOH, regulate starch slurry pH value 10, stirring is warmed up to 40 ℃, and alkalization 0.5h adds the Mono Chloro Acetic Acid of starch quality 50% then, stirring down keeps slurry temperature at 55 ℃, reaction 4h with extremely neutral with slurry among the dense HCL, carries out centrifugation with the slurry after the neutralization, starch is used centrifugation after 80% the washing with alcohol again, after the oven dry carboxymethyl starch alkenyl succinate ester finished product.
Embodiment 2:
Add starch and water in retort, the furnishing quality is 45% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 45 ℃, use Na
2CO
2Regulate starch milk pH value to 9, in starch milk, add the alkenyl succinic anhydride of starch quality 5%, use the pH value of the alkali hierarchy of control simultaneously 9; React after 2 hours,, filter with sour adjust pH to 6.5, wash 3 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly; Adding concentration is 95% ethanol in retort, the starch alkenyl succinate ester that makes is added in the retort, the furnishing quality is 40% starch slurry than concentration, under the stirring action, adding concentration is 40% NaOH, regulate starch slurry pH value 12, stirring is warmed up to 45 ℃, and alkalization 1h adds the Mono Chloro Acetic Acid of starch quality 65% then, stirring down keeps slurry temperature at 60 ℃, reaction 6h with extremely neutral with slurry among the dense HCL, carries out centrifugation with the slurry after the neutralization, starch is used centrifugation after 80% the washing with alcohol again, after the oven dry carboxymethyl starch alkenyl succinate ester finished product.
Embodiment 3:
In retort, add starch and water, the furnishing quality is 60% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 60 ℃, regulate starch milk pH value to 10 with NaOH, the alkenyl succinic anhydride that adds starch quality 10% in starch milk uses the pH value of the alkali hierarchy of control 10 simultaneously; React after 3 hours,, filter with sour adjust pH to 7, wash 3 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly; Adding concentration is 99% ethanol in retort, the starch alkenyl succinate ester that makes is added in the retort, the furnishing quality is 55% starch slurry than concentration, under the stirring action, adding concentration is 40% NaOH, regulate starch slurry pH value 14, stirring is warmed up to 50 ℃, and alkalization 2h adds the Mono Chloro Acetic Acid of starch quality 85% then, stirring down keeps slurry temperature at 65 ℃, reaction 8h with extremely neutral with slurry among the dense HCL, carries out centrifugation with the slurry after the neutralization, starch is used centrifugation after 80% the washing with alcohol again, after the oven dry carboxymethyl starch alkenyl succinate ester finished product.
Embodiment 4:
In retort, add starch and water, the furnishing quality is 30% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 30 ℃, regulate starch milk pH value to 8 with NaOH, the alkenyl succinic anhydride that adds starch quality 1% in starch milk uses the pH value of the alkali hierarchy of control 7.5 simultaneously; React after 1 hour,, filter with sour adjust pH to 6, wash 2 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly, drying; Concentration is sprayed in the starch alkenyl succinate ester of doing for 30%NaOH liquid, and the sprinkling amount is controlled at 5% of starch quality, mixes powerful the stirring after 1 hour, and starch is pulverized, and crosses 80 mesh sieves, and starch must alkalize; Starch after pulverizing and the mass ratio of Mono Chloro Acetic Acid by 5: 1 are dropped in the mixer, after mixing, it is sent in the dry type reaction machine, temperature remains on 50 ℃ and reacted 1 hour, dries then, pulverizes promptly to get carboxymethyl starch alkenyl succinate ester finished product.
Embodiment 5:
Add starch and water in retort, the furnishing quality is 45% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 45 ℃, use Na
2CO
2Regulate starch milk pH value to 9, in starch milk, add the alkenyl succinic anhydride of starch quality 5%, use the pH value of the alkali hierarchy of control simultaneously 9; React after 2 hours,, filter with sour adjust pH to 6.5, wash 2 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly, drying; Concentration is sprayed in the starch alkenyl succinate ester of doing for 40%NaOH liquid, and the sprinkling amount is controlled at 10% of starch quality, mixes powerful the stirring after 2 hours, and starch is pulverized, and crosses 120 mesh sieves, and starch must alkalize; Starch after pulverizing and the mass ratio of Mono Chloro Acetic Acid by 7: 1 are dropped in the mixer, after mixing, it is sent in the dry type reaction machine, temperature remains on 70 ℃ and reacted 2 hours, dries then, pulverizes promptly to get carboxymethyl starch alkenyl succinate ester finished product.
Embodiment 6:
In retort, add starch and water, the furnishing quality is 60% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 60 ℃, regulate starch milk pH value to 10 with NaOH, the alkenyl succinic anhydride that adds starch quality 10% in starch milk uses the pH value of the alkali hierarchy of control 10 simultaneously; React after 3 hours,, filter with sour adjust pH to 7, wash 3 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly, drying; Concentration is sprayed in the starch alkenyl succinate ester of doing for 50%NaOH liquid, and the sprinkling amount is controlled at 15% of starch quality, mixes powerful the stirring after 3 hours, and starch is pulverized, and crosses 200 mesh sieves, and starch must alkalize; Starch after pulverizing and the mass ratio of Mono Chloro Acetic Acid by 10: 1 are dropped in the mixer, after mixing, it is sent in the dry type reaction machine, temperature remains on 90 ℃ and reacted 3 hours, dries then, pulverizes promptly to get carboxymethyl starch alkenyl succinate ester finished product.
Claims (3)
1, a kind of double-modified starch is characterized in that, chemistry carboxymethyl starch alkenyl succinate ester by name, and the structural formula general formula is:
R is the thiazolinyl of 8～12 carbon atoms in the formula.
2, a kind of double-modified starch production method is characterized in that, adds starch and water in retort, and the furnishing quality is 30～60% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 30～60 ℃, with NaOH or Na
2CO
2Regulate starch milk pH value to 8～10, in starch milk, add the alkenyl succinic anhydride of starch quality 1～10%, use the pH value of the alkali hierarchy of control simultaneously 7.5～10; React after 1～3 hour,, filter with sour adjust pH to 6～7, wash 2～3 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly; Adding concentration is 90～99% ethanol in retort, the starch alkenyl succinate ester that makes is added in the retort, the furnishing quality is 25～55% starch slurry than concentration, under the stirring action, adding concentration is 40% NaOH, regulate starch slurry pH value 10～14, stirring is warmed up to 40～50 ℃, and alkalization 0.5～2h adds the Mono Chloro Acetic Acid of starch quality 50～85% then, stirring down keeps slurry temperature at 55～65 ℃, reaction 4～8h with extremely neutral with slurry among the dense HCL, carries out centrifugation with the slurry after the neutralization, starch is used centrifugation after 80% the washing with alcohol again, after the oven dry carboxymethyl starch alkenyl succinate ester finished product.
3, a kind of double-modified starch production method is characterized in that, adds starch and water in retort, and the furnishing quality is 30～60% starch slurry than concentration, continue to stir and with the temperature adjusting of starch slurry at 30～60 ℃, with NaOH or Na
2CO
2Regulate starch milk pH value to 8～10, in starch milk, add the alkenyl succinic anhydride of starch quality 1～10%, use the pH value of the alkali hierarchy of control simultaneously 7.5～10; React after 1～3 hour,, filter with sour adjust pH to 6～7, wash 2～3 times after, centrifugal, the starch alkenyl succinate ester that dewaters wetly, drying; With concentration is that 30～50%NaOH liquid sprays in the starch alkenyl succinate ester of doing, and the sprinkling amount is controlled at 5～15% of starch quality, mixes powerful the stirring after 1～3 hour, and starch is pulverized, and crosses 80～200 mesh sieves, and starch must alkalize; With the starch after pulverizing and Mono Chloro Acetic Acid by in 5～10: 1 the mass ratio input mixer, after mixing, it is sent in the dry type reaction machine, and temperature remains on 50～90 ℃ of reactions 1～3 hour, dries then, pulverizes promptly to get carboxymethyl starch alkenyl succinate ester finished product.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456914B (en) * | 2007-12-14 | 2011-02-02 | 沈阳工业大学 | Method for preparing hydrophobic starch |
| CN101628944B (en) * | 2009-07-15 | 2011-05-18 | 聚祥(厦门)淀粉有限公司 | Complex modified starch |
| CN102199222A (en) * | 2010-03-26 | 2011-09-28 | 中国石油大学(北京) | Amphiphilic starch and preparation method thereof |
| CN102952302A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Preparation method of antistatic powdery chloroprene rubber |
| CN107522790A (en) * | 2017-09-22 | 2017-12-29 | 西南大学 | A kind of difunctional New Modified Starch and preparation method thereof |
| CN113667026A (en) * | 2021-05-20 | 2021-11-19 | 华南理工大学 | High-viscosity instant carboxymethyl octenyl composite modified starch emulsion thickener and preparation method and application thereof |
-
2004
- 2004-04-09 CN CN 200410030778 patent/CN1563097A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456914B (en) * | 2007-12-14 | 2011-02-02 | 沈阳工业大学 | Method for preparing hydrophobic starch |
| CN101628944B (en) * | 2009-07-15 | 2011-05-18 | 聚祥(厦门)淀粉有限公司 | Complex modified starch |
| CN102199222A (en) * | 2010-03-26 | 2011-09-28 | 中国石油大学(北京) | Amphiphilic starch and preparation method thereof |
| CN102952302A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Preparation method of antistatic powdery chloroprene rubber |
| CN102952302B (en) * | 2011-08-19 | 2014-11-26 | 中国石油天然气股份有限公司 | Preparation method of antistatic powdery chloroprene rubber |
| CN107522790A (en) * | 2017-09-22 | 2017-12-29 | 西南大学 | A kind of difunctional New Modified Starch and preparation method thereof |
| CN113667026A (en) * | 2021-05-20 | 2021-11-19 | 华南理工大学 | High-viscosity instant carboxymethyl octenyl composite modified starch emulsion thickener and preparation method and application thereof |
| CN113667026B (en) * | 2021-05-20 | 2022-11-18 | 华南理工大学 | High-viscosity instant carboxymethyl octenyl composite modified starch emulsion thickener and preparation method and application thereof |
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