CN1271087C - Process for preparing high substituted degree hydroxyalkyl starch - Google Patents
Process for preparing high substituted degree hydroxyalkyl starch Download PDFInfo
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- CN1271087C CN1271087C CN 200510033407 CN200510033407A CN1271087C CN 1271087 C CN1271087 C CN 1271087C CN 200510033407 CN200510033407 CN 200510033407 CN 200510033407 A CN200510033407 A CN 200510033407A CN 1271087 C CN1271087 C CN 1271087C
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Abstract
The present invention relates to a method for preparing high substitution degree hydroxyalkyl starch. Hydroxyalkyl starch belongs to non-ionic starch ether and is widely used in daily chemical product, cosmetic thickening agents, construction material adhesives, etc. Methods for preparing the hydroxyalkyl starch, such as a wet method, a dry method, a solvent method, etc. have the disadvantages of long reaction time, low substitution degree, expensive solvent, easy combustion, easy explosion, high toxicity, hard recycling, etc. The present invention has the method that alpha-starch is mixed with catalysts in an oxygen-free sealed reaction container, an alkylationre agent with certain water is added in the reaction container to soak for 20 to 40 hours, and then the high substitution degree hydroxyalkyl starch with the substitution degree (DS) of 2 to 3 is prepared. The method does not need heating in reaction processes and can avoid explosion caused by the alkylation agent simultaneously, and the method is convenient to industrial production.
Description
Technical field
The present invention relates to the preparation method of starch hydroxyalkylation prepared in reaction high substituted degree hydroxyalkyl starch.It mainly is starch is produced the high substitution value starch ethers through the hydroxyalkylation reaction manufacturing technology.
Background technology
Hydroxyalkyl starch belongs to the nonionic starch ethers, has good water-solubility and stability of viscidity, is widely used in printing-ink, fibrous warps starching, food and medicine product thickening cakingagent, daily-use chemical industry and makeup thickening material and material of construction tamanori etc.In recent years, only U.S.'s annual production is more than 100,000 ton.
The method for making of hydroxyalkyl starch has wet method, dry method and solvent method etc.Wet processing is the most common, and starch adds salt and makes the particle swelling inhibitor under the water and milk state, under alkaline catalysts and alkylating reagent effect, makes product at 35 ℃-50 ℃ reaction 8h-24h.The shortcoming of wet method is the product purification difficult, long reaction time, substitution value low (DS＜0.1); Dry method be starch contain under the small amount of moisture with solid alkali and alkylating reagent gas at 85 ℃, make under 0.3MPa pressure and the sealed state.Dry method is a gas-solid phase reaction, product substitution value height, the danger but alkylating reagent is easily blasted; Solvent method is with organic solvent such as methyl alcohol, ethanol, Virahol, benzene etc. starch to be disperseed, under alkaline catalysts with the alkylating reagent reaction, product substitution value height, but exist solvent expensive, inflammable, poisonous, reclaim shortcomings such as difficulty; Recently also be suspended in the organic solvent by the independent water solution system that adopts emulsifying agent, starch, water, alkali, alkylating reagent to form and react, product separates from reaction mixture with solid particulate form.This method mild condition, product is refining simple, and reaction efficiency＞75%, DS are between 0.5-2.5, and shortcoming is the system instability, the processing requirement height.
Summary of the invention
At the deficiencies in the prior art and shortcoming, the invention provides a kind of preparation method of high substitution value starch.
This method is under the airtight condition of anaerobic, is raw material with the Alpha-starch, under basic catalyst or salt, amines catalyst effect, with moisture alkylating reagent effect, under 0～38 ℃, reacted 20～40 hours, making high substitution value DS is 2～3 hydroxyalkyl starchs.
Adopt pre-gelatinized starch (claiming a-starch again) to make raw material, under basic catalyst or salt, amines catalyst effect,, make high substituted degree hydroxyalkyl starch with the alkylating reagent reaction.Temperature of reaction is 0 ℃-38 ℃, need not heat during reaction, also need not stir and stumble, just in encloses container, alkylating reagent soaked a-starch for some time after, remove reagent and obtain product.Starch is pulvis in the reaction process, makes the product separate easily to help suitability for industrialized production.
Adopting a-starch to make reaction raw materials, is best with no crystallinity.Test method is that a-starch is soaked in the cold water, does not have the polarisation cross with polarized light microscope observing and occurs, and illustrates that the starch crystals degree is destroyed, is easy to chemical reagent and enters.The starch of pre-half steaming still is the polarisation cross, alkylating reagent is infiltrated be obstructed, and the products therefrom substitution value is low and inhomogeneous, influences quality product.Make the a-starch material and can use starch such as wheat, rice, jowar, corn, cassava, potato, make by roll extrusion farinaceous size under the high temperature.The a-starch granules of making alkylated reaction is the smaller the better, should be less than 150 mesh sieve holes (Chinese Industrial Standards (CIS) sieve), generally wanted 150-200 mesh sieve hole (Chinese Industrial Standards (CIS) sieve), and in addition, as the starch that food is used, heavy metal content will meet state-set standard.Produce the also available dextrin of high substituted degree hydroxyalkyl starch.Dextrin is a starch through the product of different methods degraded, the product that is produced not as a-starch with the hydroxyalkyl starch viscosity of dextrin production.
Make the hydroxyalkylation catalysts with alkali, commonly used have sodium hydroxide, potassium hydroxide, a yellow soda ash etc., and also available salt or amines catalyst are as vitriol, carboxylate salt, tertiary amine etc.The most frequently used with sodium hydroxide.During use it is worn into behind the 0.02-0.04mm powder and a-starch uniform mixing, with the alkylating reagent reaction, if addition amount of sodium hydroxide is few, speed of response is slow again, and the product substitution value is low, and therefore, the sodium hydroxide optimum amount is the 1%-2% of starch weight.
Alkylating reagent is used oxyethane, propylene oxide or butylene oxide ring always.The above two boiling points are respectively 13 ℃ and 35 ℃, explosive, and their explosive range is very wide, and the alkylating reagent volume all can set off an explosion between 36%-78% after the air mixed.Therefore, reaction must be carried out under the airtight condition of anaerobic, and used reactor is that stainless steel is all-sealed, and the band explosion-proof equipment vacuumizes earlier before the reaction, feeds nitrogen again residual air is thrown out, and just adds alkylating reagent and reacts.Need not heat during reaction, generally soak starch 24h and promptly get product.As producing the low degree of substitution product, the reaction times can be shortened.Therefore, real reaction product substitution value is from 0, between the 5-3.0 or substitution value between 0.1～3, regulate.In the reaction process, the starch final water content is 10%-15%.The having of water is beneficial to sodium hydroxide and is ionized into ion and plays the catalyzed reaction effect.In fact general starch itself has contained 5% the moisture of having an appointment, these water adsorption are among starch, do not ooze out, make and be swift in response, the adding of a part of water is by with after alkylating reagent mixes in addition, join together in Alpha-starch and the mixture of catalysts, wherein the add-on of water is 2～10% of an Alpha-starch amount, adds moisture more again, during interpolation, can not pour water among the starch into, in order to avoid cause the local gelatinization of starch and blot the water phenomenon, can only be with water with after alkylating reagent mixes, join in the starch and go at once, to keep the particle form of starch, be beneficial to product separation and purify, guarantee the product homogeneity.After reaction finished, the elimination alkylating reagent led to hot water in reacting kettle jacketing, residual reagent is steamed walk to obtain rough hydroxyalkyl starch.If be used for food uses, must be further with the 50%-90% washing with alcohol, take off ethanol, citric acid is regulated PH6.5-7.0, drying, pulverize, sieve purified product.
The method that is used for measuring substitution value of the present invention is as follows:
With the hydroxypropylated starch is example, and the principle of measuring the hydroxypropylated starch substitution value is identical with the mensuration propylene glycol, and with 1, the 2-propylene glycol is done standardized solution in the mensuration.1,2-propylene glycol, hydroxypropylated starch can generate the enol form and the olefine aldehydr formula dehydration neutralized rearrangement mixture of propionic aldehyde in the vitriol oil, this mixture generates violet complex at vitriol oil medium and triketohydrindene hydrate, use spectrophotometric determination, survey its absorbancy at the 595nm place, with standard 1, the 2-propylene glycol relatively can be derived hydroxypropyl content.
Above-mentioned reaction has utilized the open structure and the alkylating reagent reaction of a-starch, and at room temperature carry out, avoided the explosive danger of alkylating reagent, also avoided this reagent that the side reaction of auto-polymerization easily takes place under high temperature, high pressure, also reduce the hydrolytic action of alkylating reagent, obtained high substituted degree hydroxyalkyl starch.Reaction process starch remains solid state powder, is easy to separating reaction reagent, is easy to refined product, can be fit to suitability for industrialized production.
The advantage of the method for the invention, be open structure and the alkylating reagent reaction that has utilized Alpha-starch, and reaction process need not heating, avoided the explosive danger of alkylating reagent, also avoided this reagent that the side reaction of auto-polymerization easily takes place under high temperature, high pressure, also reduce the hydrolytic action of alkylating reagent, obtained high substituted degree hydroxyalkyl starch; Reaction process starch remains solid state powder, is easy to separating reaction reagent, is easy to refined product, can be fit to suitability for industrialized production.
Embodiment
Embodiment 1
The method for making of high substitution value hydroxypropyl starch.In the stainless steel cauldron that has chuck and explosion-proof equipment, 50Kg wheat Alpha-starch with moisture 5% (general Alpha-starch moisture 5%) and 1Kg granularity join in the reactor after mixed for the 0.02mm sodium hydroxide powder, after closing the lid, vacuumized 20 minutes, logical again nitrogen 20 minutes, join in the reactor after then the propylene oxide 180Kg of weight percent and 4Kg water being mixed, soak 24h, need not stir and heat during immersion, elimination propylene oxide then, in reacting kettle jacketing, feed 80 ℃ of hot water again,, obtain the hydroxypropylated starch of substitution value 2.5～3.0 in order to steam remaining propylene oxide.Product again through 90% washing with alcohol, reclaim ethanol, citric acid mix neutralization, dry, pulverize, sieving obtains the purified hydroxypropylated starch.Under the constant situation of above-mentioned technology, shorten the reaction times, also can obtain the hydroxypropylated starch of low degree of substitution.Propylene oxide after the recovery can also be used for the next batch reaction.
Embodiment 2
The method for making of high substitution value hydroxyethylamyle.Conversion unit and processing compound and reaction conditions are with embodiment 1.Propylene oxide with among the oxyethane replacement embodiment 1 obtains hydroxyethylamyle, and substitution value is 2.5～3.
Claims (5)
1, a kind of preparation method of high substituted degree hydroxyalkyl starch, it is characterized in that under the airtight condition of anaerobic, with the Alpha-starch is raw material, at basic catalyst, under salt or the amines catalyst effect, with moisture alkylating reagent effect, under 0～38 ℃, reacted 20～40 hours, making high substitution value DS is 2～3 hydroxyalkyl starchs, described raw material Alpha-starch is the Alpha-starch of particle diameter less than 150 order Chinese Industrial Standards (CIS)s sieve sieve aperture, when using catalyzer it is worn into behind the 0.02-0.04mm powder and a-starch uniform mixing, catalyst levels is the 1%-2% of starch weight, described moisture alkylating reagent is meant that the adding of water is by with after alkylating reagent mixes, make moisture alkylating reagent earlier, join together in Alpha-starch and the mixture of catalysts, wherein the add-on of water is 2～10% of an Alpha-starch amount again, and described alkylating reagent is an oxyethane, propylene oxide, or butylene oxide ring.
2, preparation method according to claim 1 is characterized in that wheat, Chinese sorghum, soybean, rice, corn, cassava or the yam starch of described Alpha-starch for handling through pre-gelatinization, or is the dextrin of above-mentioned starch preparation.
3, preparation method according to claim 1 is characterized in that being that described catalyzer is sodium hydroxide, potassium hydroxide, yellow soda ash, vitriol, carboxylate salt or tertiary amine.
4,, it is characterized in that being that described catalyzer is a sodium hydroxide according to claim 1 or 3 described methods.
5, method according to claim 1, the particle diameter that it is characterized in that described Alpha-starch raw material were 150-200 order Chinese Industrial Standards (CIS) sieve sieve aperture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510033407 CN1271087C (en) | 2005-03-07 | 2005-03-07 | Process for preparing high substituted degree hydroxyalkyl starch |
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| CN 200510033407 CN1271087C (en) | 2005-03-07 | 2005-03-07 | Process for preparing high substituted degree hydroxyalkyl starch |
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| CN1271087C true CN1271087C (en) | 2006-08-23 |
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| CN 200510033407 Expired - Fee Related CN1271087C (en) | 2005-03-07 | 2005-03-07 | Process for preparing high substituted degree hydroxyalkyl starch |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100491401C (en) * | 2006-07-28 | 2009-05-27 | 湖北省农业科学院辐照加工研究所 | Process of preparing non-ionic starch by initiating irradiation |
| CN101942032B (en) * | 2010-09-07 | 2012-05-30 | 中科院广州化学有限公司 | Method for preparing methyl starch |
| CN102344498B (en) * | 2011-10-26 | 2013-07-17 | 邹平福海科技发展有限公司 | Special starch ether for mortar and production method thereof |
| CN104814271A (en) * | 2015-04-28 | 2015-08-05 | 防城港市雅美好饲料有限公司 | Preparation method for manufacturing feed with pre-gelatinized starch |
| CN104799093A (en) * | 2015-04-28 | 2015-07-29 | 防城港市雅美好饲料有限公司 | Preparation method of pregelatinized starch for aquatic feed |
| CN107226869A (en) * | 2017-06-29 | 2017-10-03 | 华南理工大学 | A kind of method that soda acid collaboration pretreatment prepares high substituted degree hydroxyl butyl starch |
| CN110229241B (en) * | 2019-06-21 | 2021-07-20 | 华南理工大学 | Method for preparing potato hydroxypropyl starch based on cold plasma |
| CN115960271B (en) * | 2023-01-17 | 2024-04-05 | 齐鲁工业大学(山东省科学院) | High-substitution hydroxypropyl starch and preparation method and application thereof |
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