CN108239174B - Sulfonated composite modified starch - Google Patents
Sulfonated composite modified starch Download PDFInfo
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- CN108239174B CN108239174B CN201611209941.1A CN201611209941A CN108239174B CN 108239174 B CN108239174 B CN 108239174B CN 201611209941 A CN201611209941 A CN 201611209941A CN 108239174 B CN108239174 B CN 108239174B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
- C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
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Abstract
The invention provides sulfonated composite modified starch, which is prepared from the following components in parts by weight: 100 parts of starch, 1-6 parts of sodium hydroxide, 1-10 parts of ammonium persulfate solution (1-10%), 1-10 parts of ammonium ferrous sulfate solution (1-10%), 1-10 parts of 1, 3-propyl sultone and 1-23% of water. The method has the advantages that the method is simple in production process, mild in condition and free of organic solvents polluting the environment, and the prepared sulfonated composite modified starch has high viscosity stability and strong permeability, can greatly improve the adhesive property after gelatinization, and has excellent temperature and salt resistance.
Description
Technical Field
The invention relates to sulfonated composite modified starch.
Technical Field
Starch is a natural polysaccharide which is rich in source and harmless to the environment, has good biodegradability, and has wide application in the fields of food, industry and the like, such as being used as a low-cost water retention agent in meat paste products, a thickening agent for seasoning foods, a filler for biodegradable plastics, and the gelatinized starch is used for adjusting the viscosity of drilling mud in the petroleum industry or sizing light yarns in textiles.
The structure of the starch is a starch macromolecule ring-type main chain consisting of glucose groups, the rigidity is poor, the flexibility is poor, the glass transition temperature is high, and the hydroxyl content in starch molecules even reaches 31.5 percent, so that the starch has the property of polyol, namely the starch can be used for generating ether with alcohol and ester with acid, is easy to be oxidized by an oxidant, and is a hydrophilic macromolecule. However, the quality of the natural starch is very unstable, and the starch is insoluble in cold water, poor in paste fluidity, poor in viscosity and thermal stability and crisp and hard in starch film due to the self structure of the starch, so that the industrial application of the starch is limited. Researchers develop a modification technology according to the structure and the physicochemical property to prepare starch meeting the performance requirement, the modification technology of the starch is to cut off and rearrange molecular chains of the starch or introduce other chemical groups by physical, chemical or enzymatic means so as to change the structure of the starch, namely, different means are adopted, and different modified starches can be obtained.
The sulfonated modified starch is an important starch modified product, and the sulfonic group is a strongly hydrophilic and strongly hydrated anionic group, and has strong adsorption effect and excellent temperature and salt resistance. The preparation method has various preparation methods, mainly comprises chlorosulfonic acid, fuming sulfuric acid, amine complexes, sulfonates and the like as sulfonating agents, and is mainly wet production at present, namely, starch and the sulfonating agents react in an organic solvent to generate sulfonated starch, so that a large amount of organic solvent is consumed, the environment is polluted, residual organic solvent after the reaction is difficult to remove, the whole process production flow is long, and the production cost is high. And the dry production process has the advantages of small material water content, simple process, high reaction efficiency, low energy consumption and little pollution.
CN201511023279 relates to a preparation method of a sulfonated modified composite modified starch slurry, which comprises the steps of firstly carrying out cationic modification on starch by using an etherifying agent 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, then carrying out esterification reaction on the starch and octenyl succinic anhydride, and finally reacting the prepared material with sodium bisulfite to prepare the sulfonated modified composite modified starch slurry, wherein the method has complex process and is difficult to industrialize; CN 102775507A provides a preparation method of sulfonated starch: the method adopts dry production, has simple process and low energy consumption, but still has the defects of organic solvent residue, need of subsequent treatment and environmental pollution.
Therefore, the modified starch which has excellent product performance, simple production process, mild condition and low cost, is environment-friendly and is suitable for industrial production is provided.
Disclosure of Invention
In order to solve the technical problems, the invention provides sulfonated composite modified starch, which oxidizes hydroxyl on a starch molecular chain and introduces hydrophilic sulfonic acid groups. The modified starch prepared by the method is not only easy to biodegrade, but also soluble in cold water, has low gelatinization temperature and good fluidity, and can greatly improve the adhesion performance after gelatinization.
The technical scheme provided by the invention is as follows:
the sulfonated composite modified starch mainly comprises the following components in parts by weight:
starch 100 parts
1-6 parts of sodium hydroxide
1-10 parts of ammonium persulfate solution (1-10%)
1-10 parts of ferrous ammonium sulfate solution (1-10%)
1-10 parts of 1, 3-propyl sultone
1-23 parts of water
Adding starch and sodium hydroxide powder into a container with a stirrer according to the weight ratio, uniformly stirring and mixing, fully alkalizing, adding an ammonium persulfate solution while stirring, uniformly mixing, raising the temperature to 50-60 ℃ for oxidation reaction, wherein the oxidation time is 1-2 hours; after the oxidation reaction is finished, cooling the substance to 30-40 ℃, and adding ferrous ammonium sulfate to remove more ammonium persulfate; adding a proper amount of water, adding 1, 3-propyl sultone, stirring and uniformly mixing, raising the temperature to 75-85 ℃ for sulfonation reaction, and reacting for 3-5 hours; and drying the material after the sulfonation reaction is finished at 110-130 ℃, and then crushing the material into powder with the granularity of 60-120 meshes to obtain the modified starch product.
The ammonium persulfate solution and the ferrous ammonium sulfate solution are added in a spraying and feeding mode, and the spraying speed is 30-50 ml/min. The spray feeding mode is favorable for uniformly mixing materials in dry production.
The concentration of the ammonium persulfate solution used is preferably 10%; the concentration of the ammonium ferrous sulfate solution used is preferably 10%.
The total hardness of water used is not more than 50; adding a proper amount of water to adjust the water content of the material to be 20-25%. The water quality with different hardness in the production process of the modified starch can influence the bridging reaction of the starch, so the hardness of the water needs to be controlled, and distilled water can be used as the production water. The water content of materials is usually lower in the production process of modified starch, and the materials need to be humidified so as to be beneficial to fully diffusing chemical reagents in starch during mixing and ensure the mixing uniformity. But the moisture is required to be distilled out in the subsequent drying process, so the moisture content of the material is proper for the energy conservation.
The starch is one or more of tapioca starch, corn starch, potato starch, wheat starch and rice starch.
Compared with the prior art, the invention has the following beneficial effects:
(1) the sulfonated composite modified starch prepared by the invention has the advantages of simple production process, mild conditions, low cost, no post-treatment, no three wastes and environmental protection, and can obtain modified starch meeting the requirements without using organic solvents in the production process.
(2) Hydroxyl on a starch molecular chain is oxidized, so that the starch adhesive has good fluidity, high viscosity stability and strong permeability, and can greatly improve the adhesive property after gelatinization; and hydrophilic and strongly hydrated sulfonic acid groups are introduced, so that the modified polyvinyl chloride has excellent temperature and salt resistance.
(3) The modified starch prepared by the invention has a very stable tissue structure, can be dissolved and swelled in cold water, has long storage time, and has wide application prospect in oil field drilling and light yarn sizing processes.
Detailed Description
Example 1
Adding 100g of cassava starch and 1g of sodium hydroxide powder into a container with a stirrer, uniformly stirring, fully alkalizing, adding 1% ammonium persulfate solution in a spraying and feeding manner while stirring, wherein the spraying speed is 30 ml/min; after uniformly mixing, heating the mixture to 50 ℃ for oxidation reaction, wherein the oxidation time is 1 hour; after the oxidation reaction is finished, cooling the material to 30 ℃, adding 1% of ammonium ferrous sulfate in a spraying and feeding mode to remove more ammonium persulfate, wherein the spraying speed is 30-50 ml/min; adding a proper amount of water, adjusting the water content of the material to be 20%, adding 1g of 1, 3-propyl sultone, stirring and uniformly mixing, raising the temperature to 75 ℃ for sulfonation reaction, and reacting for 3 hours; drying the material after the sulfonation reaction at 110 ℃, and then crushing the material into powder with the granularity of 60 meshes to prepare the modified starch product. The modified starch size film was determined to have an elongation at break of 4.58% and an adhesion of 153.1N.
Example 2
Adding 100g of cassava starch and 2g of sodium hydroxide powder into a container with a stirrer, uniformly stirring, fully alkalizing, adding a 4% ammonium persulfate solution (w/v) in a spraying and feeding manner while stirring, wherein the spraying speed is 36 ml/min; after mixing uniformly, the temperature is raised to 53 ℃ for oxidation reaction, and the oxidation time is 1.3 hours; after the oxidation reaction is finished, cooling the substance to 33 ℃, adding 4% ferrous ammonium sulfate in a spraying and feeding manner to remove more ammonium persulfate, wherein the spraying speed is 36 ml/min; adding a proper amount of water, adjusting the water content of the material to be 22%, adding 3g of 1, 3-propyl sultone, stirring and uniformly mixing, raising the temperature to 78 ℃ for sulfonation reaction, and reacting for 3.6 hours; and drying the material after the sulfonation reaction is finished at 117 ℃, and then crushing the material into powder with the granularity of 80 meshes to obtain the modified starch product. The modified starch size film was determined to have an elongation at break of 4.62% and an adhesion of 155.2N.
Example 3
Adding 100g of cassava starch and 4g of sodium hydroxide powder into a container with a stirrer, uniformly stirring, fully alkalizing, adding 7% ammonium persulfate solution (w/v) in a spraying and feeding manner while stirring, wherein the spraying speed is 43 ml/min; after uniformly mixing, heating the temperature to 57 ℃ for oxidation reaction, wherein the oxidation time is 1.7 hours; after the oxidation reaction is finished, cooling the material to 37 ℃, adding 7% ferrous ammonium sulfate in a spraying and feeding mode to remove more ammonium persulfate, wherein the spraying speed is 43 ml/min; adding a proper amount of water, adjusting the water content of the material to be 23%, adding 6g of 1, 3-propyl sultone, stirring and uniformly mixing, raising the temperature to 81 ℃ for sulfonation reaction, and reacting for 4.3 hours; and drying the material after the sulfonation reaction is finished at 124 ℃, and then crushing the material into powder with the granularity of 100 meshes to obtain the modified starch product. The modified starch size film was determined to have an elongation at break of 4.75% and an adhesion of 158.3N.
Example 4
Adding 100g of cassava starch and 6g of sodium hydroxide powder into a container with a stirrer, uniformly stirring, fully alkalizing, adding 10% ammonium persulfate solution (w/v) in a spraying and feeding manner while stirring, wherein the spraying speed is 50 ml/min; after uniformly mixing, heating the mixture to 60 ℃ for oxidation reaction for 2 hours; after the oxidation reaction is finished, cooling the substance to 40 ℃, adding 10% ferrous ammonium sulfate in a spraying and feeding manner to remove more ammonium persulfate, wherein the spraying speed is 50 ml/min; adding a proper amount of water, adjusting the water content of the material to be 25%, adding 10g of 1, 3-propyl sultone, stirring and uniformly mixing, raising the temperature to 85 ℃ for sulfonation reaction, and reacting for 5 hours; and drying the material after the sulfonation reaction is finished at 130 ℃, and then crushing the material into powder with the granularity of 120 meshes to prepare the modified starch product. The modified starch size film was determined to have an elongation at break of 4.71% and an adhesion of 161.3N.
Example 5
Adding 100g of potato starch and 6g of sodium hydroxide powder into a container with a stirrer, uniformly stirring, fully alkalizing, adding 10% ammonium persulfate solution (w/v) in a spraying and feeding manner while stirring, wherein the spraying speed is 50 ml/min; after uniformly mixing, heating the mixture to 60 ℃ for oxidation reaction for 2 hours; after the oxidation reaction is finished, cooling the substance to 40 ℃, adding 10% ferrous ammonium sulfate in a spraying and feeding manner to remove more ammonium persulfate, wherein the spraying speed is 50 ml/min; adding a proper amount of water, adjusting the water content of the material to be 25%, adding 10g of 1, 3-propyl sultone, stirring and uniformly mixing, raising the temperature to 85 ℃ for sulfonation reaction, and reacting for 5 hours; and drying the material after the sulfonation reaction is finished at 130 ℃, and then crushing the material into powder with the granularity of 120 meshes to prepare the modified starch product.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The sulfonated composite modified starch is characterized by mainly comprising the following components in parts by weight:
starch 100 parts
1-6 parts of sodium hydroxide
1-10 parts of ammonium persulfate solution with the concentration of 1-10%
1-10% of ammonium ferrous sulfate solution and 1-10 parts of
1-10 parts of 1, 3-propyl sultone
1-23 parts of water
Adding starch and sodium hydroxide powder under stirring according to the weight ratio, uniformly stirring, fully alkalizing, adding an ammonium persulfate solution while stirring, uniformly mixing, and heating for oxidation reaction; after the oxidation reaction is finished, cooling, and adding ammonium ferrous sulfate to remove redundant ammonium persulfate; adding a proper amount of water, adding 1, 3-propyl sultone, stirring and uniformly mixing, and heating to perform sulfonation reaction; and drying the material after the sulfonation reaction is finished, and then crushing the material into powder to obtain the modified starch product.
2. The sulfonated composite modified starch according to claim 1, wherein: the ammonium persulfate solution and the ferrous ammonium sulfate solution are added in a spraying and feeding mode, and the spraying speed is 30-50 mL/min.
3. The sulfonated composite modified starch according to claim 1, wherein: the concentration of the ammonium persulfate solution is 10 percent; the concentration of the used ammonium ferrous sulfate solution is 10 percent.
4. The sulfonated composite modified starch according to claim 1, wherein: the total hardness of water used is not more than 50; adding a proper amount of water to adjust the water content of the material to be 20-25%.
5. The sulfonated composite modified starch according to claim 1, 2, 3 or 4, wherein: the starch is one or more of tapioca starch, corn starch, potato starch, wheat starch and rice starch.
6. The sulfonated composite modified starch as claimed in claim 1, wherein the oxidation reaction temperature is 50-60 ℃ and the oxidation time is 1-2 hours.
7. The sulfonated composite modified starch as claimed in claim 1, wherein the sulfonation reaction temperature is 75-85 ℃ and the sulfonation reaction time is 3-5 hours.
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| CN111234041A (en) * | 2020-02-27 | 2020-06-05 | 安徽工程大学 | Acidolysis-crosslinking-sulfonation composite modified starch slurry and preparation method thereof |
| CN112210020B (en) * | 2020-09-28 | 2022-02-22 | 河南省化工研究所有限责任公司 | Preparation method and application of cold water instant high amylose starch |
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| US4086419A (en) * | 1976-02-24 | 1978-04-25 | National Starch And Chemical Corporation | Preparation of starch sulfate esters |
| CN103044717B (en) * | 2012-12-13 | 2016-02-24 | 广西农垦明阳生化集团股份有限公司 | A kind of preparation method of biodegradable plastic composite modified starch |
| CN103435709B (en) * | 2013-07-26 | 2016-02-24 | 广西大学 | Oxidative esterification composite modified starch and preparation method thereof |
| CN106517849B (en) * | 2015-09-10 | 2018-11-23 | 绵阳莫仕科技有限公司 | A kind of preparation method of oxidation-sulfonated starch water-reducing agent |
| CN105461818B (en) * | 2016-01-05 | 2018-04-13 | 中国石油大学(华东) | The semidry method preparation method of 2 hydroxyl, 3 sulfonic group propyl group starch ether |
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