CN101348528A - Preparation of amorphous particulate carboxymethyl starch - Google Patents
Preparation of amorphous particulate carboxymethyl starch Download PDFInfo
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- CN101348528A CN101348528A CNA2008101981678A CN200810198167A CN101348528A CN 101348528 A CN101348528 A CN 101348528A CN A2008101981678 A CNA2008101981678 A CN A2008101981678A CN 200810198167 A CN200810198167 A CN 200810198167A CN 101348528 A CN101348528 A CN 101348528A
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Abstract
The invention provides a method capable of making a starch carboxylmethyl with high dissolution velocity in water, high stability and high transparency through high efficiency chemical reaction. The method comprises the following steps that (1) the raw material of starch is prepared into a 1 to 40 mass percent emulsified starch in an 30 to 60 volume percent ethanol solution; (2) the emulsified starch is decrystalized through heating or raising pH with addition of alkali; (3) 1 to 20 percent of chloroactic acid or sodium chloroactic against the weight of the starch is added with alkali to achieve a molar ratio between chloroactic acid or sodium chloroactic to sodium hydroxide of 1-2: 1-2, and the reaction lasts for 1-10 hours to accomplish the modification of the hydroxylmethyl group and; (4) a neutralization is carried out with an acid to regulate the pH to be between 6.5 and 7.0, followed by filtration and subsequent repeated rinsing with a 30 to 95 volume percent ethanol; followed by drying, selecting, and packaging to obtain the final product. The product can be widely applied to the fields of medicine/pharmacy, food, textile, printing, petroleum, daily chemicals, construction material, foundry, and packaging.
Description
Technical field
The present invention relates to the starch conversion field, specifically is to carry out decrystallized and the carboxymethyl etherification modification to starch in alcohol solvent, prepares amorphous particulate carboxymethyl starch.Present technique can directly be used in modified starch manufacturing enterprise, and the carboxymethyl starch product of being produced can be widely used in the fields such as medicine, food, weaving, printing and dyeing, petroleum drilling, daily-use chemical industry and building materials, casting, packing.
Background technology
Have amorphous domain and crystal region in the starch granules, amorphous domain has higher perviousness, and chemical reaction mainly occurs in this zone, if there is more amorphous domain in starch granules, will help the carrying out that react, improve reactive behavior, and reaction profile be even.The crystallizing system of amorphous particulate form starch is destroyed, and changes into the amorphous system, and volume expands to some extent, internal structure is no longer so tight, but still the granule-morphology that can be kept perfectly, this starch granules has higher perviousness, can more effective fully the contact with chemical reagent react.The amorphous particulate form starch main preparation methods has chemical high crosslinking, the medium moisture method of control, salts solution protection method, microwave wet heat treatment method, alcohol solvent protection method etc.On the one hand, because the alcohol solvent protection method is easy to control, prepare effectively, and ethanol can reclaim, thereby reduced production cost, is convenient to the use of scale operation; On the other hand, the production carboxymethyl starch mainly is to use solvent method in China, the solvent that uses is again based on ethanol, therefore, the present invention realizes the combination of two technological processs, promptly earlier starch is carried out decrystallizedly in the ethanol environment, directly in alcohol solvent, add etherifying agent then and directly carry out etherification reaction, formed new fabricating technology of the present invention.
The present low problem of industrial enterprise's production carboxymethyl starch ubiquity reaction efficiency, when especially preparing carboxymethyl starch with high substitution degree, drop into a large amount of sodium hydroxide and Mono Chloro Acetic Acid, not only increased production cost, also produce a large amount of acid-base waste fluids, increased the load that washing with alcohol and ethanol reclaim.Adopt technical scheme of the present invention can reduce cost and raising reaction efficiency, and, the more superior carboxymethyl starch product of performance can be obtained.
Summary of the invention
At above technology and problem, the invention provides a kind of high chemical reaction efficiency that has, and can produce molten water speed soon, the method for carboxymethyl starch of high stability and the transparency more.
The preparation method of carboxymethyl starch of the present invention comprises the steps:
(1) starch milk is sized mixing: raw starch is joined in 30%～60% volume of ethanol solution at normal temperatures, making the weight percent concentration of mixing the back starch milk is 1%～40%; The weight percent concentration of starch milk is 1%～40%, is meant the ratio of weight with the weight of the suspension of starch milk, the formation of second alcohol and water of butt starch.
(2) starch granules is decrystallized: with the starch milk suspension that regulates, through the method for heat temperature raising or add the method that alkali improves pH, realize the decrystallized and loose transformation of starch granules;
(3) carboxymethylation of starch: after the temperature regulation of the starch emulsion after decrystallized is 25-85 ℃, add relative starch weight and be 1%～20% Mono Chloro Acetic Acid or sodium chloroacetate, and additional alkali number, making Mono Chloro Acetic Acid or sodium chloroacetate and sodium hydroxide mol ratio is 1-2: 1-2, reacted 1～10 hour, and finished carboxymethyl-modification;
(4) aftertreatment of carboxymethyl starch: reduce to room temperature after carboxymethylation reaction is finished, it is 6.5～7.0 that adding acid is neutralized to pH; Filter then and with 30%～95% volume of ethanol repetitive scrubbing; Pack drying, screening back again.
Described raw starch can be one or more mixtures of the starch separated in corn, potato, cassava or the wheat.
The method of described heat temperature raising is that starch milk is heated to 80-85 ℃, disappears with the polarisation cross of polarizing microscope detection to the starch granules more than 90%, and the decrystallized and loose of promptly having finished starch granules changes;
The described method that adds alkali raising pH, be meant starch milk is heated to 80-85 ℃ or remain to 25-55 ℃, constantly add sodium hydroxide solution, improve pH, disappear with the polarisation cross of polarizing microscope detection to the starch granules more than 90%, stop to add alkali, the decrystallized and loose of promptly having finished starch granules changes.
Described acid is one or more in glacial acetic acid, hydrochloric acid, sulfuric acid, the phosphoric acid.
Described drying means is air-flow, baking oven, cylinder or spraying drying.
The carboxymethyl starch of utilizing the present invention to prepare has coldwater-soluble, dissolving evenly fast, the characteristics of high stability and the transparency.
Embodiment
Embodiment 1
At normal temperatures the 10g W-Gum is joined the 990g volumetric concentration and is in 30% the ethanolic soln, keep stirring and container airtight, make and mix afterwards that the weight percent concentration of starch milk is 1%.
The even stirring heating of starch milk is warmed up to 80 ℃, and insulation is lasting stirs, and intermittently draw samples is observed down in polarizing microscope, and until the polarisation cross disappearance of the starch granules more than 90%, the decrystallized and loose of promptly having finished starch granules changes.
It is 85 ℃ that starch emulsion after decrystallized is kept temperature, and the relative starch weight of adding 0.1g is 1% Mono Chloro Acetic Acid, and additional alkali number, and making Mono Chloro Acetic Acid and sodium hydroxide mol ratio is 1: 2, reacts 1 hour, finishes the carboxymethyl-modification of starch.
Reduce to room temperature after carboxymethylation reaction is finished, add glacial acetic acid and be neutralized to pH=6.5; Filter then and be 30% ethanol repetitive scrubbing with volumetric concentration; After air stream drying, screening, pack again.
Embodiment 2
At normal temperatures the 100g tapioca (flour) is joined the 900g volumetric concentration and is in 40% the ethanolic soln, keep stirring and container airtight, make and mix afterwards that the weight percent concentration of starch milk is 10%.
The even stirring heating of starch milk is warmed up to 55 ℃, keep continuously stirring and slowly add sodium hydroxide solution, improve constantly pH, and intermittently draw samples is observed down in polarizing microscope, polarisation cross until the starch granules more than 90% disappears, stop to add alkali, the decrystallized and loose of promptly having finished starch granules changes.
It is 55 ℃ that starch emulsion after decrystallized is kept temperature, and the relative starch weight of adding 10g is 10% Mono Chloro Acetic Acid, and additional alkali number, and making Mono Chloro Acetic Acid and sodium hydroxide mol ratio is 1: 1, reacts 5 hours, finishes the carboxymethyl-modification of starch.
Reduce to room temperature after carboxymethylation reaction is finished, add hydrochloric acid and be neutralized to pH=7.0; Filter then and be 50% ethanol repetitive scrubbing with volumetric concentration; After oven drying, screening, pack again.
Embodiment 3
At normal temperatures the 200g yam starch is joined the 800g volumetric concentration and is in 50% the ethanolic soln, keep stirring and container airtight, make and mix afterwards that the weight percent concentration of starch milk is 20%.
The even stirring heating of starch milk is warmed up to 82 ℃, and insulation is lasting stirs, and intermittently draw samples is observed down in polarizing microscope, and until the polarisation cross disappearance of the starch granules more than 90%, the decrystallized and loose of promptly having finished starch granules changes.
It is 70 ℃ that starch emulsion after decrystallized is kept temperature, and the relative starch weight of adding 40g is 20% Mono Chloro Acetic Acid, and additional alkali number, and making Mono Chloro Acetic Acid and sodium hydroxide mol ratio is 2: 1, reacts 10 hours, finishes the carboxymethyl-modification of starch.
Reduce to room temperature after carboxymethylation reaction is finished, add sulfuric acid and be neutralized to pH=6.5; Filter then and be 70% ethanol repetitive scrubbing with volumetric concentration; After roller drying, screening, pack again.
Embodiment 4
At normal temperatures the 300g wheat starch is joined the 700g volumetric concentration and is in 60% the ethanolic soln, keep stirring and container airtight, make and mix afterwards that the weight percent concentration of starch milk is 30%.
The even stirring heating of starch milk is warmed up to 25 ℃, keep continuously stirring and slowly add sodium hydroxide solution, improve constantly pH, and intermittently draw samples is observed down in polarizing microscope, polarisation cross until the starch granules more than 90% disappears, stop to add alkali, the decrystallized and loose of promptly having finished starch granules changes.
It is 25 ℃ that starch emulsion after decrystallized is kept temperature, and the relative starch weight of adding 45g is 15% sodium chloroacetate, and additional alkali number, and making sodium chloroacetate and sodium hydroxide mol ratio is 1: 2, reacts 8 hours, finishes the carboxymethyl-modification of starch.
Reduce to room temperature after carboxymethylation reaction is finished, add phosphoric acid and be neutralized to pH=7.0; Filter then and be 95% ethanol repetitive scrubbing with volumetric concentration; Spray-dried again, screening back packing.
Embodiment 5
At normal temperatures 400g tapioca (flour) and W-Gum are joined the 600g volumetric concentration and are in 45% the ethanolic soln, keep stirring and container airtight, make and mix afterwards that the weight percent concentration of starch milk is 40%.
The even stirring heating of starch milk is warmed up to 85 ℃, and insulation is lasting stirs, and intermittently draw samples is observed down in polarizing microscope, and until the polarisation cross disappearance of the starch granules more than 90%, the decrystallized and loose of promptly having finished starch granules changes.
It is 60 ℃ that starch emulsion after decrystallized is kept temperature, and the relative starch weight of adding 4g is 1% sodium chloroacetate, and additional alkali number, and making sodium chloroacetate and sodium hydroxide mol ratio is 1: 2, reacts 4 hours, finishes the carboxymethyl-modification of starch.
Reduce to room temperature after carboxymethylation reaction is finished, add glacial acetic acid and hydrochloric acid and be neutralized to pH=6.5; Filter then and be 90% ethanol repetitive scrubbing with volumetric concentration; After oven drying, screening, pack again.
Embodiment 6
At normal temperatures 350g W-Gum, yam starch and tapioca (flour) mixture are joined the 650g volumetric concentration and are in 35% the ethanolic soln, keep stirring and container airtight, make and mix afterwards that the weight percent concentration of starch milk is 35%.
The even stirring heating of starch milk is warmed up to 40 ℃, keep continuously stirring and slowly add sodium hydroxide solution, improve constantly pH, and intermittently draw samples is observed down in polarizing microscope, polarisation cross until the starch granules more than 90% disappears, stop to add alkali, the decrystallized and loose of promptly having finished starch granules changes.
It is 40 ℃ that starch emulsion after decrystallized is kept temperature, and the relative starch weight of adding 70g is 20% sodium chloroacetate, and additional alkali number, and making sodium chloroacetate and sodium hydroxide mol ratio is 1: 2, reacts 2 hours, finishes the carboxymethyl-modification of starch.
Reduce to room temperature after carboxymethylation reaction is finished, add glacial acetic acid, hydrochloric acid, sulfuric acid and phosphoric acid and be neutralized to pH=7.0; Filter then and be 85% ethanol repetitive scrubbing with volumetric concentration; After roller drying, screening, pack again.
Embodiment 7
At normal temperatures the mixture of 350g W-Gum, yam starch, tapioca (flour) and wheat starch is joined the 650g volumetric concentration and is in 35% the ethanolic soln, keep stirring and container airtight, make and mix afterwards that the weight percent concentration of starch milk is 35%.
The even stirring heating of starch milk is warmed up to 40 ℃, keep continuously stirring and slowly add sodium hydroxide solution, improve constantly pH, and intermittently draw samples is observed down in polarizing microscope, polarisation cross until the starch granules more than 90% disappears, stop to add alkali, the decrystallized and loose of promptly having finished starch granules changes.
It is 40 ℃ that starch emulsion after decrystallized is kept temperature, and the relative starch weight of adding 70g is 20% sodium chloroacetate, and additional alkali number, and making sodium chloroacetate and sodium hydroxide mol ratio is 1: 2, reacts 2 hours, finishes the carboxymethyl-modification of starch.
Reduce to room temperature after carboxymethylation reaction is finished, add glacial acetic acid, hydrochloric acid and phosphoric acid and be neutralized to pH=7.0; Filter then and be 85% ethanol repetitive scrubbing with volumetric concentration; After roller drying, screening, pack again.
Be directly relatively below through the performance of the carboxymethyl starch of carboxymethylation reaction preparation and the carboxymethyl starch that adopts the inventive method preparation with former W-Gum, CMS in three forms
1And CMS
2Representative is that former W-Gum is directly through the carboxymethyl starch of carboxymethylation reaction preparation and the amorphous particulate carboxymethyl starch of former W-Gum employing the inventive method preparation respectively.
The CMS of different shelf-times of table 1 sticks with paste fluid viscosity (mPas)
CMS in the table 1
1And CMS
2Have identical substitution value, work as CMS
1Be stored in the 12nd day viscosity and compared tangible reduction in the past, and CMS
2Viscosity does not change basically in the time of the 12nd day, as can be known CMS
2Compare CMS
1Stability better.
The CMS of table 2 different degree of substitution sticks with paste liquid transmittance (%)
As known from Table 2, CMS
2And CMS
1Along with all constantly increases of raising transmittance of substitution value, but the CMS of identical substitution value
2Compare CMS
1Transmittance all high.
The CMS dissolution time (h) of table 3 different degree of substitution
As known from Table 3, CMS
2And CMS
1Along with the consoluet time of the raising of substitution value all constantly increases, but the CMS of identical substitution value
2Compare CMS
1Dissolution time all lack, illustrate that the amorphous particulate carboxymethyl starch of the inventive method preparation is faster than the carboxymethyl starch dissolved of ative starch preparation.
Claims (5)
1. the preparation method of an amorphous particulate carboxymethyl starch comprises the steps:
(1) starch milk is sized mixing: raw starch is joined in 30%～60% volume of ethanol solution at normal temperatures, making the weight percent concentration of mixing the back starch milk is 1%～40%; The weight percent concentration of starch milk is 1%～40%, is meant the ratio of weight with the weight of the suspension of starch milk, the formation of second alcohol and water of butt starch.
(2) starch granules is decrystallized: with the starch milk suspension that regulates, through the method for heat temperature raising or add the method that alkali improves pH, realize the decrystallized and loose transformation of starch granules;
(3) carboxymethylation of starch: after the temperature regulation of the starch emulsion after decrystallized is 25-85 ℃, add relative starch weight and be 1%～20% Mono Chloro Acetic Acid or sodium chloroacetate, and additional alkali number, making Mono Chloro Acetic Acid or sodium chloroacetate and sodium hydroxide mol ratio is 1-2: 1-2, reacted 1～10 hour, and finished carboxymethyl-modification;
(4) aftertreatment of carboxymethyl starch: reduce to room temperature after carboxymethylation reaction is finished, it is 6.5～7.0 that adding acid is neutralized to pH; Filter then and with 30%～95% volume of ethanol repetitive scrubbing; Pack drying, screening back again.
2. method according to claim 1 is characterized in that: the raw starch described in the step (1) can be one or more mixtures of the starch separated in corn, potato, cassava or the wheat.
3. method according to claim 1 and 2, it is characterized in that: the method for the heat temperature raising described in the step (2), be that starch milk is heated to 80-85 ℃, disappear with the polarisation cross of polarizing microscope detection to the starch granules more than 90%, the decrystallized and loose of promptly having finished starch granules changes;
The described method that adds alkali raising pH, be meant starch milk is heated to 80-85 ℃ or remain to 25-55 ℃, constantly add sodium hydroxide solution, improve pH, disappear with the polarisation cross of polarizing microscope detection to the starch granules more than 90%, stop to add alkali, the decrystallized and loose of promptly having finished starch granules changes.
4. method according to claim 3 is characterized in that: the acid described in the step (4) is one or more in glacial acetic acid, hydrochloric acid, sulfuric acid, the phosphoric acid.
5. method according to claim 4 is characterized in that: the drying means described in the step (4) is air-flow, baking oven, cylinder or spraying drying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101981678A CN101348528A (en) | 2008-08-29 | 2008-08-29 | Preparation of amorphous particulate carboxymethyl starch |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101981678A CN101348528A (en) | 2008-08-29 | 2008-08-29 | Preparation of amorphous particulate carboxymethyl starch |
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| CNA2008101981678A Pending CN101348528A (en) | 2008-08-29 | 2008-08-29 | Preparation of amorphous particulate carboxymethyl starch |
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| CN102731664A (en) * | 2012-07-17 | 2012-10-17 | 郑桂富 | Preparation method of pharmaceutical adjuvant sodium carboxymethyl starch |
| CN103242457A (en) * | 2013-05-02 | 2013-08-14 | 宁波大学 | Method for extracting taro starch and application of taro starch |
| CN103509125A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for hydrophobically modified carboxymethyl starch used for drilling fluid |
| CN103772513A (en) * | 2012-10-20 | 2014-05-07 | 中国烟草总公司郑州烟草研究院 | Preparation method and application of pyrolyzed-carboxymethylated amyloid cigarette humectant |
| CN103772531A (en) * | 2012-10-20 | 2014-05-07 | 中国烟草总公司郑州烟草研究院 | Preparation method and application of acidolyzed-carboxymethylated amyloid cigarette humectant |
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| CN105693872A (en) * | 2016-04-05 | 2016-06-22 | 杭州弘博新材料有限公司 | Preparation method of salt-resistant carboxymethyl starch |
| CN106496338A (en) * | 2016-10-31 | 2017-03-15 | 华南理工大学 | A kind of preparation technology of molten paste method high-substitution carboxymethyl modified starch |
| CN106749712A (en) * | 2017-01-16 | 2017-05-31 | 无锡市善源生物科技有限公司 | A kind of method that semidry method prepares CMS |
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| CN109265571A (en) * | 2018-08-17 | 2019-01-25 | 山东神州翔宇科技集团有限公司 | A kind of clean preparation method of composite modified starch |
| CN110372804A (en) * | 2019-07-13 | 2019-10-25 | 湖北江汉利达石油物资装备有限公司 | Anti-salt temperature-resistant starch drilling well fluid loss additive and preparation method thereof |
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2008
- 2008-08-29 CN CNA2008101981678A patent/CN101348528A/en active Pending
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| CN103509125A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for hydrophobically modified carboxymethyl starch used for drilling fluid |
| CN103509125B (en) * | 2012-06-21 | 2016-04-20 | 中国石油化工股份有限公司 | The drilling fluid preparation method of hydrophobically modified carboxy methyl starch |
| CN102731664A (en) * | 2012-07-17 | 2012-10-17 | 郑桂富 | Preparation method of pharmaceutical adjuvant sodium carboxymethyl starch |
| CN103772513B (en) * | 2012-10-20 | 2016-08-03 | 中国烟草总公司郑州烟草研究院 | A kind of preparation method and applications of pyrolysis-carboxymethylated starch matter humectant for smoke |
| CN103772513A (en) * | 2012-10-20 | 2014-05-07 | 中国烟草总公司郑州烟草研究院 | Preparation method and application of pyrolyzed-carboxymethylated amyloid cigarette humectant |
| CN103772531A (en) * | 2012-10-20 | 2014-05-07 | 中国烟草总公司郑州烟草研究院 | Preparation method and application of acidolyzed-carboxymethylated amyloid cigarette humectant |
| CN103772515A (en) * | 2012-10-20 | 2014-05-07 | 中国烟草总公司郑州烟草研究院 | Preparation method and application of acidolyzed-oxidized amyloid cigarette humectant |
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| CN103242457A (en) * | 2013-05-02 | 2013-08-14 | 宁波大学 | Method for extracting taro starch and application of taro starch |
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| CN104710967A (en) * | 2013-12-17 | 2015-06-17 | 中国石油化工集团公司 | Self-plugging releasing temperature resistant temporary plugging agent used for water-based drilling fluid and preparation method thereof |
| CN104710967B (en) * | 2013-12-17 | 2019-01-01 | 中国石油化工集团公司 | A kind of water-base drilling fluid is with from de-plugging temperature resistance diverting agent and preparation method thereof |
| CN105153318A (en) * | 2015-07-24 | 2015-12-16 | 江南大学 | Preparation method for starch-based microgel |
| CN105153318B (en) * | 2015-07-24 | 2017-09-26 | 江南大学 | A kind of preparation method of starch base microgel |
| CN105693872A (en) * | 2016-04-05 | 2016-06-22 | 杭州弘博新材料有限公司 | Preparation method of salt-resistant carboxymethyl starch |
| CN105693872B (en) * | 2016-04-05 | 2018-12-04 | 杭州弘博新材料有限公司 | A kind of preparation method of salt-resistance carboxymethyl starch |
| CN106496338A (en) * | 2016-10-31 | 2017-03-15 | 华南理工大学 | A kind of preparation technology of molten paste method high-substitution carboxymethyl modified starch |
| CN106749712A (en) * | 2017-01-16 | 2017-05-31 | 无锡市善源生物科技有限公司 | A kind of method that semidry method prepares CMS |
| CN106749712B (en) * | 2017-01-16 | 2019-04-09 | 无锡市善源生物科技有限公司 | A kind of method of semidry method preparation carboxymethyl starch |
| CN109134946A (en) * | 2018-07-12 | 2019-01-04 | 杨红洲 | A kind of granular material environmental protection binder and preparation method thereof |
| CN109265571A (en) * | 2018-08-17 | 2019-01-25 | 山东神州翔宇科技集团有限公司 | A kind of clean preparation method of composite modified starch |
| CN110372804A (en) * | 2019-07-13 | 2019-10-25 | 湖北江汉利达石油物资装备有限公司 | Anti-salt temperature-resistant starch drilling well fluid loss additive and preparation method thereof |
| CN112569401A (en) * | 2020-10-19 | 2021-03-30 | 南京大学 | Degradable starch polysaccharide medical material and preparation method thereof |
| CN114716575A (en) * | 2022-03-01 | 2022-07-08 | 武汉轻工大学 | Preparation method of starch microgel |
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