CN101942033B - High-methoxyl content methyl starch as well as preparation method and application thereof - Google Patents

High-methoxyl content methyl starch as well as preparation method and application thereof Download PDF

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CN101942033B
CN101942033B CN2010102738178A CN201010273817A CN101942033B CN 101942033 B CN101942033 B CN 101942033B CN 2010102738178 A CN2010102738178 A CN 2010102738178A CN 201010273817 A CN201010273817 A CN 201010273817A CN 101942033 B CN101942033 B CN 101942033B
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starch
preparation
reaction
methoxyl content
microwave
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CN101942033A (en
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侯成敏
陈玉放
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Guangzhou Chemical Co Ltd of CAS
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Guangzhou Chemical Co Ltd of CAS
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Abstract

The invention discloses high-methoxyl content methyl starch as well as a preparation method and application thereof. By pretreating activating starch with sodium chloride and potassium hydroxide and combining a microwave-assisted reaction technology, the efficient reaction of dimethyl carbonate and starch is realized, and the high-methoxyl content methyl starch with 5-15.8 percent of methoxyl is obtained. The preparation method has the advantages of high reaction heat efficiency and short reaction time and high production efficiency due to microwave heating, no use of organic solvent, low cost, easy control of reaction temperature, high reaction efficiency, and easy control of the process; almost nontoxic dimethyl carbonate is used as a methylation reagent, with byproducts of methanol and carbon dioxide which are safe and environmental-friendly, are easy for treatment and can be recycled for synthesizing dimethyl carbonate raw materials. The high-methoxyl content methyl starch of the invention can be widely applied to the fields of petroleum, textile, daily chemicals, papermaking, buildings, foods, and the like.

Description

Methyl starch of high methoxyl content and preparation method thereof and application
Technical field
The present invention be more particularly directed to a kind of methyl starch and preparation method thereof and application of high methoxyl content, belong to the field of chemical synthesis.
Background technology
Methyl starch (Methyl Starch) is one of principal item of modified starch, belongs to ethers starch, is a kind of water-soluble polymeric ether compounds, it is characterized by: white or yellow powder, odorless, tasteless, nontoxic, the easy moisture absorption; Water-soluble formation colloidal solution is to light, thermally-stabilised; Be insoluble to organic solvents such as ethanol, ether, chloroform; Can be used as emulsifying agent, dispersion agent, thickening material, membrane-forming agent, water-holding agent etc., be widely used in industrial sectors such as oil, weaving, daily use chemicals, papermaking, building, food.The main working method of methyl starch has methyl iodide/silver suboxide method, sodium hydride/methyl-sulphoxide/methyl iodide method, sodium hydroxide/methyl-sulphoxide/Silver Nitrate/methyl iodide method, concentrated sodium hydroxide/methyl-sulfate method at present.Methyl halide costs an arm and a leg, prepared severe condition such as the range request anaerobic is anhydrous in these methods, is difficult to industriallization; Methyl-sulfate has severe toxicity, carinogenicity, and safe operation process property is low, and the efficient that methylates is low, and the problems that these methods exist make the application of methyl starch and development be restricted.
Methylcarbonate has passed through non-toxic agent in 1992 in Europe and has registered; Recently the more than ten years be widely used as aminated compoundss such as nitrile compounds such as phenolic cpd, acetonitrile, aniline such as phenol methylating reagent to substitute methyl halide, methyl-sulfate; But methylcarbonate also not as the methylating reagent of alcohol compound hydroxyl, more is not used as the methylating reagent of polymer glucide.
In CN 101168568; Adopt normal temperature and pressure and common equipment to make methoxy content and have only 3% methyl starch; The efficient that methylates and degree are desirable not enough, and the practical ranges of product has great limitation capable, also are difficult to carry out for the moment large-scale Industry Promotion.
Summary of the invention
Primary and foremost purpose of the present invention is the shortcoming that overcomes preparation methyl starch method in the prior art, and a kind of preparation method of methyl starch of high methoxyl content is provided.
Another object of the present invention is to provide the methyl starch of the high methoxyl content that obtains through said preparation method.
A purpose more of the present invention is to provide the application of the methyl starch of said high methoxyl content.
The present invention adopts following scheme to realize: a kind of preparation method of methyl starch of high methoxyl content comprises following steps:
(1) starch activation: in starch, add the sodium-chlor be equivalent to starch quality 4~10%, add potassium hydroxide aqueous solution again,, obtain mixed liquor A in 54~56 ℃ of stirring reactions 1~2 hour; Re-using is that at least one times of volume of ethanol solution of mixed liquor A precipitates, and crosses to filter pretreated starch; The consumption of Pottasium Hydroxide is to be equivalent to 37.5~67.5% of starch quality;
(2) microwave-assisted reaction: wet chemical and the methylcarbonate gradation of using volume to be equivalent to 5.5~10 times of starch qualities are added in the pretreated starch of step (1) preparation; Behind each reinforced finishing; Mix, place 2~40 kilowatts microwave reactor to carry out microwave reaction 1~2 minute, after the last microwave treatment; Continue microwave treatment again 0.5~1 minute, and finished reaction; The consumption of salt of wormwood is equivalent to starch quality 55~100%;
(3) aftertreatment: then be cooled to room temperature, the pH value of cooling off back solution is adjusted to 6~8, obtain mixed liquid B; Re-using is that at least one times of volume of ethanol solution of mixed liquid B precipitates, sedimentary purpose be remove anhydrate, inorganic salt and superfluous methylcarbonate, filter the back and use the methylcarbonate washing precipitation, filtration, drying obtains the methyl starch of high methoxyl content;
The methyl starch methoxy content of said high methoxyl content is 5~15.8%;
Starch described in the step (1) is at least the starch of technical grade, is preferably at least a in W-Gum, tapioca(flour), yam starch, sweet potato starch or the potato starch, more preferably tapioca(flour) or yam starch;
Amount of sodium chloride described in the step (1) is preferably and is equivalent to starch quality 5~10%;
The concentration of potassium hydroxide aqueous solution is preferably mass volume ratio 15% described in the step (1);
The concentration of ethanolic soln is preferably volume percent 75~78% described in the step (1);
The concentration of wet chemical is preferably mass volume ratio 10% described in the step (2);
The number of times of gradation described in the step (2) is got over for a long time, and methoxy content is high more; The condition optimization that gradation adds adds for dividing 2~4 equivalent;
The preferred sulfuric acid that uses of pH value described in the step (3) is regulated;
Said vitriolic concentration is preferably volume percent 2~5%;
The concentration of ethanolic soln is preferably volume percent 75~78% described in the step (3);
The number of times of washing preferably is at least 3 times described in the step (3);
The exsiccant temperature is preferably 105~109 ℃ described in the step (3);
The solvent of the above solution is water;
A kind of methyl starch of high methoxyl content obtains through above-mentioned preparation method;
The methyl starch of said high methoxyl content is applied to fields such as oil, weaving, daily use chemicals, papermaking, building and food.
The present invention has following advantage and effect with respect to prior art:
The present invention combines the microwave-assisted reaction technology, realizes the highly effective reaction of methylcarbonate and starch, significantly improved the degree that methylates of starch, has obtained methoxy content and be the starch that methylates of 5~15.8% high methoxyl content.Preparing method provided by the invention compares with existing production technology, has the following advantages: microwave heating is used in (1), and reaction heat efficient is high, and the reaction times is short, and production efficiency is high; (2) not with an organic solvent, use water as solvent, with low cost, temperature of reaction is easy to control; Starch is with sodium-chlor and Pottasium Hydroxide pre-treatment and activation, and reaction efficiency further improves; Methylcarbonate and the gradation of salt of wormwood catalyzer add, and technological process is easy to control; Use almost non-toxic methylcarbonate to do methylating reagent, by-product methyl alcohol and carbonic acid gas, safety and environmental protection is easy to handle, and also can reuse the Synthesis of dimethyl carbonate raw material.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
(1) starch activation: take by weighing 10 gram yam starchs and put into container; Add 0.5 gram sodium-chlor; Add mass volume ratio again and be 15% potassium hydroxide aqueous solution 25ml; In 54 ℃ of stir-activatings and alkalinisation treatment 1 hour, add the 50ml volume percent and be 75~78% aqueous ethanolic solution and precipitate, filter and obtain pretreated starch;
(2) microwave-assisted reaction: with 55ml methylcarbonate and 55ml mass volume ratio is that 10% wet chemical divides four equivalent to add; Behind each reinforced finishing; Stirring and evenly mixing places 2 kilowatts microwave reactor to react 1 minute, after the 4th microwave treatment; Continue microwave treatment again 1 minute, and finished reaction;
(3) aftertreatment: be cooled to room temperature; Use volume percent be 2% dilute sulphuric acid to regulate pH value be 6~8, add the 70ml volume percent again and be 75~78% aqueous ethanolic solution deposition, filtration; With methylcarbonate washing precipitation three times; Filter once more, 105 ℃ are dry down, pulverize the methyl starch of high methoxyl content.
(4) detect: through the appendix VII G methoxy content measuring method of Chinese Pharmacopoeia 2005 editions, primary process is: precision takes by weighing the about 0.1g of trial-product, puts in the flask; Add fused phenol 2.5mL and hydroiodic acid HI 5mL; Connect said apparatus, in addition in two receiving vessels, add the glacial acetic acid solution 6ml and the 4ml of 10% Potassium ethanoate respectively; Respectively add bromine 0.2ml again, through arm with N 2Air-flow slowly and balancedly (1~2 bubble p.s.) feeds in the flask, and flask is immersed oil bath, slowly heating, and controlled temperature just makes the boiling liquid steam rise to half height of prolong, continues heating 45 minutes, takes out flask, cooling under aeration status; Pull down two absorption bottles, with their content impouring 250ml iodine flask (interior Sheng 25% sodium acetate soln 5mL), water cleans absorption bottle; Make TV be about 125mL, add formic acid 0.3mL, the color of rotating iodine flask to bromine disappears; Add formic acid 0.6mL again; Close plug jolting makes excessive bromine completely dissolve, places 1~2 minute; Add potassiumiodide 1.0g, dilute sulphuric acid 5mL and starch indicating liquid 1mL, shake up, with the titration of 0.1mol/L Sulfothiorine vs.Carrying out blank test with this law simultaneously proofreaies and correct.Methoxy content (%)=0.05172* (V-V0)/m, wherein V is the volume (mL) of the used Sulfothiorine of titration sample, and V0 is the volume (mL) of the used Sulfothiorine of titration blank sample, and m is the quality (g) of sample.
The methoxy content that detects present embodiment gained methyl starch is 9%.
Embodiment 2
(1) starch activation: take by weighing tapioca(flour) 10 grams; Add sodium-chlor 0.8 gram; The potassium hydroxide solution 40ml that adds mass volume ratio 15% again; In 54 ℃ of stir-activatings and alkalinisation treatment 2 hours, add the 60ml volume percent and be 75~78% aqueous ethanolic solution and precipitate, filter and obtain pretreated starch;
(2) microwave-assisted reaction: with 65ml methylcarbonate and 65ml mass volume ratio is that 10% wet chemical divides four equivalent addings; After adding material at every turn; Stirring and evenly mixing places 10 kilowatts microwave reactor to react 2 minutes, after the 4th microwave treatment; Continue microwave treatment again 0.5 minute, and finished reaction;
(3) aftertreatment: be cooled to room temperature; Use volume percent be 5% dilute sulphuric acid to regulate pH value be 6~8, add the 100mL volume percent and be 75~78% aqueous ethanolic solution and precipitate filtration; Methylcarbonate washing precipitation three times; Filter, in 107 ℃ dry down, pulverize the methyl starch of high methoxyl content.
The methoxy content of gained methyl starch is 12%, and testing method is with embodiment 1.
Embodiment 3
(1) starch activation: take by weighing W-Gum 10 grams; Add sodium-chlor 0.7 gram; The potassium hydroxide solution 30ml that adds mass volume ratio 15% again; In 56 ℃ of stir-activatings and alkalinisation treatment 1 hour, add the 80mL volume percent and be 75~78% aqueous ethanolic solution and precipitate, filter and obtain pretreated starch;
(2) microwave-assisted reaction: divide four equivalent to add the wet chemical of 75ml methylcarbonate and 75ml mass volume ratio 10%; After adding material at every turn; Stirring and evenly mixing places 20 kilowatts microwave reactor to react 2 minutes, after the 4th microwave treatment; Continue microwave treatment again 1 minute, and finished reaction;
(3) aftertreatment: be cooled to room temperature; Use volume percent be 5% dilute sulphuric acid to regulate pH value be 6~8, add the 50mL volume percent and be 75~78% aqueous ethanolic solution and precipitate filtration; Methylcarbonate washing precipitation three times; Filter, in 109 ℃ dry down, pulverize the methyl starch of high methoxyl content.
The methoxy content of gained methyl starch is 14%, and testing method is with embodiment 1.
Embodiment 4
(1) starch activation: take by weighing yam starch 10 grams; Add sodium-chlor 1 gram; The potassium hydroxide aqueous solution 45ml that adds mass volume ratio 15% again; In 56 ℃ of stir-activatings and alkalinisation treatment 2 hours, using the 90mL volume percent was that 75~78% aqueous ethanolic solution precipitates, and filters and obtains pretreated starch;
(2) microwave-assisted reaction: divide four equivalent to add the wet chemical of 85ml methylcarbonate and 85ml mass volume ratio 10%; After adding material at every turn; Stirring and evenly mixing places 40 kilowatts microwave reactor to react 2 minutes, after the 4th microwave treatment; Continue microwave treatment again 1 minute, and finished reaction;
(3) aftertreatment: be cooled to room temperature; Use volume percent be 2% dilute sulphuric acid to regulate pH value be 6~8, add the 50mL volume percent and be 75~78% aqueous ethanolic solution and precipitate filtration; Methylcarbonate washing precipitation three times; Filter, in 105 ℃ dry down, pulverize the methyl starch of high methoxyl content.
The methoxy content of gained methyl starch is 15.8%, and testing method is with embodiment 1.
Embodiment 5
(1) starch activation: take by weighing sweet potato starch 10 grams; Add sodium-chlor 0.4 gram, add the potassium hydroxide solution 40ml of mass volume ratio 15% again, in 54 ℃ of stir-activatings and alkalinisation treatment 2 hours; The use volume percent is 75~78% aqueous ethanolic solution 100mL deposition, filters and obtains pretreated starch;
(2) microwave-assisted reaction: with 100ml methylcarbonate and the equivalent adding at twice of 100ml mass volume ratio 10% solution of potassium carbonate; After adding material, stirring and evenly mixing places 20 kilowatts microwave reactor to react 2 minutes at every turn; After the microwave treatment, continued microwave treatment again 1 minute for the second time;
(3) aftertreatment: be cooled to room temperature, using 5% dilute sulphuric acid 5mL to regulate pH value is 6~8, and adding 50mL volume percent is that 75~78% aqueous ethanolic solution precipitates; Filter, methylcarbonate washing precipitation three times is filtered; In 105 ℃ down dry, pulverize the methyl starch of high methoxyl content.
The methoxy content of gained methyl starch is 5%, and testing method is with embodiment 1.
Embodiment 6
(1) starch activation: take by weighing yam starch 10 grams; Add sodium-chlor 0.6 gram; The potassium hydroxide solution 45ml that adds mass volume ratio 15% again; In 54 ℃ of stir-activatings and alkalinisation treatment 2 hours, using volume percent was 75~78% aqueous ethanolic solution 80mL deposition, filters and obtains pretreated starch;
(2) microwave-assisted reaction: divide three equivalent to add 75ml methylcarbonate and 75ml 10% solution of potassium carbonate; After adding material, stirring and evenly mixing places 30 kilowatts microwave reactor to react 2 minutes at every turn; After the microwave treatment, continued microwave treatment again 1 minute for the third time;
(3) aftertreatment: be cooled to room temperature, using 3% dilute sulphuric acid 7mL to regulate pH value is 6~8, and adding 100mL volume percent is that 75~78% aqueous ethanolic solution precipitates; Filter, methylcarbonate washing precipitation three times is filtered; In 105 ℃ down dry, pulverize the methyl starch of high methoxyl content.
The methoxy content of gained methyl starch is 7.9%, and testing method is with embodiment 1.
Measure of merit:
The methyl starch of embodiment 1~6 prepared high methoxyl content was placed in cold water 12 hours, all can be obtained dissolved, full-bodied transparence thing.When being respectively applied for it in coating, can significantly improve the adhesivity and the sag resistance of coating.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. the preparation method of the methyl starch of a high methoxyl content is characterized in that comprising following steps:
(1) starch activation: in starch, add the sodium-chlor be equivalent to starch quality 4~10%, add potassium hydroxide aqueous solution again,, obtain mixed liquor A in 54~56 ℃ of stirring reactions 1~2 hour; With being that at least one times of volume of ethanol solution of mixed liquor A precipitates, crossing and filter pretreated starch again; The consumption of Pottasium Hydroxide is to be equivalent to 37.5~67.5% of starch quality;
(2) microwave-assisted reaction: add in the pretreated starch of step (1) preparation with wet chemical with the methylcarbonate gradation that volume is equivalent to 5.5~10 times of starch qualities; Behind each reinforced finishing; Mix, place 2~40 kilowatts microwave reactor to carry out microwave reaction 1~2 minute, after the last microwave treatment; Continue microwave treatment again 0.5~1 minute, and finished reaction; The consumption of salt of wormwood is equivalent to starch quality 55~100%;
(3) aftertreatment: then be cooled to room temperature, the pH value of cooling off back solution is adjusted to 6~8, obtain mixed liquid B; With being that at least one times of volume of ethanol solution of mixed liquid B precipitates, filter, use the methylcarbonate washing precipitation then, filter, drying obtains methoxy content and is the methyl starch of 5%~15.8% high methoxyl content.
2. preparation method according to claim 1 is characterized in that: the starch described in the step (1) is at least a in W-Gum, tapioca(flour), yam starch or the sweet potato starch.
3. preparation method according to claim 1 is characterized in that: amount of sodium chloride is for being equivalent to starch quality 5%~10% described in the step (1).
4. preparation method according to claim 1 is characterized in that: the concentration of potassium hydroxide aqueous solution is mass volume ratio 15% described in the step (1).
5. preparation method according to claim 1 is characterized in that: the concentration of ethanolic soln is volume percent 75~78% described in the step (1).
6. preparation method according to claim 1 is characterized in that: the concentration of wet chemical is mass volume ratio 10% described in the step (2).
7. preparation method according to claim 1 is characterized in that: the pH value described in the step (3) is for to regulate through sulfuric acid.
8. preparation method according to claim 1 is characterized in that: the number of times of washing is at least 3 times described in the step (3); The exsiccant temperature is 105~109 ℃ described in the step (3).
9. the methyl starch of a high methoxyl content, each described preparation method obtains through claim 1~8.
10. the methyl starch of the said high methoxyl content of claim 9 is applied to oil field, field of textiles, household chemicals field, field of papermaking, building field and/or field of food.
CN2010102738178A 2010-09-07 2010-09-07 High-methoxyl content methyl starch as well as preparation method and application thereof Expired - Fee Related CN101942033B (en)

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CN104558202A (en) * 2015-01-20 2015-04-29 西安理工大学 Green preparation method of methyl cellulose
CN106699909A (en) * 2016-12-15 2017-05-24 重庆第二师范学院 Preparation technology for methyl starch

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4839060A (en) * 1987-04-28 1989-06-13 Suncor, Inc. Methylated starch compositions and their use as flocculating agents for mineral wastes, such as bauxite residues
CN101045802A (en) * 2006-03-24 2007-10-03 沃尔弗纤维素有限责任两合公司 Methyl starch ether of inorganic building material
CN101168568A (en) * 2007-11-09 2008-04-30 中国科学院广州化学研究所 Method for preparing methyl starch

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4839060A (en) * 1987-04-28 1989-06-13 Suncor, Inc. Methylated starch compositions and their use as flocculating agents for mineral wastes, such as bauxite residues
CN101045802A (en) * 2006-03-24 2007-10-03 沃尔弗纤维素有限责任两合公司 Methyl starch ether of inorganic building material
CN101168568A (en) * 2007-11-09 2008-04-30 中国科学院广州化学研究所 Method for preparing methyl starch

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