CN101747441A - Preparation method of sodium carboxymethyl cellulose with high degree of substitution and high viscosity - Google Patents
Preparation method of sodium carboxymethyl cellulose with high degree of substitution and high viscosity Download PDFInfo
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- CN101747441A CN101747441A CN200810183562A CN200810183562A CN101747441A CN 101747441 A CN101747441 A CN 101747441A CN 200810183562 A CN200810183562 A CN 200810183562A CN 200810183562 A CN200810183562 A CN 200810183562A CN 101747441 A CN101747441 A CN 101747441A
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Abstract
The invention discloses a preparation method of sodium carboxymethyl cellulose with high degree of substitution and high viscosity, which can greatly reduce production cost. The preparation method comprises the following steps: (1) mixing a certain amount of sodium hydroxide water solution and ethanol water solution according to a certain proportion by weight in advance, cooling the mixture to room temperature, and softening wood pulp into floccule, wherein the weight of the solid sodium hydroxide is 0.01-0.5 time of the weight of the wood pulp; (2) firstly, adding 70-80% of solid sodium hydroxide, then sequentially adding the wood pulp and the mixed liquid into a kneading machine, and adding cross-linking agent for carrying out quaternization for the first time; (3) after quaternization is carried out for the first time, adding residual solid sodium hydroxide for carrying out quaternization for the second time; after quaternization is carried out for the second time, carrying out etherification, and heating up to 75-80 DEG C for carrying out high-temperature etherification for 40-80 minutes; and (4) regulating the pH of the material to be 6.5-8.5 with phenolphthalein, and drying, crushing and sieving the material to obtain the needed product. The method realizes high degree of substitution by adding alkali and acid for many times and realizes high viscosity by adding the cross-linking agent.
Description
Technical field
The present invention relates to a kind of method for preparing sodium carboxymethyl cellulose with high degree of substitution and high viscosity.
Background technology
Carboxymethyl cellulose (being called for short CMC) obtains natural cellulose through chemical modification, be one of industrial most important water-soluble polymers, develops rapidly at present.Carboxymethyl cellulose is the most representative ionic ether of cellulose, and normally used is its sodium salt.Xylo-Mucine (be called for short Na-CMC) be natural cellulose (being raw material with velveteen or wood pulp usually) under alkaline condition with Mono Chloro Acetic Acid generation etherification reaction, different by the situation that carboxymethyl replaced according to the raw material specification difference with the hydroxyl hydrogen in the Mierocrystalline cellulose D-glucose unit, the water-soluble high-molecular compound that different degree of substitution that obtains and different molecular weight distribute.Xylo-Mucine has the advantageous property of many uniquenesses, is widely used in industrial production such as building, cement, oil, food, weaving, washing composition, coating, medicine, papermaking and electronic devices and components.
Usually, the Na-CMC product of high substitution value adopts the aq slurry process of high bath raio, product substitution value height, and use properties is superior, but that its shortcoming is a production cost is very high.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that a kind of sodium carboxymethyl cellulose with high degree of substitution and high viscosity that can reduce production costs greatly will be provided.
For addressing the above problem, the technical solution used in the present invention is: the preparation method of described sodium carboxymethyl cellulose with high degree of substitution and high viscosity comprises the steps:
1. be weight concentration that 40～50% aqueous sodium hydroxide solution is 70～98% aqueous ethanolic solution with weight concentration by weight 1: 0.5～3 mixed in advance, the mixed solution that obtains is cooled to room temperature, again wooden oar shredding is become cotton-shaped, the mol ratio of wood oar and sodium hydroxide is controlled at 1: 2.2～6.0, and the amount of aqueous ethanolic solution is 1～10 times of wooden oar; The 0.01-0.5 solid sodium hydroxide doubly of preparing gross weight in addition and be wooden oar is stand-by;
2. will account for the solid sodium hydroxide of gross weight 70～80% and alcohol in advance puts in the kneader and mixes, in order wooden oar and mixed solution are joined in the kneader then and alkalize, throwing the wooden oar time was controlled at 10-20 minute, be controlled at 10-30 minute with the mixed solution time, feed intake and close the kneader dog-house after finishing, add linking agent, alkalization temperature is controlled between 20～30 ℃, and the reaction times is 20～40 minutes;
3. carry out the double alkalisation reaction: remaining solid sodium hydroxide is put in the kneader, and alkalization temperature is controlled between 25-35 ℃, and the reaction times is 10-20 minute; Carry out etherification reaction after the end, the molar ratio of wooden oar and etherifying agent is controlled at 1: 1.0-2.8; During adding etherifying agent, the time was controlled at 30-60 minute, and temperature is controlled between 30-55 ℃; Be warming up to 75～80 ℃ of high temperature etherification reactions after etherifying agent adds gradually 40～80 minutes, and finished etherification reaction;
4. etherification reaction finishes the back and transfers pH value with phenolphthalein, and the pH value of control material is 6.5～8.5, drying, pulverizes and sieves, and obtains the sodium carboxymethyl cellulose with high degree of substitution and high viscosity product.
Etherifying agent recited above is chloroacetic spirituous solution, and wherein chloroacetic weight accounts for 50～80%.
Advantage of the present invention is: the present invention realizes high viscosity by repeatedly adding alkali, repeatedly adding sour way realization high substitution value by adding linking agent, and production cost is lower.
Embodiment
The invention will be further described below by specific embodiment.
Embodiment 1:
1. in advance 48.5% aqueous sodium hydroxide solution is mixed with 94.0% aqueous ethanolic solution, blending ratio was controlled at 1: 1.56, was cooled to room temperature, wooden oar shredding was become cotton-shaped, the molar ratio of wood oar and sodium hydroxide was controlled at 1: 2.76, and the amount of aqueous ethanolic solution is 2.32 times of wooden oar.0.28 times solid sodium hydroxide preparing gross weight in addition and be wooden oar is stand-by.
2. in advance 70% solid sodium hydroxide and alcohol are put in the kneader and mixed, after wood pulp and mixed solution are joined in the kneader alkalize in order, throwing the wooden oar time was controlled at 10-20 minute, be controlled at 10-30 minute with the mixed solution time, feed intake and close the kneader dog-house after finishing, add linking agent, alkalization temperature is controlled between 20-30 ℃, and the reaction times is 20-40 minute.
3. carry out the double alkalisation reaction: the solid sodium hydroxide of remainder is put in the kneader, and alkalization temperature is controlled between 25-35 ℃, and the reaction times is 10-20 minute.Carry out etherification reaction after the end, etherifying agent adopts the Mono Chloro Acetic Acid spirituous solution of 50-80%, and the molar ratio of wooden oar and etherifying agent was controlled at 1: 2.05.
4. during adding etherifying agent, the time was controlled at 30-60 minute, and temperature is controlled between 30-55 ℃, the not overtemperature of trying one's best.
5. high temperature (70-80 ℃) is etherification reaction 40-80 minute, and insulation must be protected foot, finishes etherification reaction; Insulation finishes, and use the phenolphthalein adjust pH, and the pH that controls material is at 6.5-8.5, rake formula drying.6. crushing screening obtains required product.1%B type viscosity 10cps, substitution value 1.213, purity 96.46%.
Embodiment 2:
1. in advance 47.5% aqueous sodium hydroxide solution is mixed with 94.5% aqueous ethanolic solution, blending ratio was controlled at 1: 1.5, was cooled to room temperature, wooden oar shredding was become cotton-shaped, the molar ratio of wood oar and sodium hydroxide was controlled at 1: 2.8, and the amount of aqueous ethanolic solution is 2.2 times of wooden oar.0.25 times solid sodium hydroxide preparing gross weight in addition and be wooden oar is stand-by.
2. in advance 75% solid sodium hydroxide and alcohol are put in the kneader and mixed, after wood pulp and mixed solution are joined in the kneader alkalize in order, throwing the wooden oar time was controlled at 10-20 minute, be controlled at 10-30 minute with the mixed solution time, feed intake and close the kneader dog-house after finishing, add linking agent, alkalization temperature is controlled between 20-30 ℃, and the reaction times is 20-40 minute.
3. carry out the double alkalisation reaction: the solid sodium hydroxide of remainder is put in the kneader, and alkalization temperature is controlled between 25-35 ℃, and the reaction times is 10-20 minute.Carry out etherification reaction after the end, etherifying agent adopts the Mono Chloro Acetic Acid spirituous solution of 50-80%, and the molar ratio of wooden oar and etherifying agent was controlled at 1: 2.0.
4. during adding etherifying agent, the time was controlled at 30-60 minute, and temperature is controlled between 30-55 ℃, the not overtemperature of trying one's best.
5. high temperature (70-80 ℃) is etherification reaction 40-80 minute, and insulation must be protected foot, finishes etherification reaction; Insulation finishes, and neutralization washing phenolphthalein adjust pH, the pH that controls material be at 6.5-8.5, rake formula drying.
6. crushing screening obtains required product.1%B type viscosity 2500cps, substitution value 1.212, purity 95.86%.
Embodiment 3:
1. in advance 48.0% aqueous sodium hydroxide solution is mixed with 94.0% aqueous ethanolic solution, blending ratio was controlled at 1: 1.6, was cooled to room temperature, wooden oar shredding was become cotton-shaped, the molar ratio of wood oar and sodium hydroxide was controlled at 1: 2.7, and the amount of aqueous ethanolic solution is 2.3 times of wooden oar.0.28 times solid sodium hydroxide preparing gross weight in addition and be wooden oar is stand-by.
2. in advance 80% solid sodium hydroxide and alcohol are put in the kneader and mixed, after wood pulp and mixed solution are joined in the kneader alkalize in order, throwing the wooden oar time was controlled at 10-20 minute, be controlled at 10-30 minute with the mixed solution time, feed intake and close the kneader dog-house after finishing, add linking agent, alkalization temperature is controlled between 20-30 ℃, and the reaction times is 20-40 minute.
3. carry out the double alkalisation reaction: the solid sodium hydroxide of remainder is put in the kneader, and alkalization temperature is controlled between 25-35 ℃, and the reaction times is 10-20 minute.Carry out etherification reaction after the end, etherifying agent adopts the Mono Chloro Acetic Acid spirituous solution of 50-80%, and the molar ratio of wooden oar and etherifying agent was controlled at 1: 2.2.
4. during adding etherifying agent, the time was controlled at 30-60 minute, and temperature is controlled between 30-55 ℃, the not overtemperature of trying one's best.
5. high temperature (70-80 ℃) is etherification reaction 40-80 minute, and insulation must be protected foot, finishes etherification reaction; Insulation finishes, and neutralization washing phenolphthalein adjust pH, the pH that controls material be at 6.5-8.5, rake formula drying.
6. crushing screening obtains required product.1%B type viscosity 2368cps, substitution value 1.246, purity 96.14%.
Claims (2)
1. the preparation method of sodium carboxymethyl cellulose with high degree of substitution and high viscosity comprises the steps:
1. be weight concentration that 40～50% aqueous sodium hydroxide solution is 70～98% aqueous ethanolic solution with weight concentration by weight 1: 0.5～3 mixed in advance, the mixed solution that obtains is cooled to room temperature, again wooden oar shredding is become cotton-shaped, the mol ratio of wood oar and sodium hydroxide is controlled at 1: 2.2～6.0, and the amount of aqueous ethanolic solution is 1～10 times of wooden oar; The 0.01-0.5 solid sodium hydroxide doubly of preparing gross weight in addition and be wooden oar is stand-by;
2. will account for the solid sodium hydroxide of gross weight 70～80% and alcohol in advance puts in the kneader and mixes, in order wooden oar and mixed solution are joined in the kneader then and alkalize, throwing the wooden oar time was controlled at 10-20 minute, be controlled at 10-30 minute with the mixed solution time, feed intake and close the kneader dog-house after finishing, add linking agent, alkalization temperature is controlled between 20～30 ℃, and the reaction times is 20～40 minutes;
3. carry out the double alkalisation reaction: remaining solid sodium hydroxide is put in the kneader, and alkalization temperature is controlled between 25-35 ℃, and the reaction times is 10-20 minute; Carry out etherification reaction after the end, the molar ratio of wooden oar and etherifying agent is controlled at 1: 1.0-2.8; During adding etherifying agent, the time was controlled at 30-60 minute, and temperature is controlled between 30-55 ℃; Be warming up to 75～80 ℃ of high temperature etherification reactions after etherifying agent adds gradually 40～80 minutes, and finished etherification reaction;
4. etherification reaction finishes the back and transfers pH value with phenolphthalein, and the pH value of control material is 6.5～8.5, drying, pulverizes and sieves, and obtains the sodium carboxymethyl cellulose with high degree of substitution and high viscosity product.
2. preparation method according to claim 1 is characterized in that: described etherifying agent is chloroacetic spirituous solution, and wherein chloroacetic weight accounts for 50～80%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167749A (en) * | 2011-02-22 | 2011-08-31 | 广西大学 | Method for preparing high-substitution and high-viscosity sodium carboxymethyl cellulose from bagasse |
| CN102295706A (en) * | 2011-09-05 | 2011-12-28 | 安徽山河药用辅料股份有限公司 | Method for preparing croscarmellose sodium medicinal auxiliary material by using wood fibers |
| CN102675474A (en) * | 2012-05-23 | 2012-09-19 | 重庆力宏精细化工有限公司 | Preparation method of ultrahigh-viscosity sodium carboxymethyl cellulose |
| CN103755816A (en) * | 2013-12-20 | 2014-04-30 | 中国石油大学(北京) | Preparation method of sodium carboxymethylcellulose |
| CN105017544A (en) * | 2015-08-13 | 2015-11-04 | 江南大学 | Preparation of water-blocking biodegradable membrane containing low-viscosity rice-hull-based carboxymethyl cellulose |
| CN106117371A (en) * | 2016-06-28 | 2016-11-16 | 陈建峰 | A kind of preparation method of carboxymethyl cellulose with high degree sodium |
| CN106432515A (en) * | 2016-08-02 | 2017-02-22 | 赵天泽 | Preparation method of high substitution degree carboxymethyl cellulose sodium and application thereof |
| CN113710708A (en) * | 2019-05-01 | 2021-11-26 | 陶氏环球技术有限责任公司 | Process for producing crosslinked cellulose ethers |
| CN115873145A (en) * | 2023-03-08 | 2023-03-31 | 山东东瑞生物技术有限公司 | Preparation method of carboxymethyl chitosan |
-
2008
- 2008-12-19 CN CN200810183562A patent/CN101747441A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167749A (en) * | 2011-02-22 | 2011-08-31 | 广西大学 | Method for preparing high-substitution and high-viscosity sodium carboxymethyl cellulose from bagasse |
| CN102167749B (en) * | 2011-02-22 | 2012-12-12 | 广西大学 | Method for preparing high-substitution and high-viscosity sodium carboxymethyl cellulose from bagasse |
| CN102295706A (en) * | 2011-09-05 | 2011-12-28 | 安徽山河药用辅料股份有限公司 | Method for preparing croscarmellose sodium medicinal auxiliary material by using wood fibers |
| CN102675474A (en) * | 2012-05-23 | 2012-09-19 | 重庆力宏精细化工有限公司 | Preparation method of ultrahigh-viscosity sodium carboxymethyl cellulose |
| CN102675474B (en) * | 2012-05-23 | 2013-12-11 | 重庆力宏精细化工有限公司 | Preparation method of ultrahigh-viscosity sodium carboxymethyl cellulose |
| CN103755816A (en) * | 2013-12-20 | 2014-04-30 | 中国石油大学(北京) | Preparation method of sodium carboxymethylcellulose |
| CN105017544A (en) * | 2015-08-13 | 2015-11-04 | 江南大学 | Preparation of water-blocking biodegradable membrane containing low-viscosity rice-hull-based carboxymethyl cellulose |
| CN106117371A (en) * | 2016-06-28 | 2016-11-16 | 陈建峰 | A kind of preparation method of carboxymethyl cellulose with high degree sodium |
| CN106432515A (en) * | 2016-08-02 | 2017-02-22 | 赵天泽 | Preparation method of high substitution degree carboxymethyl cellulose sodium and application thereof |
| CN106432515B (en) * | 2016-08-02 | 2018-02-16 | 赵天泽 | A kind of preparation method and applications of carboxymethyl cellulose with high degree sodium |
| CN113710708A (en) * | 2019-05-01 | 2021-11-26 | 陶氏环球技术有限责任公司 | Process for producing crosslinked cellulose ethers |
| CN115873145A (en) * | 2023-03-08 | 2023-03-31 | 山东东瑞生物技术有限公司 | Preparation method of carboxymethyl chitosan |
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Application publication date: 20100623 |