CN108409874B - Preparation method of etherified corn starch with high substitution degree - Google Patents
Preparation method of etherified corn starch with high substitution degree Download PDFInfo
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Abstract
The invention provides a preparation method of etherified corn starch with high degree of substitution, which is characterized in that the etherified corn starch with high degree of substitution is prepared by a solvent method under the condition that nano microcrystalline cellulose exists by taking corn starch as a raw material; the high degree of substitution means that the degree of substitution is greater than 0.2; the nano microcrystalline cellulose is nano microcrystalline cellulose NCC with the fiber length of 100-500 nm. The nano-cellulose is used as a catalyst to prepare the etherified starch, and the method is simple to operate, obvious in effect and small in pollution. Simple steps, convenient operation and strong practicability.
Description
Technical Field
The invention belongs to the field of preparation of high-substitution-degree starch, and particularly relates to a preparation method of high-substitution-degree etherified corn starch.
Background
Starch is a carbohydrate formed by photosynthesis of plants, is an important energy storage form of the plants, has the yield second to cellulose, and is a purely natural renewable resource with rich sources. The starch has the characteristics of low price, easy degradation, environmental friendliness and the like, so that the starch is widely applied to various industrial fields. Compared with the original starch, the etherified starch has the advantages of low gelatinization temperature, strong hydrophilicity, good film forming property, excellent water retention property and the like, and the problem that how to reduce the use of chemicals, improve the etherification substitution degree and promote the application performance and market value is needed to be solved at present is solved.
Cellulose is a natural green high molecular material and is a renewable resource. Nanocellulose can be isolated from a variety of cellulose sources including plants, animals, bacteria, algae, etc., and nanocrystalline cellulose refers to cellulose having a spatial dimension on the order of nanometers. The advantages of high strength, light weight, reproducibility, biodegradability and the like of the nano-cellulose enable the application research of the nano-cellulose in the field of chemical materials to be more and more.
In recent years, with the gradual highlighting of environmental problems, the demand for green chemical modification technology and degradable products is higher and higher. Therefore, how to introduce more environment-friendly products into the modern chemical industry instead of the traditional chemical agents is an important direction for the development of the chemical industry at present.
white-Zhonglan et al, on the research on the preparation of carboxymethyl cellulose and carboxymethyl starch mixture from potato starch residue, prepared carboxymethyl cellulose (CMC) and carboxymethyl starch (CMS) mixtures from potato starch residue as raw material. However, due to the utilization of waste and conventional cellulose generated in the production process of potato starch, only etherified starch with a low degree of substitution can be prepared.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of etherified corn starch with high substitution degree. The nano-cellulose is used as a catalyst to modify the starch, so that the consumption of chemicals is reduced, and the influence on the whiteness of the starch is small; the preparation method has low cost, and is degradable and pollution-free.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of etherified corn starch with high degree of substitution is provided, which takes corn starch as raw material, and adopts a solvent method to prepare etherified starch with high degree of substitution in the presence of nano microcrystalline cellulose;
the high degree of substitution means that the degree of substitution is greater than 0.2;
the nano microcrystalline cellulose is nano microcrystalline cellulose NCC with the fiber length of 100-500 nm.
Preferably, the mass ratio of the corn starch to the nano microcrystalline cellulose is 100: 0.5 to 5.
Preferably, the solvent method comprises the following specific steps: alkalizing corn starch and nano microcrystalline cellulose in sodium hydroxide-ethanol solution with certain concentration; and adding an etherifying agent for etherification, washing and centrifuging after the etherification reaction is finished, adjusting the pH value to be neutral, and drying to obtain the catalyst.
Preferably, the mass volume ratio of the corn starch to the ethanol is 10-12g to 25-30 ml.
Preferably, the mass ratio of the corn starch to the sodium hydroxide is 100: 16-20.
Preferably, the etherifying agents are monochloroacetic acid and sodium chloroacetate.
Preferably, the mass ratio of the corn starch to the etherifying agent is 100: 5-20, namely: the amount of etherifying agent is in the range of 5-20% relative to the oven dried mass of starch.
Researches find that the starch etherification effect is poor when the alkalization time is less than 0.5h, and the influence on the etherification degree of the starch is not great when the alkalization time is more than 3h and is continuously increased, so that the preferable alkalization reaction condition in the application is that the alkalization reaction is carried out for 0.5 to 3h at the temperature of between 40 and 50 ℃.
Preferably, the etherification reaction time is 40-50 ℃ for 3-10 h.
The invention also provides the etherified corn starch with high degree of substitution prepared by any one of the methods.
The invention has the advantages of
(1) The starch modification of the invention takes the nano-cellulose as the catalyst, thus reducing the consumption of chemicals and having little influence on the whiteness of the starch;
(2) the etherified starch takes corn starch and nano-cellulose NCC as main raw materials, has low cost, is degradable and has no pollution;
(3) the preparation method is simple, high in substitution degree, strong in practicability and easy to popularize.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The present invention will be further described with reference to specific examples.
An etherified starch with a higher substitution degree is prepared by compounding corn starch and nano-cellulose and then etherifying; the substitution degree of the existing modified starch is generally 0.01-0.1, and the substitution degree of carboxymethyl starch is higher and is generally more than 0.2; therefore, a high degree of substitution of 0.2 or more is generally considered.
The etherified starch is prepared by taking nano-cellulose as a catalyst;
the catalyst is nano microcrystalline cellulose NCC with the fiber length of 100-500 nm;
the dosage of the nano-cellulose used as a catalyst is 0.5 to 5 percent (relative to the dosage of starch);
firstly, mixing nano-cellulose and starch, and adding NaOH to carry out alkalization treatment;
the starch etherifying agent is monochloroacetic acid and sodium chloroacetate;
the invention provides a green pollution-free catalyst for catalytic reaction, and monochloroacetic acid and sodium chloroacetate are used as etherifying agents for modification.
In the invention: the nano microcrystalline cellulose is prepared by an acid hydrolysis method or is obtained by market purchase. The nano-cellulose plays a role of a catalyst, so that the etherification degree of the starch can be improved, and the etherification time can be shortened. The nano-cellulose is added in the starch etherification process, so that the consumption of chemicals can be reduced, the environmental pollution is reduced, and the starch etherification degree can be improved.
The starch etherification system is monochloroacetic acid/nano-cellulose, sodium chloroacetate/nano-cellulose;
the research of the application finds that: because the length of the nano-cellulose is nano-scale, the nano-cellulose is easy to intercalate in the starch, the accessibility of the starch and the etherifying agent is enlarged, and the etherified starch has higher substitution degree. For this reason, the length of the nanocellulose preferred for the present application is 100-500 nm. The smaller the length of the nano-cellulose, the easier the nano-cellulose is intercalated in the starch, and the accessibility of the starch and the etherifying agent is enlarged.
The dosage of the nano-cellulose used as the catalyst is 0.5 to 5 percent (relative to the dosage of the starch).
And mixing the nano-cellulose and the starch for 0.5h, and then carrying out etherification reaction.
The preparation method of the etherified starch comprises the following steps:
weighing 10-12g of starch, dissolving the starch in 25-30ml of absolute ethyl alcohol, stirring the mixture by using a glass rod, pouring the mixture into a 250ml three-neck flask, adding 0.5-10 wt% (relative to the weight of absolute dry starch) of nano cellulose, stirring and mixing the mixture for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding a certain amount of NaOH to alkalize the mixture for 0.5-3h, adding a certain amount of etherifying agent into the three-neck flask, mechanically stirring the mixture for 3-10h, stopping etherification reaction, washing the mixture by using a methanol solution with a volume fraction of 80%, centrifuging the mixture until the product does not contain sodium chloride (checked by using a silver nitrate aqueous solution), adjusting the pH value to be neutral by using glacial acetic acid, and drying the product in a 45 ℃ oven to obtain white powdery etherif.
The principle of the invention is as follows:
the nano-cellulose is used as a catalyst, and intercalation compounding is carried out in starch, so that the etherification process is more sufficient; the nano-cellulose has the advantages of large specific surface area, high strength and the like, can be compounded with starch and then subjected to etherification reaction, and the etherified starch prepared by catalysis of the nano-cellulose has high etherification degree.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
Example 1
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 0.5 wt% (relative to the absolute dry starch mass) of nano-cellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 16 wt% of NaOH for alkalization for 0.5h, adding 5 wt% of monochloroacetic acid solution (with the concentration of 70 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 4h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product does not contain sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH of the product to be neutral by using glacial acetic acid, and drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
Measuring the substitution degree of the etherified product by an acid titration method, accurately weighing 0.5g of sample, placing the sample in a 50ml small beaker, adding 40ml of 2mol/l HCl solution, stirring for 3h by an electromagnetic stirrer, filtering, and adding 80 volume percent methanol solution to wash the acidified sample until the washing liquid does not contain chloride ions. Dissolving the starch with 40ml of 0.1mol/L NaOH standard solution, dissolving the solution under heating, dripping the solution with 0.1mol/L standard HCl solution when the solution is hot until the red color of the phenolphthalein indicator just fades, recording the volume of the consumed HCl standard solution, and measuring the Degree of Substitution (DS) of the starch to be 0.70, wherein the Degree of Substitution (DS) is calculated according to the following formula:
a-millimoles of NaOH consumed to neutralize 1g of acid carboxymethyl starch;
VNaOH-volume of NaOH standard solution added, ml;
CNaOH-concentration of NaOH standard solution, mol/L;
VHCl-titration of the volume of excess NaOH standard solution consumed HCl standard solution, ml;
CHCl-concentration of HCl standard solution, mol/L;
m-mass of acid carboxymethyl starch used for the determination, g;
0.162-millimoles of anhydroglucose units of starch;
0.058-net gain in millimolar mass of anhydroglucose units following replacement of one hydroxyl group in the anhydroglucose unit by a carboxymethyl group.
Example 2
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring by a glass rod, adding 3 wt% (relative to the weight of the absolutely dry starch) of nano-cellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 18 wt% of NaOH for alkalization for 1h, adding 5 wt% of monochloroacetic acid solution (with the concentration of 70 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 5h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product does not contain sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherification product was determined by acid titration to be 0.73.
Example 3
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring by a glass rod, adding 5 wt% (relative to the absolute dry starch mass) of nano cellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 20 wt% of NaOH for alkalization for 2h, adding 5 wt% of monochloroacetic acid solution (with the concentration of 70 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 6h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product does not contain sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherification product was determined by acid titration to be 0.81.
Example 4
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring by a glass rod, adding 7 wt% (relative to the weight of the absolutely dry starch) of nano cellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 20 wt% of NaOH for alkalization for 2h, adding 10 wt% of monochloroacetic acid solution (with the concentration of 70 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 10h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product does not contain sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherification product was determined by acid titration to be 0.85.
Example 5
Weighing 12g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring by a glass rod, adding 9 wt% (relative to the absolute dry starch mass) of nano cellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 20 wt% of NaOH for alkalization for 3h, adding 20 wt% of monochloroacetic acid solution (with the concentration of 70 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 10h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product does not contain sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and drying the product in a 45 ℃ oven to obtain white powdery etherified starch.
The degree of substitution of the etherification product was determined by acid titration to be 0.74.
Example 6
Weighing 12g of starch and dissolving the starch with 25ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 2 wt% (relative to the absolute dry starch mass) of nano-cellulose, stirring and mixing for 0.5h, adding 20 wt% of NaOH for alkalization for 1h, adding 20 wt% of sodium chloroacetate solution (with the concentration of 50 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 3h, washing and centrifuging the product with 80% volume fraction of methanol solution until the product is free of sodium chloride (checked with silver nitrate aqueous solution), adjusting the pH to be neutral with glacial acetic acid, and then drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherification product was determined by acid titration to be 0.47.
Example 7
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 4 wt% (relative to the absolute dry starch mass) of nano-cellulose, stirring and mixing for 0.5h, adding 20 wt% of NaOH to alkalize for 1h at 40 ℃, adding 20 wt% of sodium chloroacetate solution (with the concentration of 50 wt%) to the three-neck flask, stopping etherification reaction after mechanical stirring for 4h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product does not contain sodium chloride (checking by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and then drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherification product was determined by acid titration to be 0.55.
Example 8
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 5 wt% (relative to the absolute dry starch mass) of nano-cellulose, stirring and mixing for 0.5h, adding 20 wt% of NaOH to alkalize for 1h at 50 ℃, adding 20 wt% of sodium chloroacetate solution (with the concentration of 50 wt%) to the three-neck flask, stopping etherification reaction after mechanical stirring for 6h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product does not contain sodium chloride (checking by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and then drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherification product was determined by acid titration to be 0.57.
Example 9
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 6 wt% (relative to the absolute dry starch mass) of nano-cellulose, stirring and mixing for 0.5h, adding 20 wt% of NaOH to alkalize for 1h at 40 ℃, adding 15 wt% of sodium chloroacetate solution (with the concentration of 50 wt%) to the three-neck flask, stopping etherification reaction after mechanical stirring for 4h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product does not contain sodium chloride (checking by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and then drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherification product was determined by acid titration to be 0.52.
Example 10
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 1 wt% (relative to the weight of the absolutely dry starch) of lignocellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 20 wt% of NaOH for alkalization for 0.5h, adding 15 wt% of monochloroacetic acid solution (with the concentration of 50 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 5h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product is free of sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH of the product to be neutral by using glacial acetic acid, and drying the product in a 45 ℃ oven to obtain white powdery etherified starch.
The degree of substitution of the etherified product was determined by acid titration to determine a degree of substitution of starch of 0.18.
Example 11
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 1 wt% (relative to the weight of the absolutely dry starch) of methyl cellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 20 wt% of NaOH for alkalization for 0.5h, adding 20 wt% of monochloroacetic acid solution (with the concentration of 50 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 5h, washing and centrifuging the product by using 80% volume fraction of methanol solution until the product is free of sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH of the product to be neutral by using glacial acetic acid, and drying the product in a 45 ℃ oven to obtain white powdery etherified starch.
The degree of substitution of the etherified product was determined by acid titration to determine a degree of substitution of starch of 0.21.
Example 12
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 1 wt% (relative to the absolute dry starch mass) of hydroxypropyl methylcellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 18 wt% of NaOH for alkalization for 3h, adding 20 wt% of sodium chloroacetate solution (with the concentration of 50 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 5h, washing and centrifuging the product by using 80% by volume of methanol solution until the product is free of sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherified product was determined by acid titration to determine a degree of substitution of starch of 0.25.
Example 13
Weighing 10g of starch and dissolving the starch with 30ml of absolute ethyl alcohol, pouring the mixture into a 250ml three-neck flask after stirring with a glass rod, adding 1 wt% (relative to the weight of the absolutely dry starch) of hydroxyethyl cellulose, stirring and mixing for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding 20 wt% of NaOH for alkalization for 1h, adding 10 wt% of sodium chloroacetate solution (with the concentration of 50 wt%) into the three-neck flask, stopping etherification reaction after mechanical stirring for 5h, washing and centrifuging the product by using 80% by volume of methanol solution until the product is free of sodium chloride (checked by using silver nitrate aqueous solution), adjusting the pH to be neutral by using glacial acetic acid, and drying the product in an oven at 45 ℃ to obtain white powdery etherified starch.
The degree of substitution of the etherified product was determined by acid titration to determine a degree of substitution of starch of 0.19.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of etherified corn starch with high degree of substitution is characterized in that the etherified corn starch with high degree of substitution is prepared by a solvent method under the condition that nano microcrystalline cellulose exists by taking corn starch as a raw material;
the high degree of substitution means that the degree of substitution is greater than 0.2;
the nano microcrystalline cellulose is nano microcrystalline cellulose NCC with the fiber length of 100-500 nm;
weighing 10-12g of starch, dissolving the starch with 25-30ml of absolute ethyl alcohol, stirring the starch by using a glass rod, pouring the mixture into a 250ml three-neck flask, adding nano microcrystalline cellulose accounting for 0.5-10 wt% of the absolute dry starch, stirring and mixing the mixture for 0.5h, adjusting the temperature of a water bath to 50 ℃, adding a certain amount of NaOH solution to alkalize the mixture for 0.5-3h, adding a certain amount of etherifying agent into the three-neck flask, mechanically stirring the mixture for 3-10h, stopping etherification reaction, washing the mixture by using 80% volume fraction of methanol solution, centrifuging the mixture until a product is detected to be free of sodium chloride by using a silver nitrate aqueous solution, adjusting the pH value to be neutral by using glacial acetic acid, and drying the product in a 45 ℃ oven to obtain white powdery etherified starch;
the etherifying agent is monochloroacetic acid or sodium chloroacetate;
the mass ratio of the corn starch to the etherifying agent is 100: 5-20.
2. The method of claim 1, wherein the mass to volume ratio of the corn starch to the ethanol is 10-12g:25-30 ml.
3. The method of claim 1, wherein the mass ratio of corn starch to sodium hydroxide is 100: 16-20.
4. The method of claim 1, wherein the alkalization reaction is at 40-50 ℃ for 0.5-3 h.
5. The process according to claim 1, wherein the etherification reaction is carried out at 40 to 50 ℃ for 3 to 10 hours.
6. A highly substituted etherified corn starch prepared by the process of any one of claims 1 to 5.
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