CN107226869A - A kind of method that soda acid collaboration pretreatment prepares high substituted degree hydroxyl butyl starch - Google Patents
A kind of method that soda acid collaboration pretreatment prepares high substituted degree hydroxyl butyl starch Download PDFInfo
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- CN107226869A CN107226869A CN201710514866.8A CN201710514866A CN107226869A CN 107226869 A CN107226869 A CN 107226869A CN 201710514866 A CN201710514866 A CN 201710514866A CN 107226869 A CN107226869 A CN 107226869A
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- C08B31/00—Preparation of derivatives of starch
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Abstract
The method that the hydroxyl butyl starch of high substituted degree is prepared the invention discloses a kind of collaboration pretreatment of soda acid.This method adds starch in Organic Alcohol, adds after concentrated hydrochloric acid effect, and washing suction filtration obtains low-kappa number starch；Low-kappa number starch is made into starch milk to be placed in thermostat water bath, sodium hydroxide solution is at the uniform velocity added dropwise, is neutralized, washing is dry that soda acid collaboration handles starch；Starch after soda acid collaboration is handled is placed in ethanol, is added sodium hydroxide and 1, after the reaction of 2 epoxy butanes, is neutralized, wash, dry, produce target product.The present invention is raw material with starch and 1,2 epoxy butanes, using soda acid combination pretreatment mode, prepares the hydroxyl butyl starch that substitution value is up to 1~1.80.
Description
Technical field
The present invention relates to a kind of hydroxyl butyl starch, and in particular to soda acid collaboration pretreatment prepares high substituted degree hydroxyl butyl starch
Method；In natural polymer field of chemical modification.
Background technology
Starch is polymeric carbohydrate, the polysaccharide being made up of the sugar unit of single type, is heavy in granular form
Product is transformed, with protein, fiber, grease, sugar and mineral matter in the seed, stem tuber or root of plant through photosynthesis
Deng presence jointly.Due to still returning to the Nature, quilt in the form of carbon dioxide and water after its wide material sources, cheap, degraded
It is considered the high polymer material of natural reproducible not polluted completely.The basic component unit of starch is that D-grape is warded off, grape
It is exactly starch molecule that sugar, which is sloughed and passed through after hydrone by glycosidic bond the formed covalent polymer that links together,.Starch molecule has
Many hydroxyls, with the respond similar with low molecule hydroxy compounds, if be esterified, be etherified, being aoxidized, grafting,
The reaction such as Cross-linked forms many derivatives (converted starch), thus can improve defect in starch structure and performance.Modified
Starch has more excellent property, has more preferable application effect, while also opening new purposes.
Hydroxyalkyl starch belongs to non-ionic starch derivative, and good hydrophilic property, viscosity stability is high, with excellent application
Performance.The hydroxyalkyl starch developed mainly has HES and hydroxypropul starch, and hydroxyl butyl starch is then seldom.Form sediment
Powder derivative all represents the substitution degree of substituent with substitution value (DS).Substitution value refers to each D-adjoin quilt in glucopyranoside base
The average hydroxyl number of substituent substitution.Most of glucosyl groups have 3 hydroxyls that can be substituted in starch, so DS maximum
For 3.When substituent further reacted with reagent to be formed polymerize substituent when, represent that with molar substitution (MS) every mole adjoins
The amount of the material of substituent in glucopyranoside base.In general, MS be less than 0.3 for low degree of substitution, MS is 0.3~1
Deng substitution value, MS be more than 1 for high substituted degree.
Hydroxyalkyl starch has a variety of synthetic methods, is broadly divided into：Dry method, water dispersion, non-aqueous solvent method and mini-emulsion process.
Dry method can obtain the high product of pure white, powdery, substitution value, but finished product is difficult to purify, and have explosion danger, industry is difficult at present
Change.Mini-emulsion process improves to some extent on solvent method, and reaction efficiency is more than 75%, and substitution value MS is 0.05~2.5, but system is not
Enough stable, technological requirement is high.At present, the domestic main production MS by solvent of water is less than 0.3 low degree of substitution hydroxyalkyl starch.MS
Hydroxyalkyl starch more than 0.3 is mostly prepared by solvent method.Liu Shuhua (study on the synthesis of depth hydroxypropylation cornstarch, Zheng
State grain institute journal, volume 18, the 4th phase) hydroxypropul starch of high substituted degree is prepared by high-temperature high-pressure reaction kettle, but give birth to
Produce equipment requirement high, it is difficult to realize industrialization.Yu Huan (influence of the hydroxyl butylation level to cornstarch physicochemical property, modern times food
Product science and technology, volume 30, the 12nd phase) to prepare hydroxyl butyl beautiful for the method directly reacted in organic solvent by starch and epoxy butane
Rice starch, its substitution value is up to 0.41.More high substituted degree and the preparation method then rare research for being easy to industrialized production.Etherificate becomes
Property after starch obtained certain improvement in nature in freeze-thaw stability, paste liquid transparency etc. compared with the starch before denaturation and carried
Height, but still the requirement of industry-by-industry can not be met, it is badly in need of the exploitation etherification starch that substitution value is higher, property is more stable and newly produces
Product.
The content of the invention
For the problems of background above and deficiency, it is an object of the invention to by carrying out soda acid association to ative starch
With pretreatment, with reference to organic solvent method, prepare high substituted degree, reaction efficiency is high and is easily isolated purification and industrial metaplasia
The hydroxyl butyl starch of production.
Acidification of the present invention makes branched amylopectin molecules diminish, and aperture occurs in starch surface, while the hot cold ratio of viscosities of increase
Value, strengthens its gelation.Basification can be swelled starch molecule, loose starch granules, hydroxyl is become negative oxygen ion, parent
With property enhancing.Use ethanol for dispersant, then avoid starch molecule from being gelatinized, serious degraded increases hydrophily；It is particularly of the invention
Using double alkalisation method, being fully swelled without pasting for starch molecule is ensure that on the basis of acidification and basification
Change, while substantially increasing the substitution value of hydroxyl butyl starch, also improve the performance of hydroxyl butyl starch each side.Institute of the present invention
The high substituted degree hydroxyl butyl starch of preparation remains in that preferable particle shape.
Starch gelatinization temperature is improved after soda acid collaboration pretreatment of the present invention, makes the reaction of hydroxyl butylation can be at higher temperature
Degree is lower to be carried out, and substantially increases reaction efficiency.Because hydroxyl butyl group is typical hydrophilic radical, hydroxyl butyl starch gelatinization
Temperature is substantially reduced, and gelatinization is easier.Gelatinized corn starch liquid viscosity is low after Heat Gelatinization, and paste liquid transparency is high, is adapted to configuration high concentration
Starch solution, and strengthen the application in terms of gel.
The hydroxyl butyl starch substitution value of the present invention is exactly to be represented with molar substitution (MS).
In traditional industry Acid modified starch is produced with watery hydrochloric acid or sulfuric acid with starch reaction certain time at 25~55 DEG C.
And the yield of Acid modified starch is reduced with the increase of acid concentration and hydrolysis time in aqueous phase.Both at home and abroad to Acid modified starch
Research main distribution situation in the change of the influence of the degree of polymerization, granule size and form, molecular weight and strand, paste
Heat endurance etc..To starch, the modified research of acid seldom, the research of etherificate substitution value is improved to this kind of starch then in Organic Alcohol
Less.The basification reaction such as starch can be promoted to be etherified, be esterified, but it is industrial it is more is that Aqueous phase is reacted, preparation
The etherification starch of low degree of substitution.More apply of alcohol alkaline process is preparing granular starch dissolvable in cold water, but it is more be also limited to life
The properties of production. art and paste, are incorporated into the research that other denaturation means carry out complex denaturation, and current studies in China is seldom,
It is combined with low-kappa number, has no report.The research of domestic etherification starch is mainly ethoxy, hydroxypropul starch, preparation technology
It is ripe.But the research to high substituted degree hydroxyl butyl starch is then few.Though the existing like product listing of foreign countries, technical know-how
Property it is strong, bring great difficulty to research work.
Acid treatment is one kind most ancient in all starch conversion methods, and the modified major advantage of acid is not significantly affect
Change the functional characteristic of starch on the basis of grain structure.Starch after acidolysis its molecular weight reduce, into paste after its liquid viscosity
It is significantly reduced.Denaturated starch by acid heat paste viscosity is far below ative starch.But denaturated starch by acid makes starch due to sour hydrolysis
The degree of branching is reduced, so that denaturated starch by acid has higher gelling ability, forms stable gel in higher concentrations.Thus its
On food industry such as soft sweets, starch jelly, the warp thread in Cypres, improvement adaptability and the textile industry of paper industry
More more preferable applications are obtained in terms of slurry.
In alkaline solution, because starch is a kind of weak ion-exchanger ,-OH proton is dissociated, so that starch molecule
It is negatively charged, it is mutually exclusive between electronegative molecule, cause starch granules swell, the particle being swelled is to neighbouring starch molecule knot
Crystal produces tension force and distorts them, starch is reached optimal solvent swelling state.In alcoholic solution, starch keeps complete particle
Form.While alkali can also be catalyzed, the activated centre generated in epoxy butane open loop, alkalinization is more, and the substitution of hydroxyl butyl starch is imitated
Fruit is better, and epoxy butane utilization rate is higher.
In Organic Alcohol, alcohol destroys the double-stranded hydrophobic bond of starch granules internal chaining and hydrogen bond, and acid can penetrate into shallow lake
Powder threaded interior hydrolyzing glucosidic bonds so that starch granules structure changes.Sour water solution causes amylopectin and amylose
Degraded, not only produces more amyloses, and starch structure is become loose, and there is small hole on starch surface, favorably
Make starch expansion in alcoholic solution without being gelatinized in alkali.Double alkalisation then causes starch fully to activate, and epoxy butane is increased significantly
Utilization rate so that degree of being finally replaced is improved.
Short strand and liquid liquid homogeneous system non-thing phase system more solid than long strand and liquid, is more easy to react.Institute
High substituted degree hydroxyl butyl starch is prepared to carry out soda acid collaboration pretreatment to starch, lower gelatinization point and more is made it have
Stable gelling properties, with very big realistic meaning.
The object of the invention is achieved through the following technical solutions：
A kind of method that soda acid collaboration pretreatment prepares high substituted degree hydroxyl butyl starch, comprises the following steps：
1) by starch dispersion in Organic Alcohol, it is made into the starch milk that mass percent is 30~40%；
2) by step 1) products obtained therefrom stirs at room temperature, adds concentrated hydrochloric acid, it is stirred for uniform；Every gram of starch on dry basis adds
Enter concentrated hydrochloric acid for 1~4mL；
3) by step 2) products therefrom is placed in 40~55 DEG C of water-baths, and 3~6h is stirred under 200~250rpm speed；
4) stop heating, with sodium carbonate liquor neutralization procedure 3) products obtained therefrom to pH be 6.5~7.5；
5) by step 4) products therefrom washs with ethanol/water, dries；
6) by step 5) products therefrom be made into Organic Alcohol 5%~15% starch milk；
7) by step 6) products therefrom is placed in 30~40 DEG C of thermostat water baths, and sodium hydroxide solution is at the uniform velocity added dropwise, react
Continue 30~60min；Added sodium hydroxide concentration is the quality 0.02~0.08% of starch on dry basis；
8) by step 7) reaction products therefrom suction filtration, is washed with ethanol/water, is 6.5~7.5 with concentrated hydrochloric acid regulation pH, takes out
Filter, is washed, drying；
9) by step 8) reaction products therefrom is scattered in Organic Alcohol, adds the hydroxide of starch on dry basis quality 2~8%
Sodium；Nitrogen is passed through, 1, the 2- epoxy butanes of starch on dry basis quality 100~250% are added；8~14h is reacted at 50~70 DEG C；
10) by step 9) reaction products therefrom neutralized with watery hydrochloric acid, use ethanol/water washes clean, dry, obtain high substituted degree
Hydroxyl butyl starch.
Further to realize the object of the invention, it is preferable that the Organic Alcohol can be methanol, ethanol or isopropanol.
Preferably, step 2) stir speed (S.S.) is 200~250rpm.
Preferably, step 10) neutralize when examined with silver nitrate solution, until without white precipitate generation.
Preferably, step 5), step 8) and step 10) in, described drying is in 40 DEG C~50 DEG C thermostatic drying chambers
Dry 24h.
Preferably, step 5), step 8) and step 10) described in ethanol/water volume ratio 20~80：100.
Preferably, the starch is one in cornstarch, farina, tapioca, green starch, pea starch
Plant or a variety of.
Preferably, step 9) in be passed through 5~10min of nitrogen.
Preferably, the mass fraction of the concentrated hydrochloric acid is 36%.
Preferably, the mass fraction of the watery hydrochloric acid is 5%~10%；Step 9) in Organic Alcohol mass fraction for 85~
95%.
The present invention has the following advantages that compared with prior art：
(1) present invention will prepare hydroxyl butyl starch after starch progress soda acid collaboration pretreatment using organic solvent method first,
Substitution value is up to 1.80 or so.
(2) traditional handicraft is disposably to put into alkali in solvent, causes starch dissolution speed slow, skewness, shadow
The alkalization effect of starch is rung, so as to influence to be etherified effect；The present invention makes starch fully expand without pasting starch double alkalisation
Change, substantially increase reaction efficiency.
(3) low boiling point (78.15 DEG C) of starch dispersant ethanol, nontoxic, is easily removed from reaction, it is adaptable to which industry is raw
Production.
(4) course of reaction of the present invention is easily controllable, and equipment is simple, and reaction efficiency is high, and the starch of preparation is always graininess
State, is conducive to the later stage to be modified and application.
(5) present invention is cooperateed with by soda acid and pre-processed, and purification, suction filtration are simple, and product is applied to other modification applications.
Embodiment
To more fully understand the present invention, with reference to embodiment, the present invention is described further, but the reality of the present invention
Mode is applied not limit so.
In example below, the assay method of hydroxyl butyl starch substitution value is as follows：
The drafting of 1 standard curve
1) 0.0025gm/L hutanal standard liquids have first been configured, 0.00,1.00 is accurately pipetted respectively with liquid-transfering gun,
2.00,4.00,6.00,8.00,10.00mL in 100mL volumetric flasks, scale is settled to distilled water.0.00 is can obtain,
5.00,10.00,15.00,20.00,25.00 × 10-5G/mL standard liquid.
2) this 5 kinds of standard hutanal solution 1.00mL are drawn respectively in scale test tubes of the 25mL with plastic plug, will be tried
Pipe is slightly tilted, and is slowly added to the 8mL concentrated sulfuric acids, is covered plug, is rocked after being well mixed, is inserted in frozen water and rapidly cool down, treat temperature
Degree is down to 25 DEG C.
3) 0.6mL 3% ninhydrin standard indicator solution is added along test tube wall with liquid-transfering gun, at 25 DEG C after shaking up
60min is placed in water-bath, allows red complex fully to generate, diluting concentrated sulfuric acid is added to 25mL graduation marks, it is slight reverse mixed
It is even, stand 5min.
4) solution being pipetted into 1ml cuvettes rapidly, reference being made with distilled water, its absorbance is determined at 470nm, must be inhaled
Luminosity-concentration standard curve.
The measure of 2 substitution values
1) it is accurate to weigh abundant dried hydroxyl butyl starch sample 0.08-0.10g in 100mL volumetric flasks, add
25mL 1.0mol/L-1 dilution heat of sulfuric acid, boiling water bath is heated to sample and is completely dissolved, then static solution is cooled to room
Temperature, 100mL is settled to distilled water.
2) solution 1mL is drawn with liquid-transfering gun, is put into the 25mL glass scales test tubes with plastic plug, test tube is immersed
It is careful that the 8mL concentrated sulfuric acids are added dropwise in cold water.Turn upside down after mixing, test tube is positioned in 100 DEG C of boiling water baths, strict control adds
The hot time is 3min, and test tube is moved into ice-water bath quenching rapidly.
3) treat that solution temperature is down to 25 DEG C, the careful accurate ninhydrin reagent solution along inboard wall of test tube dropwise addition 3%
0.6mL, turns upside down and shakes up, and must not vibrate, and is transferred in 25 DEG C of water-baths and keeps 60min, it is therefore an objective to makes red complex abundant
Generation.
4) concentrated sulfuric acid is added to test tube graduation mark 25mL, and test tube is reversed up and down and is ensured well mixed (must not be aggressively shaken).
Immediately in transfer solution to 1cm cuvettes, reference is made with reagent blank, using ultraviolet specrophotometer, it is determined at 470nm
Absorbance,
5) compared with standard curve, find the content of corresponding hutanal, substitution value is calculated using formula.
The molar substitution (MS) of hydroxyl butyl starch is calculated as follows：
C=D × (MSample/WSample-MIt is former/MIt is former)×25×1.00×100)
MS=2.25C/100-C
C:The percentage composition of hydroxyl butyl, unit：%；
D:Sample or blank sample extension rate；
MSample：The concentration (g/mL) of contained hutanal in the sample checked on standard curve；
MIt is former：The concentration (g/mL) of contained hutanal in the ative starch checked on standard curve；
WSample：Sample quality (g)；
WIt is former：Former cornstarch quality (g).
Comparative example 1
1) waxy corn starch is scattered in 95% ethanol, is made into the starch milk of 30% mass fraction, added while stirring
Enter the aqueous slkali that sodium hydroxide is starch on dry basis 3%, be passed through nitrogen 5min, rapidly join as the 1 of starch on dry basis quality 150%,
2- epoxy butanes, 70 DEG C of heating water bath 12h.Products obtained therefrom is neutralized to the watery hydrochloric acid of 10% mass fraction of 10% mass fraction
PH is 7.0, with ethanol/water (75v/v) filtering and washing, and in 45 DEG C of oven drying 24h, gained hydroxyl butyl starch is white powder,
Detected through the above method, its substitution value is 0.36.
Comparative example 2
1) waxy corn starch is scattered in ethanol, is configured to mass fraction for 30% starch milk, is placed in three-necked flask
In.Stir at room temperature, add starch on dry basis quality 1.4mL/g concentrated hydrochloric acid, stir 0.3h.Warming-in-water is stirred to 50 DEG C
Mix 3h.Stop heating, it is 7.1 that pH is neutralized to sodium carbonate liquor, and products obtained therefrom is washed with ethanol/water (50v/v), in 45 DEG C of bakings
Case dries 24h, obtains low-kappa number waxy corn starch.
2) low-kappa number waxy corn starch is scattered in 95% ethanol, is made into the starch milk of 30% mass fraction, side
Stir side and add the aqueous slkali that sodium hydroxide is starch on dry basis quality 3%, be passed through nitrogen 5min, rapidly join as starch on dry basis matter
1, the 2- epoxy butanes of amount 150%, 70 DEG C of heating water bath 12h.Products obtained therefrom is neutralized to mass fraction for 10% watery hydrochloric acid
PH is 6.9, with ethanol/water (75v/v) filtering and washing, and in 45 DEG C of oven drying 24h, gained hydroxyl butyl starch is white powder,
Detected through the above method, its substitution value is 1.39.
Comparative example 3
1) take waxy corn starch to be scattered in ethanol, be made into mass fraction for 10% starch milk in three-necked flask.40
DEG C water-bath, is at the uniform velocity added dropwise containing the aqueous slkali that sodium hydroxide is the mass of starch on dry basis quality 0.06%, reacts 50min.Products obtained therefrom
It is 6.8 that pH is neutralized to the watery hydrochloric acid of 10% mass fraction, is washed, in 45 DEG C of oven drying 24h, obtained with ethanol/water (50v/v)
Oxygenation pretreatment waxy corn starch.
2) oxygenation pretreatment waxy corn starch is scattered in 95% ethanol, is made into the starch milk that mass fraction is 30%,
The aqueous slkali that sodium hydroxide is starch on dry basis quality 3% is added while stirring, is passed through nitrogen 5min, is rapidly joined as starch on dry basis
1, the 2- epoxy butanes of quality 150%, 70 DEG C of heating water bath 12h.Products obtained therefrom is neutralized to the watery hydrochloric acid of 10% mass fraction
PH is 6.8, with ethanol/water (75v/v) filtering and washing, and in 45 DEG C of oven drying 24h, gained hydroxyl butyl starch is white powder,
Detect that its substitution value is 1.13 through the above method.
Embodiment 1
1) waxy corn starch is scattered in ethanol, is configured to mass fraction for 30% starch milk, is placed in three-necked flask
In.Stir at room temperature, add starch on dry basis quality 1.4mL/g concentrated hydrochloric acid, stir 0.3h.Warming-in-water is stirred to 50 DEG C
Mix 3h.Stop heating, it is 6.8 that pH is neutralized to sodium carbonate liquor, and products obtained therefrom is washed with ethanol/water (50v/v), in 45 DEG C of bakings
Case dries 24h, obtains low-kappa number waxy corn starch.
2) take low-kappa number waxy corn starch to be scattered in ethanol, be made into mass fraction for 10% starch milk, Yu Sankou
In flask.40 DEG C of water-baths, are at the uniform velocity added dropwise containing the aqueous slkali that sodium hydroxide is starch on dry basis quality 0.06%, react 50min.Gained
It is 6.8 that product, which is neutralized to pH with the watery hydrochloric acid of 10% mass fraction, is washed with ethanol/water (50v/v), in 45 DEG C of oven dryings
24h, obtains soda acid collaboration pretreatment waxy corn starch.
3) soda acid collaboration pretreatment waxy corn starch is scattered in 95% ethanol, is made into the shallow lake that mass fraction is 30%
Powder breast, adds the aqueous slkali that sodium hydroxide is starch on dry basis 3%, is passed through nitrogen 5min, rapidly join and done for starch while stirring
1, the 2- epoxy butanes of matrix amount 150%, 70 DEG C of heating water bath 12h.Products obtained therefrom is neutralized with the watery hydrochloric acid of 10% mass fraction
It is 7.1 to pH, with ethanol/water (75v/v) filtering and washing, in 45 DEG C of oven drying 24h, gained hydroxyl butyl starch is white powder
End, detects that its substitution value is 1.79 through the above method.
The present embodiment is visible, and the raising of low-kappa number and oxygenation pretreatment to hydroxyl butyl starch substitution value plays the role of very big.
Under the action of an acid, starch molecule amount reduces, and starch surface is destroyed, and occurs many apertures, and starch structure in amylum body
It is loose, the characteristic of ative starch is changed, is conducive to starch during alkalization to expand.During alkali process, loose starch molecule expansion activation,
Hydroxyl is set to become negative oxygen ion, compatibility enhancing.Double alkalisation makes starch expansion fully and is not gelatinized, and amylase activity increases
By force, utilization rate increases, compared to ative starch, and hydroxyl butyl starch substitution value obtained by low-kappa number and oxygenation pretreatment is greatly improved, soda acid
Collaboration pretreatment gained hydroxyl butyl starch substitution value is then higher.
The main etherification starch that low degree of substitution is prepared in aqueous phase in traditional industry, and main object is ethoxy, hydroxypropyl
Base starch.Hydroxyl butyl starch research for high substituted degree is then seldom, and external hydroxyl butyl starch product is ripe and maintains secrecy, institute
It is significant with the research to hydroxyl butyl starch.
The preparation of existing etherification starch is broadly divided into dry method, water dispersion, non-aqueous solvent method and mini-emulsion process.Dry method can
To obtain the product that pure white, powdery, substitution value are high, but finished product is difficult to purify, and has explosion danger, is difficult to industrialize at present.It is micro-
Emulsification law system is not sufficiently stable, and technological requirement is high.Etherification starch substitution value obtained by water dispersion is low.High-temperature high-pressure reaction kettle also can
Etherification starch substitution value is effectively improved, but equipment requirement is high, it is also difficult to industrialize.Alcohol alkaline process improves the method for substitution value in state
Inside have involved, but then non-someone studied the method for soda acid collaboration pretreatment raising substitution value.And this invention combine acid,
Alkali prepares the hydroxyl butyl starch of high substituted degree to the synergy of starch, process safety, it is simple, be easily isolated.The particle of preparation
Shape starch also helps further modification, with big value.
Embodiment 2
1) cornstarch is scattered in methanol, is configured to mass fraction for 35% starch milk, is placed in three-necked flask.Room
Stirred under temperature, add starch on dry basis quality 1.7mL/g concentrated hydrochloric acid, stir 0.3h.Warming-in-water stirs 4h to 45 DEG C.
Stop heating, it is 6.8 that pH is neutralized to sodium carbonate liquor, and products obtained therefrom is washed with ethanol/water (70v/v), it is dry in 45 DEG C of baking ovens
Dry 24h, obtains low-kappa number cornstarch.
2) take low-kappa number cornstarch to be scattered in ethanol, be made into the starch milk that mass fraction is 10%, be placed in three mouthfuls
In flask.40 DEG C of water-baths, are at the uniform velocity added dropwise containing the aqueous slkali that sodium hydroxide is starch on dry basis quality 0.04%, react 45min.Gained
It is 6.8 that product, which is neutralized to pH with the watery hydrochloric acid of 8% mass fraction, is washed with 95% ethanol, in 45 DEG C of oven drying 24h, obtains sour
Alkali collaboration pretreatment cornstarch.
3) soda acid collaboration pretreatment cornstarch is scattered in 85% ethanol, is made into the starch that mass fraction is 35%
Breast, adds the aqueous slkali that sodium hydroxide is starch on dry basis quality 4%, is passed through nitrogen 10min, rapidly joins as starch while stirring
1, the 2- epoxy butanes of butt quality 100%, 70 DEG C of heating water bath 14h.Products obtained therefrom is neutralized with the watery hydrochloric acid of 8% mass fraction
It is 6.8 to pH, with ethanol/water (50v/v) filtering and washing, in 45 DEG C of oven drying 24h, gained hydroxyl butyl starch is white powder
End, detects that its substitution value is 1.71 through the above method.
Embodiment 3
1) farina is scattered in isopropanol, is configured to mass fraction for 35% starch milk, is placed in three-necked flask
In.Stir at room temperature, add starch on dry basis quality 2mL/g concentrated hydrochloric acid, stir 40min.Warming-in-water is to 45 DEG C, stirring
5h.Stop heating, it is 6.8 to pH to be neutralized to sodium carbonate liquor neutral, and products obtained therefrom is washed with ethanol/water (60v/v), in 45
DEG C oven drying 24h, obtains low-kappa number farina.
2) take low-kappa number farina to be scattered in isopropanol, be made into mass fraction and burnt for 12% starch milk in three mouthfuls
In bottle.40 DEG C of water-baths, are at the uniform velocity added dropwise containing the aqueous slkali that sodium hydroxide is the mass of starch on dry basis 0.05%, react 50min.Gained is produced
It is 6.8 that product, which are neutralized to pH with the watery hydrochloric acid of 8% mass fraction, is washed with 95% ethanol, in 45 DEG C of oven drying 24h, obtains soda acid
Collaboration pretreatment farina.
3) soda acid collaboration pretreatment farina is scattered in 90% isopropanol, is made into the shallow lake that mass fraction is 40%
Powder breast, adds the aqueous slkali that sodium hydroxide is starch on dry basis 5%, is passed through nitrogen 10min, rapidly join and done for starch while stirring
1, the 2- epoxy butanes of matrix amount 180%, 70 DEG C of heating water bath 12h.It is 7.2 that products obtained therefrom, which is neutralized to pH with watery hydrochloric acid, uses second
Alcohol/water (30v/v) filtering and washing, in 45 DEG C of oven drying 24h, gained hydroxyl butyl starch is white powder, is examined through the above method
It is 1.52 to survey its substitution value.
Embodiment 4
1) tapioca is scattered in isopropanol, is configured to mass fraction for 35% starch milk, is placed in three-necked flask.
Stir at room temperature, add starch on dry basis quality 2mL/g concentrated hydrochloric acid, stir 40min.Warming-in-water stirs 4h to 45 DEG C.
Stop heating, it is 6.8 to pH to be neutralized to sodium carbonate liquor neutral, and products obtained therefrom is washed with ethanol/water (50v/v), in 45 DEG C
Oven drying 24h, obtains low-kappa number tapioca starch.
2) take low-kappa number tapioca to be scattered in isopropanol, be made into mass fraction for 12% starch milk in three-necked flask
In.35 DEG C of water-baths, are at the uniform velocity added dropwise containing the aqueous slkali that sodium hydroxide is the mass of starch on dry basis 0.05%, react 40min.Products obtained therefrom
It is 7.0 that pH is neutralized to the watery hydrochloric acid of 8% mass fraction, is washed with 95% ethanol, in 40 DEG C of oven drying 24h, obtains soda acid association
With pretreatment tapioca starch.
3) soda acid collaboration pretreatment tapioca is scattered in 90% isopropanol, is made into the starch that mass fraction is 35%
Breast, adds the aqueous slkali that sodium hydroxide is starch on dry basis 6%, is passed through nitrogen 10min, rapidly joins as starch on dry basis while stirring
1, the 2- epoxy butanes of quality 250%, 60 DEG C of heating water bath 12h.Products obtained therefrom is neutralized to the watery hydrochloric acid of 10% mass fraction
PH is 6.8, with ethanol/water (60v/v) filtering and washing, and in 45 DEG C of oven drying 24h, gained hydroxyl butyl starch is white powder,
Detect that its substitution value is 1.79 through the above method.
Embodiment 5
1) by green starch, pea starch 1：It is scattered in after 1 mixing in isopropanol, is configured to mass fraction for 30% starch
Breast, is placed in three-necked flask.Stir at room temperature, add starch on dry basis quality 2mL/g concentrated hydrochloric acid, stir 30min.Water-bath
45 DEG C are warming up to, 6h is stirred.Stop heating, be neutralized to sodium carbonate liquor it is neutral to pH be 6.8, products obtained therefrom ethanol/water
(50v/v) is washed, and in 45 DEG C of oven drying 24h, obtains low-kappa number starch.
2) take low-kappa number starch dispersion in ethanol, be made into mass fraction for 10% starch milk in three-necked flask.35
DEG C water-bath, is at the uniform velocity added dropwise containing the aqueous slkali that sodium hydroxide is the mass of starch on dry basis 0.05%, reacts 40min.Products obtained therefrom is used
It is 7.2 that the watery hydrochloric acid of 10% mass fraction, which is neutralized to pH, is washed with 95% ethanol, in 50 DEG C of oven drying 24h, obtains soda acid collaboration
Pretreated starch.
3) soda acid collaboration pretreated starch is scattered in 90% isopropanol, is made into the starch milk that mass fraction is 40%,
The aqueous slkali that sodium hydroxide is starch on dry basis 6% is added while stirring, is passed through nitrogen 10min, is rapidly joined as starch on dry basis matter
1, the 2- epoxy butanes of amount 100%, 50 DEG C of heating water bath 14h.Products obtained therefrom is neutralized to pH with the watery hydrochloric acid of 10% mass fraction
For 7.1, with ethanol/water (35v/v) filtering and washing, in 45 DEG C of oven drying 24h, gained hydroxyl butyl starch is white powder, warp
The above method detects that its substitution value is 1.48.
Gained starch heat paste viscosity of the invention is far below ative starch, and also not occurring during cooling can shape under retrogradation, high concentration
Into stable gel, with stronger application.The present invention cooperates with pretreatment mode combination double alkalisation using soda acid, and fully activation is formed sediment
Powder, increases operation rate, and prepares the hydroxyl butyl starch of high substituted degree, not only enriches etherification starch species, moreover it is possible to avoid high temperature high
The technology difficulties such as pressure.Required reaction condition is simple and easy to get, the technique such as suction filtration, purification be easy to carry out, the starch be cornstarch,
One or more in farina, tapioca, green starch, pea starch, substantially increase the system of hydroxyl butyl starch
Standby scope, enhances universality.
The embodiment of the present invention is used for the purpose of clearly demonstrating example of the present invention, rather than to the embodiment party of the present invention
The restriction of formula.
Claims (10)
1. a kind of method that soda acid collaboration pretreatment prepares high substituted degree hydroxyl butyl starch, it is characterised in that comprise the following steps：
1) by starch dispersion in Organic Alcohol, it is made into the starch milk that mass percent is 30~40%；
2) by step 1) products obtained therefrom stirs at room temperature, adds concentrated hydrochloric acid, it is stirred for uniform；Every gram of starch on dry basis adds dense
Hydrochloric acid is 1~4mL；
3) by step 2) products therefrom is placed in 40~55 DEG C of water-baths, and 3~6h is stirred under 200~250rpm speed；
4) stop heating, with sodium carbonate liquor neutralization procedure 3) products obtained therefrom to pH be 6.5~7.5；
5) by step 4) products therefrom washs with ethanol/water, dries；
6) by step 5) products therefrom be made into Organic Alcohol 5%~15% starch milk；
7) by step 6) products therefrom is placed in 30~40 DEG C of thermostat water baths, and sodium hydroxide solution is at the uniform velocity added dropwise, and reaction continues
30~60min；Added sodium hydroxide concentration is the quality 0.02~0.08% of starch on dry basis；
8) by step 7) reaction products therefrom suction filtration, is washed with ethanol/water, is 6.5~7.5 with concentrated hydrochloric acid regulation pH, suction filtration is washed
Wash, dry；
9) by step 8) reaction products therefrom is scattered in Organic Alcohol, adds the sodium hydroxide of starch on dry basis quality 2~8%；It is logical
Enter nitrogen, add 1, the 2- epoxy butanes of starch on dry basis quality 100~250%；8~14h is reacted at 50~70 DEG C；
10) by step 9) reaction products therefrom neutralized with watery hydrochloric acid, use ethanol/water washes clean, dry, obtain high substituted degree hydroxyl fourth
Base starch.
2. the method that the soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, its feature exists
In the Organic Alcohol is methanol, ethanol or isopropanol.
3. the method that the soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, its feature exists
In step 2) stir speed (S.S.) is 200~250rpm.
4. the method that soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, it is characterised in that
Step 10) neutralize when examined with silver nitrate solution, until without white precipitate generation.
5. the method that the soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, its feature exists
In step 5), step 8) and step 10) in, described drying is dries 24h in 40 DEG C~50 DEG C thermostatic drying chambers.
6. the method that the soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, its feature exists
In step 5), step 8) and step 10) described in ethanol/water volume ratio 20~80：100.
7. the method that the soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, its feature exists
In the starch is the one or more in cornstarch, farina, tapioca, green starch, pea starch.
8. the method that the soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, its feature exists
In step 9) in be passed through 5~10min of nitrogen.
9. the method that the soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, its feature exists
In the mass fraction of the concentrated hydrochloric acid is 36%.
10. the method that the soda acid collaboration pretreatment described in right 1 as requested prepares high substituted degree hydroxyl butyl starch, its feature exists
In the mass fraction of the watery hydrochloric acid is 5%~10%；Step 9) in Organic Alcohol mass fraction be 85~95%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108559004A (en) * | 2018-04-13 | 2018-09-21 | 周枫 | A kind of preparation method and application of multiple elements design converted starch |
| CN109999121A (en) * | 2019-05-10 | 2019-07-12 | 深圳市明臣眼科医疗有限公司 | Treat amblyopia Chinese medicine lotion for external use and preparation method thereof |
| CN110093792A (en) * | 2019-05-23 | 2019-08-06 | 成都市山马生物科技有限公司 | A kind of high substituted carboxymethyl starch composite reactive printing gum and preparation method |
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| CN1322215A (en) * | 1998-08-04 | 2001-11-14 | 联合碳化化学品及塑料技术公司 | Production of polysaccharide ethers |
| CN1683417A (en) * | 2005-03-07 | 2005-10-19 | 中国科学院广州化学研究所 | Process for preparing high substituted degree hydroxyalkyl starch |
| CN104497154A (en) * | 2014-12-17 | 2015-04-08 | 华南理工大学 | Preparation method of hydroxy butyl starch ether or hydroxy butyl modified starch ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1322215A (en) * | 1998-08-04 | 2001-11-14 | 联合碳化化学品及塑料技术公司 | Production of polysaccharide ethers |
| CN1683417A (en) * | 2005-03-07 | 2005-10-19 | 中国科学院广州化学研究所 | Process for preparing high substituted degree hydroxyalkyl starch |
| CN104497154A (en) * | 2014-12-17 | 2015-04-08 | 华南理工大学 | Preparation method of hydroxy butyl starch ether or hydroxy butyl modified starch ether |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559004A (en) * | 2018-04-13 | 2018-09-21 | 周枫 | A kind of preparation method and application of multiple elements design converted starch |
| CN109999121A (en) * | 2019-05-10 | 2019-07-12 | 深圳市明臣眼科医疗有限公司 | Treat amblyopia Chinese medicine lotion for external use and preparation method thereof |
| CN110093792A (en) * | 2019-05-23 | 2019-08-06 | 成都市山马生物科技有限公司 | A kind of high substituted carboxymethyl starch composite reactive printing gum and preparation method |
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