CN106496338A - A kind of preparation technology of molten paste method high-substitution carboxymethyl modified starch - Google Patents
A kind of preparation technology of molten paste method high-substitution carboxymethyl modified starch Download PDFInfo
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Abstract
The invention discloses a kind of preparation technology of molten paste method high-substitution carboxymethyl modified starch, the technique is：Starch is first heated to more than gelatinization point in solvent aqueous solution, gelatinizing or the half gelatinizing activation processing of starch granuless is carried out；The solvent method carboxy methylation of half gelatinized starch.Half gelatinization process of starch mainly includes：The operating procedures such as breast, heating half gelatinizing, intermediate washings, drying, crushing is once adjusted；Carboxy methylation process mainly includes：The operating process such as secondary tune breast, starch alkalization, monoxone etherificate and subsequent treatment.The main creation point of the present invention is, the gelatinizing activation method of starch is combined with solvent method, it is achieved that half gelatinizing of starch granuless.Both the property of ative starch had been remained, the chemical reactivity of starch had been activated again, the carboxymethylated reaction efficiency of solvent method and product substitution value has been improve, is improved the performance of product.
Description
Technical field
The present invention relates to a kind of carboxymethyl modified starch preparation technology, and in particular to a kind of molten paste method high-substitution carboxymethyl
The preparation technology of modified starch.
Background technology
Carboxymethyl starch is also called carboxymethyl starch sodium or carboxymethyl starch ether.Starch after carboxymethyl etherification, granule
Original destructurized, there is product strong water-soluble, substitution value 0.1 and can be dissolved in cold water above, be clarified, thoroughly
Bright, sticky gelatinized corn starch, the viscosity of paste are high compared with ative starch, and transparency is high, and freeze-thaw stability is good.Within the specific limits, carboxymethyl
The properties such as the viscosity of gelatinized corn starch, transparency, freeze-thaw stability are improved with the increase of substitution value.
At present, there is no strict definition to the height of degree of substitution by carboxymethyl, it is believed that substitution value being more than 0.8
Carboxymethyl starch with high substitution degree.The more carboxymethyl products of industrial application are all low degree of substitution, and general substitution value is below
0.3, and technique is also more skillful, but the research of high substituted carboxymethyl product is shorter, and carboxymethyl starch with high substitution degree is due to which
Good water solubility, water absorption are strong, and viscosity is high, and superior performance, application are more wide, so needing to form sediment high-substitution carboxymethyl
Powder preparation technique and performance are furtherd investigate.
Carboxymethyl starch with high substitution degree primary solvent method method is preparing, produce.Comparatively, wet method, dry method and half-dried
Carboxymethyl starch substitution value prepared by method is not high；Solvent method is although relatively costly, but starch granuless can be suppressed to expand, and improves anti-
Answer efficiency, product substitution value height and uniform substituent distribution.Both at home and abroad major part solvent method be with methanol, ethanol, isopropanol, third
The low-carbon (LC) organic solvent such as ketone, in the middle of various organic solvents, with isopropanol best results, reaction efficiency is high, the carboxymethyl for obtaining
Starch substitution value is high.The present invention is more relatively cheap than wide, price using source and safety is relatively good ethanol and isopropanol
As solvent, solvent process is improved, carboxymethyl starch with high substitution degree is prepared, be to improve carboxymethyl starch substitution value and reaction effect
Rate, open up its broader application a kind of new approaches and new method are provided.
Content of the invention
Carboxymethyl modified starch substitution value and reaction efficiency is not high and substitution value that the present invention is prepared for existing solvent method
A kind of low defect, there is provided preparation technology of efficient high-substitution carboxymethyl modified starch.
Concrete technical scheme of the present invention is as follows.
The present invention by first carrying out half gelatinizing activation processing of solvent to starch, then carries out the work of carboxymethyl etherification reaction to which
Process, is prepared for high-substitution carboxymethyl modified starch, hence it is evident that improve the substitution value and reaction efficiency of carboxymethyl starch, can
To meet the technical need to carboxymethyl starch with high substitution degree product.Concrete preparation process includes two steps：The first step, is starch elder generation
More than gelatinization point is heated in solvent aqueous solution, gelatinizing or the half gelatinizing activation processing of starch granuless is carried out；Second
Step, is the solvent method carboxy methylation of half gelatinized starch.Half gelatinization process of starch mainly includes：Once adjust breast, heating half gelatinizing,
The operating procedures such as intermediate washings, drying, crushing；Carboxy methylation process mainly includes：Secondary tune breast, starch alkalization, monoxone ether
Change and the operating process such as subsequent treatment.
Different from the process of preparing of conventional carboxymethyl starch, the main innovation point of the present invention is, is carrying out carboxylic first
Before base, half gelatinizing activation processing of solvent method is first carried out to starch.In water phase, gelatinizing and dissolving are different from traditional starch,
Starch granuless gelatinizing in a solvent and half gelatinizing have simply carried out incomplete expansion and gelatinizing, it is possible thereby to greatly improve carboxylic
The efficiency of methylation reaction and the uniformity of reaction, and improve the performance of final products simultaneously.
Carboxymethyl etherification modified starch prepared by the present invention has that substitution value is high, reaction efficiency is high, viscometric properties are excellent, water
The application features such as dissolubility is good, transparency is high, freeze-thaw stability is high, good film-forming property so that this kind of modified starch has bonding, protects
Multiple excellent results such as water, emulsifying, can be used widely in a lot of fields, such as in printing and dyeing, papermaking, daily use chemicals, gluing
The fields such as agent, food, medicine, oil drilling.
A kind of preparation technology of molten paste method high-substitution carboxymethyl modified starch, comprises the following steps：
（1）Breast is once adjusted：It is 40% ~ 60% ethanol or aqueous isopropanol with volumetric concentration, starch is tuned into concentration for 5%～50%
The starch milk of wt；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 70
～100 DEG C, 0.1～12h of temperature retention time makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be that 70%～100% ethanol or isopropanol are washed, filtered with concentration of volume percent, pass through
Dry, crush, sieve, obtain half gelatinized starch；
（4）Secondary tune breast：With ethanol or aqueous isopropanol that volumetric concentration is 80% ~ 100%, half gelatinized starch is tuned into concentration is
The starch milk of 5%～50% wt；
（5）Starch alkalizes：Under stirring, sodium hydroxide, reaction, control reaction temperature in the secondary starch milk that adjusts, will be added
Spend for 20～60 DEG C, 0.5～24h of response time；
（6）Monoxone is etherified：Passing through（5）Monoxone is added in the reaction system of process, and chlorination acetic acid time control is 1～30
Min, reaction temperature are 20～60 DEG C；
（7）Subsequent treatment：After etherificate terminates, with acid for adjusting pH to 6.5～7.5, it is 70%～100% ethanol or different with volumetric concentration
Propanol rinse, filtration, drying, crush, sieve, and obtain carboxymethyl starch.
In above-mentioned technique, step（1）With（4）In, the reaction medium is ethanol solution or the one kind in aqueous isopropanol
More than.
In above-mentioned technique, step（1）In, the starch include Semen Maydiss, waxy corn, Maninot esculenta crantz., Rhizoma Solani tuber osi, Semen Tritici aestivi, Radix Ipomoeae,
Semen phaseoli radiati, Oryza glutinosa, sago, banana dasheen, Semen Pisi sativi and other plant ative starchs, or through mass percent concentration 0.05% ~ 0.20%
One or more of cross-linking modified starch of above-mentioned starch of epoxychloropropane crosslinking Treatment.
In above-mentioned technique, step（5）In, in starch milk, add sodium hydroxide to include sodium hydroxide solution and solid hydrogen-oxygen
Change sodium, wherein sodium hydroxide solution mass percent concentration is 20%～55%, amount of sodium hydroxide is added for starch on dry basis quality
20%～200%.
In above-mentioned technique, step（6）In, the monoxone amount of addition is the 20%～200% of starch on dry basis quality.
In above-mentioned technique, step（7）Middle use acid for adjusting pH, acid used are glacial acetic acid or hydrochloric acid.
The main creation point of the present invention is, the gelatinizing activation method of starch is combined with solvent method, it is achieved that starch
Half gelatinizing of granule.Both the property of ative starch had been remained, the chemical reactivity of starch had been activated again, solvent method carboxylic first had been improve
The reaction efficiency of base and product substitution value, improve the performance of product.
Solvent method is the most popular method for preparing carboxymethyl starch with high substitution degree, can effectively suppress starch granuless to expand, have
Carry out beneficial to reaction system mass transfer, product substitution value is high and uniform substituent distribution, properties of product are preferable；Gelatinizing method of modifying can
To change starch granuless structure to a certain extent, being conducive to reagent to be efficiently entering inside granule carries out chemical reaction, improves carboxylic first
The substitution value and reaction efficiency of base starch.Both approaches are combined, the new work of marginal molten paste method is formed
Skill, can significantly improve the substitution value and reaction efficiency of carboxymethyl starch, and energy effectively solving carboxymethyl starch with high substitution degree is difficult to
A difficult problem for preparation.
High-substitution carboxymethyl modified starch prepared by the present invention, technique, product structure and aspect of performance relative to
The carboxymethyl starch with high substitution degree of ative starch, low degree of substitution carboxymethyl starch or other document reports has following clear superiority：
（1）In technique, the solvent method of modified starch and gelatinizing method of modifying are be combined with each other, form new molten paste method technique,
Compared with carboxymethyl starch with high substitution degree is prepared with traditional solvent method, substitution value and the reaction of carboxymethyl starch can be significantly improved
Efficiency.
（2）On product structure, through the carboxymethyl starch with high substitution degree that molten paste method is prepared, the crystalline texture of granule
Destroyed, chemosmosiss are significantly improved, and when substitution value is more than 1.0, averagely have more than one hydroxyl in each glucose unit
Base is replaced by carboxymethyl group, and the water solublity of starch greatly strengthens.
（3）Due to the molecular chain structure of starch after gelatinizing more open, in the case of same substitution value, the substep of functional group
Than more uniform, therefore, in properties of product, through the carboxymethyl starch with high substitution degree that molten paste method is prepared, with substitution value
The application features such as higher, viscometric properties are excellent, good water solubility, transparency height, freeze-thaw stability height, good film-forming property.
Specific embodiment
Make further concrete detailed description to the present invention with reference to specific embodiment, but embodiments of the present invention are not
It is limited to this, for the technological parameter especially not indicated, can refer to routine techniquess is carried out.
Embodiment 1
（1）Breast is once adjusted：With the ethanol solution that volumetric concentration is 40%, 200g corn starchs are tuned into the starch that concentration is 5%wt
Breast；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 70
DEG C, temperature retention time 12h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be 70% washing with alcohol, filtration with concentration of volume percent, drying, crush, sieve,
Obtain half gelatinized starch；
（4）Secondary tune breast：With the ethanol solution that volumetric concentration is 80%, above-mentioned half gelatinized starch is tuned into the shallow lake that concentration is 5% wt
Powder breast；
（5）Starch alkalizes：Under stirring, the hydroxide of relative starch quality 20% will be added in the secondary starch milk that adjusts
Sodium, controlling reaction temperature are 45 DEG C, response time 8h；
（6）Monoxone is etherified：Passing through（5）Monoxone relative starch quality 20%, chlorination is slowly added in the reaction system of process
In 10 min, reaction temperature is 45 DEG C to acetic acid time control；
（7）Subsequent treatment：After etherificate terminates, with salt acid for adjusting pH to 6.5, it is 70% washing with alcohol, mistake with concentration of volume percent
Filter, drying, crushes, sieves, and obtains carboxymethyl starch.
Embodiment 2
（1）Breast is once adjusted：With the ethanol solution that volumetric concentration is 50%, 200g potato starch is tuned into the shallow lake that concentration is 15%wt
Powder breast；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 75
DEG C, temperature retention time 10h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be 75% washing with alcohol, filtration with concentration of volume percent, drying, crush, sieve,
Obtain half gelatinized starch；
（4）Secondary tune breast：With the ethanol solution that volumetric concentration is 100%, it is 50% wt that above-mentioned half gelatinized starch is tuned into concentration
Starch milk；
（5）Starch alkalizes：Under stirring, the sodium hydroxide to starch quality 50% will be added in the secondary starch milk that adjusts,
Controlling reaction temperature is 20 DEG C, response time 24h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 60%, chlorination second
In 20 min, reaction temperature is 35 DEG C to sour time control；
（7）Subsequent treatment：After etherificate terminates, pH to 7.5 is adjusted with glacial acetic acid, washed for 100% ethanol with concentration of volume percent
Wash, filter, drying, crush, sieve, obtain carboxymethyl starch.
Embodiment 3
（1）Breast is once adjusted：With the ethanol solution that volumetric concentration is 60%, 200g tapiocas are tuned into the shallow lake that concentration is 25% wt
Powder breast；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 80
DEG C, temperature retention time 8h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be 80% washing with alcohol, filtration with concentration of volume percent, drying, crush, sieve,
Obtain half gelatinized starch；
（4）Secondary tune breast：With the ethanol solution that volumetric concentration is 90%, above-mentioned half gelatinized starch is tuned into the shallow lake that concentration is 25%wt
Powder breast；
（5）Starch alkalizes：Under stirring, the hydroxide to starch quality 100% will be added in the secondary starch milk that adjusts
Sodium, controlling reaction temperature are 60 DEG C, response time 0.5h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 110%, chlorination
In 1 min, reaction temperature is 60 DEG C to acetic acid time control；
（7）Subsequent treatment：After etherificate terminates, with salt acid for adjusting pH to 6.8, it is 75% washing with alcohol, mistake with concentration of volume percent
Filter, drying, crushes, sieves, and obtains carboxymethyl starch.
Embodiment 4
（1）Breast is once adjusted：With the ethanol solution that volumetric concentration is 55%, by 200g Semen Maydiss, Maninot esculenta crantz. mixing starch（According to mass ratio
For 1：1 ratio row mixing）, it is tuned into the starch milk that concentration is 35% wt；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 90
DEG C, temperature retention time 6h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be 85% washing with alcohol, filtration with concentration of volume percent, drying, crush, sieve,
Obtain half gelatinized starch；
（4）Secondary tune breast：With the ethanol solution that volumetric concentration is 85%, above-mentioned half gelatinized starch is tuned into the shallow lake that concentration is 35%wt
Powder breast；
（5）Starch alkalizes：Under stirring, the hydroxide to starch quality 150% will be added in the secondary starch milk that adjusts
Sodium, controlling reaction temperature are 40 DEG C, response time 12h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 160%, chlorination
In 5 min, reaction temperature is 60 DEG C to acetic acid time control；
（7）Subsequent treatment：Etherificate terminate after, with glacial acetic acid adjust pH to 7.0, with concentration of volume percent be 80% washing with alcohol,
Filter, drying, crush, sieve, obtain carboxymethyl starch.
Embodiment 5
（1）Breast is once adjusted：With the aqueous isopropanol that volumetric concentration is 40%, by 200g Semen Maydiss, waxy corn mixing starch（According to
Mass ratio is 1：1 ratio row mixing）, it is tuned into the starch milk that concentration is 45% wt；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is
100 DEG C, temperature retention time 0.1h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, washed, filtered for 90% isopropanol with concentration of volume percent, drying, crushing, mistake
Sieve, obtains half gelatinized starch；
（4）Secondary tune breast：With the aqueous isopropanol that volumetric concentration is 80%, above-mentioned half gelatinized starch is tuned into concentration for 30% wt
Starch milk；
（5）Starch alkalizes：Under stirring, the hydroxide to starch quality 200% will be added in the secondary starch milk that adjusts
Sodium, controlling reaction temperature are 50 DEG C, response time 5h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 200%, chlorination
In 30 min, reaction temperature is 20 DEG C to acetic acid time control；
（7）Subsequent treatment：After etherificate terminates, pH to 7.0 is adjusted with glacial acetic acid, washed for 85% isopropanol with concentration of volume percent
Wash, filter, drying, crush, sieve, obtain carboxymethyl starch.
Embodiment 6
（1）Breast is once adjusted：With the ethanol solution that volumetric concentration is 43%, by 200g through the epoxy chlorine equivalent to starch on dry basis 0.05%
The maize modified starch of propane crosslinking is tuned into the starch milk that concentration is 50% wt；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 75
DEG C, temperature retention time 0.5h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be 95% washing with alcohol, filtration with concentration of volume percent, drying, crush, sieve,
Obtain half gelatinized starch；
（4）Secondary tune breast：With the aqueous isopropanol that volumetric concentration is 95%, above-mentioned half gelatinized starch is tuned into concentration for 45% wt
Starch milk；
（5）Starch alkalizes：Under stirring, will add in the secondary starch milk that adjusts to 20% sodium hydroxide of starch quality（Molten
Liquid：20% wt of concentration, quality 100% is to starch）, controlling reaction temperature is 30 DEG C, response time 18h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 22%, chlorination second
In 20 min, reaction temperature is 40 DEG C to sour time control；
（7）Subsequent treatment：After etherificate terminates, with salt acid for adjusting pH to 7.5, washed for 90% isopropanol with concentration of volume percent,
Filter, drying, crush, sieve, obtain carboxymethyl starch.
Embodiment 7
（1）Breast is once adjusted：Mixed with the equivalent of the ethanol solution that volumetric concentration is 40% and aqueous isopropanol that volumetric concentration is 40%
200g is tuned into concentration for 45%wt through the Maninot esculenta crantz. modified starch that the epoxychloropropane equivalent to starch on dry basis 0.15% is crosslinked by compound
Starch milk；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 72
DEG C, temperature retention time 1h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, with concentration of volume percent be 100% washing with alcohol, filtration, drying, crushing, mistake
Sieve, obtains half gelatinized starch；
（4）Secondary tune breast：Mixed with the equivalent of the ethanol solution that volumetric concentration is 90% and aqueous isopropanol that volumetric concentration is 90%
Above-mentioned half gelatinized starch is tuned into the starch milk that concentration is 35% wt by compound；
（5）Starch alkalizes：Under stirring, will add in the secondary starch milk that adjusts to 50% sodium hydroxide of starch quality（Molten
Liquid：25% wt of concentration, quality 320% is to starch）, controlling reaction temperature is 30 DEG C, response time 20h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 55%, chlorination second
In 5 min, reaction temperature is 30 DEG C to sour time control；
（7）Subsequent treatment：After etherificate terminates, with salt acid for adjusting pH to 6.5, it is 95% washing with alcohol, mistake with concentration of volume percent
Filter, drying, crushes, sieves, and obtains carboxymethyl starch.
Embodiment 8
（1）Breast is once adjusted：With the ethanol solution that volumetric concentration is 52%, by 200g through the epoxy chlorine equivalent to starch on dry basis 0.20%
The Rhizoma Solani tuber osi modified starch of propane crosslinking is tuned into the starch milk that concentration is 30% wt；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 79
DEG C, temperature retention time 2h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be 92% washing with alcohol, filtration with concentration of volume percent, drying, crush, sieve,
Obtain half gelatinized starch；
（4）Secondary tune breast：With the ethanol solution that volumetric concentration is 90%, it is 25% wt that above-mentioned half gelatinized starch is tuned into concentration
Starch milk；
（5）Starch alkalizes：Under stirring, will add in the secondary starch milk that adjusts to 100% sodium hydroxide of starch quality
（Solution：30% wt of concentration, quality 333% is to starch）, controlling reaction temperature is 55 DEG C, response time 2h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 110%, chlorination
In 15min, reaction temperature is 45 DEG C to acetic acid time control；
（7）Subsequent treatment：After etherificate terminates, with salt acid for adjusting pH to 7.0, with concentration of volume percent be 100% washing with alcohol,
Filter, drying, crush, sieve, obtain carboxymethyl starch.
Embodiment 9
（1）Breast is once adjusted：With the ethanol solution that volumetric concentration is 55%, 200g sweet potato starch is tuned into the shallow lake that concentration is 25% wt
Powder breast；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 80
DEG C, temperature retention time 0.9h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be 88% washing with alcohol, filtration with concentration of volume percent, drying, crush, sieve,
Obtain half gelatinized starch；
（4）Secondary tune breast：With the ethanol solution that volumetric concentration is 90%, it is 50% wt that above-mentioned half gelatinized starch is tuned into concentration
Starch milk；
（5）Starch alkalizes：Under stirring, will add in the secondary starch milk that adjusts to 150% sodium hydroxide of starch quality
（Solution：40% wt of concentration, quality 375% is to starch）, controlling reaction temperature is 40 DEG C, response time 10h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 160%, chlorination
In 5 min, reaction temperature is 50 DEG C to acetic acid time control；
（7）Subsequent treatment：Etherificate terminate after, with glacial acetic acid adjust pH to 7.5, with concentration of volume percent be 98% washing with alcohol,
Filter, drying, crush, sieve, obtain carboxymethyl starch.
Embodiment 10
（1）Breast is once adjusted：With the ethanol solution that volumetric concentration is 50%, 200g wheaten starches are tuned into the shallow lake that concentration is 20% wt
Powder breast；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 91
DEG C, temperature retention time 3h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be 78% washing with alcohol, filtration with concentration of volume percent, drying, crush, sieve,
Obtain half gelatinized starch；
（4）Secondary tune breast：With the aqueous isopropanol that volumetric concentration is 90%, it is 5% wt that above-mentioned half gelatinized starch is tuned into concentration
Starch milk；
（5）Starch alkalizes：Under stirring, will add in the secondary starch milk that adjusts to 200% sodium hydroxide of starch quality
（Solution：50% wt of concentration, quality 400% is to starch）, controlling reaction temperature is 35 DEG C, response time 8h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 200%, chlorination
In 30 min, reaction temperature is 20 DEG C to acetic acid time control；
（7）Subsequent treatment：After etherificate terminates, with salt acid for adjusting pH to 7.0, it is 88% washing with alcohol, mistake with concentration of volume percent
Filter, drying, crushes, sieves, and obtains carboxymethyl starch.
Embodiment 11
（1）Breast is once adjusted：With the aqueous isopropanol that volumetric concentration is 60%, by 200g Semen phaseoli radiatis, Oryza glutinosa, sago, banana dasheen, Semen Pisi sativi
Mixing starch（Mix according to mass ratio row are waited）, it is tuned into the starch milk that concentration is 45% wt；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 98
DEG C, temperature retention time 10h makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, washed, filtered for 70% isopropanol with concentration of volume percent, drying, crushing, mistake
Sieve, obtains half gelatinized starch；
（4）Secondary tune breast：With the aqueous isopropanol that volumetric concentration is 100%, above-mentioned half gelatinized starch is tuned into concentration for 50% wt
Starch milk；
（5）Starch alkalizes：Under stirring, will add in the secondary starch milk that adjusts to 120% sodium hydroxide of starch quality
（Solution：Concentration % 45wt, quality 267% is to starch）, controlling reaction temperature is 50 DEG C, response time 4h；
（6）Monoxone is etherified：Passing through（5）Monoxone is slowly added in the reaction system of process to starch quality 140%, chlorination
In 1 min, reaction temperature is 60 DEG C to acetic acid time control；
（7）Subsequent treatment：After etherificate terminates, with salt acid for adjusting pH to 6.5, washed for 75% isopropanol with concentration of volume percent,
Filter, drying, crush, sieve, obtain carboxymethyl starch.
Using the high-substitution carboxymethyl modified starch of above-mentioned preparation technology gained as sample, using copper sulfate precipitate-network
Close titration measuring degree of substitution by carboxymethyl.In each AGU average, the quantity of the substituted substituent group of hydroxyl is referred to as
Substitution value, the actual substitution value of modified starch and theoretical substitution value（Substitution value during etherifying agent total overall reaction）Ratio be referred to as react
Efficiency.As a result show that the carboxymethyl modified starch substitution value and reaction efficiency that prepare by the technique respectively reach 1.21 Hes
61.38%, compared to carboxymethyl modified starch prepared by conventional ethanol solvent method（Substitution value is 1.0 or so, and reaction efficiency is 50%
Left and right）, substitution value and reaction efficiency are significantly improved.In addition, accurately weighing 1.000g（Butt）Above-mentioned modified starch, plus distillation
Water is configured to 1.0%（Mass fraction）Gelatinized corn starch, place about 30min agitation as appropriate under room temperature, starch can quickly be dissolved into paste
And be uniformly dispersed, illustrate that the carboxymethyl starch water solublity is extremely strong.The quartz colorimetric utensil for pouring the good gelatinized corn starch of above-mentioned dissolving into 1cm
In, selection wavelength is 620 nm, and makees blank, determination sample light transmittance with distilled water.It was found that the carboxymethyl modified starch
Light transmittance is 36 ~ 38 times of ative starch, shows that the transparency of the carboxymethyl modified starch is greatly increased compared with ative starch.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
The change or variation of other multi-forms.There is no need to be exhaustive to all of embodiment.All the present invention
Any modification, equivalent and improvement that is made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (6)
1. a kind of preparation technology of molten paste method high-substitution carboxymethyl modified starch, it is characterised in that comprise the following steps：
（1）Breast is once adjusted：It is 40% ~ 60% ethanol or aqueous isopropanol with volumetric concentration, starch is tuned into concentration for 5%～50%
The starch milk of wt；
（2）Heat half gelatinizing：Under stirring, to step（1）Starch milk carry out heat treated, controlling reaction temperature is 70
～100 DEG C, 0.1～12h of temperature retention time makes starch granuless that limited expansion to occur, carries out half gelatinizing modified；
（3）Middle dry：Stop heating, be that 70%～100% ethanol or isopropanol are washed, filtered with concentration of volume percent, pass through
Dry, crush, sieve, obtain half gelatinized starch；
（4）Secondary tune breast：With ethanol or aqueous isopropanol that volumetric concentration is 80% ~ 100%, half gelatinized starch is tuned into concentration is
The starch milk of 5%～50% wt；
（5）Starch alkalizes：Under stirring, sodium hydroxide, reaction, control reaction temperature in the secondary starch milk that adjusts, will be added
Spend for 20～60 DEG C, 0.5～24h of response time；
（6）Monoxone is etherified：Passing through（5）Monoxone is added in the reaction system of process, and chlorination acetic acid time control is 1～30
Min, reaction temperature are 20～60 DEG C；
（7）Subsequent treatment：After etherificate terminates, with acid for adjusting pH to 6.5～7.5, it is 70%～100% ethanol or different with volumetric concentration
Propanol rinse, filtration, drying, crush, sieve, and obtain carboxymethyl starch.
2. the preparation technology of molten paste method high-substitution carboxymethyl modified starch according to claim 1, it is characterised in that step
Suddenly（1）With（4）In, the reaction medium is one or more of ethanol solution or aqueous isopropanol.
3. the preparation technology of molten paste method high-substitution carboxymethyl modified starch according to claim 1, it is characterised in that step
Suddenly（1）In, the starch includes Semen Maydiss, waxy corn, Maninot esculenta crantz., Rhizoma Solani tuber osi, Semen Tritici aestivi, Radix Ipomoeae, Semen phaseoli radiati, Oryza glutinosa, sago, Musa basjoo Sieb. Et Zucc.
Taro, Semen Pisi sativi and other plant ative starchs, or the epoxychloropropane crosslinking Treatment through mass percent concentration 0.05% ~ 0.20%
One or more of cross-linking modified starch of above-mentioned starch.
4. the preparation technology of molten paste method high-substitution carboxymethyl modified starch according to claim 1, it is characterised in that step
Suddenly（5）In, in starch milk, add sodium hydroxide to include sodium hydroxide solution and solid sodium hydroxide, wherein sodium hydroxide solution
Mass percent concentration is 20%～55%, adds amount of sodium hydroxide for the 20%～200% of starch on dry basis quality.
5. the preparation technology of molten paste method high-substitution carboxymethyl modified starch according to claim 1, it is characterised in that step
Suddenly（6）In, the monoxone amount of addition is the 20%～200% of starch on dry basis quality.
6. the preparation technology of molten paste method high-substitution carboxymethyl modified starch according to claim 1, it is characterised in that step
Suddenly（7）Middle use acid for adjusting pH, acid used are glacial acetic acid or hydrochloric acid.
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| CN110284362A (en) * | 2018-03-19 | 2019-09-27 | 金东纸业（江苏）股份有限公司 | Size-press starch and preparation method thereof |
| CN115960271A (en) * | 2023-01-17 | 2023-04-14 | 齐鲁工业大学(山东省科学院) | High-substitution-degree hydroxypropyl starch and preparation method and application thereof |
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| 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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