CN113621086B - Preparation method of boron-free aldehyde-free hydroxyalkyl polysaccharide - Google Patents
Preparation method of boron-free aldehyde-free hydroxyalkyl polysaccharide Download PDFInfo
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- CN113621086B CN113621086B CN202110936024.8A CN202110936024A CN113621086B CN 113621086 B CN113621086 B CN 113621086B CN 202110936024 A CN202110936024 A CN 202110936024A CN 113621086 B CN113621086 B CN 113621086B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
Abstract
The invention relates to a preparation method of boron-free aldehyde-free hydroxyalkyl polysaccharide, in particular to a method for preparing hydroxyalkyl polysaccharide without using borax or glyoxal as a cross-linking agent. By optimizing the process and selecting proper polysaccharide dissolution and gelation inhibitors, the hydroxyalkyl polysaccharide can be prepared without using borax and glyoxal for end capping, and the product purity is high, and the light transmittance of the hydroxyalkyl polysaccharide at the wavelength of 500 nanometers of a 0.5 percent aqueous solution is higher.
Description
Technical Field
The invention relates to a preparation method of boron-free aldehyde-free hydroxyalkyl polysaccharide, in particular to a method for preparing hydroxyalkyl polysaccharide without using borax or glyoxal as a cross-linking agent (end capping agent) and the product characteristics thereof.
Background
In the preparation of hydroxyalkyl polysaccharides using water or a mixture of water and other polar organic substances as a medium, borax or glyoxal is generally used to slightly crosslink the polysaccharide (known as end-capping in industry) in order to prevent dissolution or gel formation of the hydroxyalkyl polysaccharide, so as to solve the problem of poor separation of the dispersion medium and the product during the production process.
However, hydroxyalkyl polysaccharides are mainly used in the cosmetic field, resulting in passive ingestion of trace amounts of boron or glyoxal by consumers. Years of research have demonstrated that excessive boron intake can damage human reproductive system function, affect fetal and childhood growth and development, and also affect human mental well-being. The international chemical safety program agency (ICPS) as early as 1998 has prescribed an allowable intake of 0.4 mg per kg body weight per person per day; the european food safety agency prescribes that minors of 1 to 17 years old are allowed to ingest 1 to 9 mg per day, respectively, according to ages, and adults are allowed to ingest 10 mg per day. In the year 2020, 12 kinds of compounds including boric acid, salts and esters thereof are listed as cosmetic forbidden components in the European Union, boric acid and sodium borate are listed as cosmetic forbidden components in taiwan of China in the same year, boric acid is listed as cosmetic forbidden components in japan as early as 2000, boric acid and borax are likewise listed as forbidden components in the catalogue of cosmetic forbidden issued in No. 28 of 5 months of 2021, and boric acid and salts thereof are listed as cosmetic limited use components in other countries and regions. Excessive intake of boron is harmful to human beings, and the concentration of boron exceeds the standard, so that the ecological environment is greatly damaged, and the growth and development of animals and plants are influenced, and even death is caused. In order to protect ecological environment, the new sewage discharge standard in China is increased with the index of boron content, and the boron content in sewage is regulated to be not more than 0.5mg/L.
Although glyoxal is not carcinogenic, it is irritating and cytotoxic and reacts with proteins to promote tumorigenesis. In addition, glyoxal generally contains a small amount of formaldehyde, which is a recognized carcinogen, due to production technology and purification problems, and the use of glyoxal in cosmetics can cause contamination of the product with formaldehyde. The american society of cosmetic raw materials evaluation (CIR) expert in 2000 concluded that glyoxal was safe for nail polish only, that is, unsafe for other cosmetics. ICPS prescribes a limited intake of 0.2 mg per kg body weight per person per day in 2004, with an ambient allowable concentration of 6 micrograms per cubic meter.
The hydroxyalkyl polysaccharide is prepared by using a mixture of water and polar organic solvent as a dispersion medium, and the polysaccharide and the hydroxyalkyl product thereof have the tendency of dissolving in water and forming gel, so that the preparation process is difficult to operate, and in order to solve the technical problem, borax or glyoxal is mostly adopted for crosslinking the polysaccharide in the traditional process. Borax is used as a cross-linking agent in both US5489674 and US 5536825; US9080952 uses glyoxal end-capping, although the inventors have attempted to remove glyoxal during post-treatment by chemical conversion techniques, there is still a small amount of glyoxal remaining in the product.
We have found that by optimizing the process and selecting the appropriate polysaccharide dissolution and gelation inhibitors, hydroxyalkyl polysaccharides can be prepared as well without borax and glyoxal capping, and that the product purity is high, with higher light transmittance at 500 nm wavelength of 0.5% aqueous solution.
Disclosure of Invention
The technical problem to be solved by the invention is to carry out hydroxyalkylation modification on polysaccharide under the condition of not using borax or glyoxal end capping agent, and the product performance index is better.
The technical scheme adopted by the invention for solving the technical problems is as follows: using water and a polar organic compound mixture as a dispersion medium; low molecular weight saccharides (including mono-and disaccharides) and monovalent water-soluble metal salts are used as polysaccharide dissolution and gel inhibitors; in order to improve the reaction efficiency, the polysaccharide is firstly decontaminated and activated in the presence of a catalyst, then is subjected to hydroxyalkylation reaction modification, and is purified, filtered and dried to obtain the boron-free and aldehyde-free hydroxyalkylation modified polysaccharide product. Based on 100 parts by weight of polysaccharide, the other materials are respectively: 50-2000 parts of polar organic compound and deionized water, 0-50 parts of low molecular weight saccharide, 0-50 parts of monovalent metal salt, 0.5-50 parts of catalyst, 0.5-100 parts of monovalent metal inorganic alkaline or organic alkaline compound, 5-150 parts of hydroxyalkyl etherifying agent and 1-100 parts of inorganic or organic acid. The water is deionized purified water; the polar organic compound is alcohols, ketones and ethers which can be mutually dissolved with water; the polysaccharide is galactomannan, starch or cellulose; the catalyst is a strong basic compound of monovalent metal; the inorganic alkaline compound is lithium, sodium and potassium hydroxide and sodium and potassium weak acid salt.
The beneficial effects of the invention are as follows: the use of harmful boron compounds and glyoxal is avoided by using low molecular weight saccharides and water-soluble monovalent metal salts to inhibit dissolution and gel formation of the polysaccharide and its modified products; the purity of the hydroxyalkylated polysaccharide product is higher, and the visible light transmittance of the 0.5 percent aqueous solution of 500 nanometers is higher through the optimization process.
Boron-free and aldehyde-free hydroxyalkyl polysaccharide preparation: the natural polysaccharide is used as raw material, deionized water and polar organic compound mixture are used as dispersion medium, and the finished product is obtained through polysaccharide impurity removal and activation, hydroxyalkylation modification, neutralization, washing and purification, filtration and drying. Before the polysaccharide is subjected to hydroxyalkylation modification, the polysaccharide is firstly subjected to impurity removal and activation in the presence of a catalyst, the polysaccharide is dispersed in a mixed medium of deionized purified water in which low-molecular-weight sugar and monovalent metal salt are dissolved and a polar organic compound, the nitrogen is used for replacing oxygen and heating to 40 ℃, then the catalyst is added, and the whole system is subjected to heating treatment in a nitrogen atmosphere to obtain the polysaccharide which is basically removed of grease, cellulose, protein and other impurities and is activated; the treated polysaccharide reacts with a hydroxyalkyl etherifying agent under alkaline condition, and after the reaction is finished, acid is added to neutralize alkali in the system, so that the system is nearly neutral; and then washing, purifying, filtering and drying to obtain a finished product.
The polysaccharide is natural galactomannan, starch, cellulose, preferably galactomannan such as guar gum, cassia gum, locust bean gum, tara gum, and locust bean gum.
The polar organic compound is water-miscible alcohols, ketones, ethers, preferably alcohols, more preferably ethanol and isopropanol.
The low molecular weight saccharide is monosaccharide, disaccharide, oligosaccharide, preferably glucose, sucrose, mannose, galactose.
The monovalent metal salt is lithium salt, sodium salt, potassium salt, preferably sodium salt.
The catalyst is a strong basic compound of monovalent metals soluble in polar solvents, sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide, preferably sodium hydroxide.
The monovalent metal alkaline compound is lithium, sodium, potassium hydroxide and sodium, potassium weak acid salt, preferably sodium hydroxide.
The alkaline organic compound is amine, pyridine or pyrrole.
The hydroxyalkyl etherifying agent is ethylene oxide, propylene oxide, alkylene oxide with six carbon or less end groups, 2-hydroxy chloropropane and 2-chloroethanol, preferably ethylene oxide and propylene oxide.
The acid is hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, or citric acid, preferably hydrochloric acid or acetic acid.
The preparation process of the boron-free aldehyde-free hydroxyalkyl polysaccharide comprises the following steps:
(1) Adding deionized water and alcohol into a reaction vessel according to a proportion at room temperature, adding low molecular weight sugar and monovalent metal salt, and after dissolution, adding polysaccharide and uniformly dispersing.
(2) And replacing air in the reaction vessel by nitrogen, pumping and filling at least three times, and adding a catalyst when the temperature is raised to 35-40 ℃ under the nitrogen atmosphere after the replacement is finished.
(3) The temperature is continuously raised to 50-120 ℃, and the reaction is activated for 30-600 minutes under the condition. Cooling, and filtering.
(4) Filtering to remove impurities, transferring the polysaccharide subjected to impurity removal activation into a reaction container, adding an alkaline compound, introducing nitrogen, pumping and replacing for three times, pressing the hydroxyalkyl etherifying agent with nitrogen, and controlling the amount and times of pressing the hydroxyalkyl etherifying agent according to the reaction condition.
(5) Heating to 35-45 deg.c for reaction for 5-300 min; heating to 50-95 deg.c and reaction for 5-600 min. Cooling to below 40deg.C, adding acid to adjust pH to about 7, and filtering when temperature is below 35deg.C.
(6) And placing the hydroxyalkyl polysaccharide obtained by filtering into a container, adding a solvent for washing and purifying, and then filtering and drying to obtain a target product.
Detailed Description
In order to better illustrate the technical process and advantages of the present invention, the following examples are used to illustrate the effects of the invention. The present invention is not limited to the contents of the examples.
Example 1
75Kg of isopropanol, 78Kg of deionized water, 1.50Kg of sucrose, 0.75Kg of sodium chloride and 25.0Kg of guar gum are sequentially added into a reaction vessel with stirring at room temperature; after the air in the reaction vessel is replaced by nitrogen for three times, the temperature is raised to 40 ℃, 3.20Kg of sodium hydroxide (solution state) catalyst is pressed in by nitrogen, and the materials in the reaction vessel are always in nitrogen atmosphere for reaction; heating to 90-95 deg.c and reaction for 40min; cooling to below 40deg.C, filtering, washing with 50% isopropanol water solution, and filtering twice; adding the washed material into a reaction container containing 150Kg of 90% isopropanol water solution, adding 1.80Kg of sodium hydroxide (in a solution state), replacing with nitrogen for three times, and filling nitrogen for protection; 21.75Kg propylene oxide was pressed in with nitrogen in two passes; heating to 40 ℃, and reacting for 30min; heating to 50 ℃, and reacting for 90min; heating to 65 ℃ and reacting for 150min; after the reaction is completed, cooling to below 40 ℃, adding acetic acid to adjust the PH to about 7, cooling to below 35 ℃ and filtering; the filter material is washed once by 80 percent isopropyl alcohol and pure isopropyl alcohol respectively in sequence, and the filter material is dried to obtain the product. The main performance indexes of the product are shown in table 1.
Example two
70Kg of isopropanol, 78Kg of deionized water, 2.00Kg of sucrose, 0.80Kg of sodium chloride and 25.0Kg of guar gum are sequentially added into a reaction vessel with stirring at room temperature; after the air in the container is replaced by nitrogen for three times, the temperature is raised to 40 ℃, 1.26Kg of sodium hydroxide catalyst is pressed in by nitrogen, and the materials in the container are always in nitrogen atmosphere for reaction; heating to 90-95 deg.c and reaction for 40min; cooling to below 40deg.C, filtering, washing with 50% isopropanol water solution, and filtering twice; adding the washed material into a reaction container containing 150Kg of 90% isopropanol water solution, simultaneously adding 1.62Kg of sodium hydroxide (in a solution state), replacing nitrogen for three times, protecting the nitrogen atmosphere, and pressing 13.95Kg of propylene oxide; heating to 40 ℃, and reacting for 30min; heating to 50 ℃, and reacting for 90min; heating to 65 ℃ and reacting for 150min; after the reaction is completed, cooling to below 40 ℃, adding acetic acid to adjust the PH to about 7, cooling to below 35 ℃ and filtering; the filter material is washed once by 80 percent isopropyl alcohol and pure isopropyl alcohol respectively in sequence, and the filter material is dried to obtain the product. The main performance indexes of the product are shown in table 1.
Example III
70Kg of isopropanol, 80Kg of deionized water, 1.50Kg of sucrose, 0.40Kg of sodium chloride and 25.0Kg of cassia gum are sequentially added into a reaction vessel with stirring at room temperature; after the air in the container is replaced by nitrogen for three times, the temperature is raised to 40 ℃, 4.50Kg of sodium hydroxide (solution state) catalyst is pressed in by nitrogen, and the materials in the container are always in nitrogen atmosphere for reaction; heating to 90-95 deg.c and reaction for 40min; cooling to below 40deg.C, filtering, washing with 45% isopropanol water solution, and filtering twice; adding the washed material into a reaction container containing 150Kg of 80% isopropanol water solution, simultaneously adding 2.14Kg of sodium hydroxide (in a solution state), replacing with nitrogen for three times, and protecting the nitrogen atmosphere; 22.80Kg of propylene oxide is pressed in; heating to 35 ℃, and reacting for 60min; heating to 60 ℃, and reacting for 150min; after the reaction is completed, cooling to below 40 ℃, adding acetic acid to adjust the PH to about 7, cooling to below 35 ℃ and filtering; the filter material is washed once by 80 percent isopropyl alcohol and pure isopropyl alcohol respectively in sequence, and the filter material is dried to obtain the product. The main performance indexes of the product are shown in table 1.
Example IV
60Kg of isopropanol, 90Kg of deionized water, 1.65Kg of sucrose, 0.30Kg of sodium chloride and 25.0Kg of cassia gum are sequentially added into a reaction vessel with stirring at room temperature; after the air in the container is replaced by nitrogen for three times, the temperature is raised to 40 ℃, 5.80Kg of sodium hydroxide (solution state) catalyst is pressed in by nitrogen, and the materials in the container are always in nitrogen atmosphere for reaction; heating to 90-95 deg.c and reaction for 40min; cooling to below 40deg.C, filtering, washing with 42% isopropanol water solution, and filtering twice; adding the washed material into a reaction container containing 150Kg of 90% isopropanol water solution, adding 0.56Kg of sodium hydroxide (in a solution state) at the same time, replacing with nitrogen for three times, and protecting the nitrogen atmosphere; pressing propylene oxide 15.8Kg; heating to 35 ℃, and reacting for 60min; heating to 60 ℃, and reacting for 150min; after the reaction is completed, cooling to below 40 ℃, adding acetic acid to adjust the PH to about 7, cooling to below 35 ℃ and filtering; the filter material is washed once by 80 percent isopropyl alcohol and pure isopropyl alcohol respectively in sequence, and the filter material is dried to obtain the product. The main performance indexes of the product are shown in table 1.
TABLE 1 hydroxypropyl polysaccharide Performance index
【1】 And (3) injection: brookfield viscosity (1% aqueous solution, 25 ℃, ph=6 to 7).
【2】 And (3) injection: 0.5% aqueous solution, 25 ℃, ph=6-7, 500 nm visible light conditions.
【3】 And (3) injection: and measuring the hydroxypropyl content by a nuclear magnetic method, and calculating to obtain the hydroxypropyl content.
【4】 And (3) injection: and determining the glycosyl content by a liquid chromatography and the modifying group content by a nuclear magnetic method.
Claims (9)
1. The preparation method of the boron-free aldehyde-free hydroxyalkyl polysaccharide is characterized by comprising the following steps of:
(1) Adding deionized water and a polar organic compound into a reaction vessel at room temperature, adding low molecular weight sugar and monovalent metal salt, and after dissolution, adding polysaccharide and uniformly dispersing;
(2) The air in the reaction vessel is replaced by nitrogen, at least three times of pumping and filling are carried out, and after the replacement is finished, the catalyst is added when the temperature is raised to 35 ℃ to 40 ℃ under the nitrogen atmosphere;
(3) Continuously heating to 50-120 ℃, activating for 30-600 minutes under the condition, cooling, and filtering;
(4) Filtering to remove impurities, transferring the polysaccharide subjected to impurity removal activation into a reaction container, adding an alkaline compound, introducing nitrogen, pumping and replacing for three times, pressing the hydroxyalkyl etherifying agent with nitrogen, heating to 35-45 ℃, and reacting for 5-300 minutes at the temperature; heating to 50-95 deg.c for reaction for 5-600 min;
(5) Cooling to below 40deg.C, adding acid to adjust pH to about 7, and filtering when the temperature is below 35deg.C;
(6) Placing the hydroxyalkyl polysaccharide obtained by filtration into a container, adding a solvent for washing and purifying, and then filtering and drying to obtain a target product; the polysaccharide is one of galactomannan, starch and cellulose, the polar organic compound is one or more of alcohols, ketones and ethers, and the monovalent metal salt is one or more of lithium salt, sodium salt and potassium salt; the catalyst is one or more of sodium oxide, potassium oxide, sodium hydroxide and potassium hydroxide which are strong alkaline compounds of monovalent metals and can be dissolved in polar solvents; the low molecular weight sugar is one or more of monosaccharide, disaccharide and oligosaccharide.
2. The method for preparing boron-free and aldehyde-free hydroxyalkyl polysaccharide according to claim 1, wherein the galactomannan is one of guar gum, cassia gum, coumarone, tara gum and locust bean gum.
3. The method for preparing boron-free and aldehyde-free hydroxyalkyl polysaccharide according to claim 1, wherein the alcohols are ethanol and isopropanol.
4. The method of producing boron-free, aldehyde-free hydroxyalkyl polysaccharide according to claim 1, wherein the low molecular weight sugar is one or more of glucose, sucrose, mannose, galactose.
5. The method for preparing boron-free and aldehyde-free hydroxyalkyl polysaccharide according to claim 1, wherein the basic compound is a monovalent metal basic compound or a basic organic compound; the monovalent metal alkaline compound is one or more of lithium, sodium and potassium hydroxide and sodium and potassium weak acid salt; the alkaline organic compound is one or more of amines, pyridines and pyrroles.
6. The method for preparing boron-free and aldehyde-free hydroxyalkyl polysaccharide according to claim 5, wherein the monovalent metal basic compound is sodium hydroxide.
7. The method for producing boron-free and aldehyde-free hydroxyalkyl polysaccharide according to claim 1, wherein the hydroxyalkylating etherifying agent is ethylene oxide, propylene oxide, six-carbon or less terminal alkylene oxide, 2-hydroxychloropropane, 2-chloroethanol.
8. The method for preparing boron-free aldehyde-free hydroxyalkyl polysaccharide according to claim 1, wherein the acid is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and citric acid.
9. The method for preparing boron-free and aldehyde-free hydroxyalkyl polysaccharide according to claim 1, wherein the content of the low molecular weight saccharide and the monovalent metal salt is not 0 at the same time, based on 100 parts by weight of the polysaccharide, 50 to 2000 parts of a mixed solvent of a polar organic compound and deionized water, 0 to 50 parts of a low molecular weight saccharide, 0 to 50 parts of a monovalent metal salt, 0.5 to 50 parts of a catalyst, 0.5 to 100 parts of an alkaline compound, 5 to 150 parts of a hydroxyalkyl etherifying agent, and 1 to 100 parts of an acid.
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| US4174440A (en) * | 1977-04-01 | 1979-11-13 | Sumitomo Chemical Company, Limited | Ionic pullulan gels and production thereof |
| US4321367A (en) * | 1980-09-02 | 1982-03-23 | The Dow Chemical Company | Method for the preparation of cross-linked polysaccharide ethers |
| US4384113A (en) * | 1982-03-23 | 1983-05-17 | The Dow Chemical Company | Stabilization of alkali polysaccharides |
| EP0281360A1 (en) * | 1987-03-02 | 1988-09-07 | STEIN, HALL & CO., INC. | Hydrophobically modified non-ionic polygalactomannan ethers |
| WO2008058768A1 (en) * | 2006-11-17 | 2008-05-22 | Lamberti Spa | Procedure for the preparation of glyoxalated cationic guar |
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| CN104974267A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Etherification-modified locust bean gum and preparation method thereof, water-base gel fracturing fluid containing the locust bean gum and application thereof |
| CN104277138B (en) * | 2014-10-30 | 2017-01-18 | 山东广浦生物科技有限公司 | Method for preparing carboxymethyl hydroxyalkyl guar gum powder by virtue of one-step etherification |
| CN106905441A (en) * | 2017-04-27 | 2017-06-30 | 中国石油集团渤海钻探工程有限公司 | A kind of hydroxypropyl TQ gums and preparation method thereof |
| CN107629139B (en) * | 2017-11-02 | 2019-12-10 | 山东广浦生物科技有限公司 | Transparent guar gum and preparation method thereof |
| WO2019119208A1 (en) * | 2017-12-18 | 2019-06-27 | 苏州昕能胶体技术有限公司 | Hydroxypropyl guar gum, preparation method therefor and use thereof |
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| US4174440A (en) * | 1977-04-01 | 1979-11-13 | Sumitomo Chemical Company, Limited | Ionic pullulan gels and production thereof |
| US4321367A (en) * | 1980-09-02 | 1982-03-23 | The Dow Chemical Company | Method for the preparation of cross-linked polysaccharide ethers |
| US4384113A (en) * | 1982-03-23 | 1983-05-17 | The Dow Chemical Company | Stabilization of alkali polysaccharides |
| EP0281360A1 (en) * | 1987-03-02 | 1988-09-07 | STEIN, HALL & CO., INC. | Hydrophobically modified non-ionic polygalactomannan ethers |
| WO2008058768A1 (en) * | 2006-11-17 | 2008-05-22 | Lamberti Spa | Procedure for the preparation of glyoxalated cationic guar |
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