CN1916027A - Method for preparing carboxymethyl cellulose in high degree of substitution - Google Patents
Method for preparing carboxymethyl cellulose in high degree of substitution Download PDFInfo
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- CN1916027A CN1916027A CN 200610078867 CN200610078867A CN1916027A CN 1916027 A CN1916027 A CN 1916027A CN 200610078867 CN200610078867 CN 200610078867 CN 200610078867 A CN200610078867 A CN 200610078867A CN 1916027 A CN1916027 A CN 1916027A
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- etherification
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- alkali
- carboxymethyl cellulose
- alcohol
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006467 substitution reaction Methods 0.000 title claims description 20
- 239000001768 carboxy methyl cellulose Substances 0.000 title abstract description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title abstract description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title abstract description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 title abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 238000006266 etherification reaction Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229920000742 Cotton Polymers 0.000 claims abstract 2
- 229940089960 chloroacetate Drugs 0.000 claims abstract 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 claims abstract 2
- 239000011261 inert gas Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229920002678 cellulose Polymers 0.000 claims description 22
- 239000001913 cellulose Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000003113 alkalizing effect Effects 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- 235000019441 ethanol Nutrition 0.000 claims 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003599 detergent Substances 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 229940035429 isobutyl alcohol Drugs 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract 2
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 238000007086 side reaction Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229920003086 cellulose ether Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- -1 alkaline batteries Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KJJPESOHTCIVIS-UHFFFAOYSA-N 2-chloroacetic acid propan-2-ol Chemical compound C(C)(C)O.ClCC(=O)O KJJPESOHTCIVIS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229940023144 sodium glycolate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 2
- ZAMLGGRVTAXBHI-UHFFFAOYSA-N 3-(4-bromophenyl)-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(CC(O)=O)C1=CC=C(Br)C=C1 ZAMLGGRVTAXBHI-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical class [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
This invention provides a method for preparing carboxymethyl cellulose with ultrahigh substituent degree. The method comprises: (1) treating cotton and lignocellulose with 18-50% NaOH aqueous solution; (2) adding chloroacetate, chloroacetic acid or its sodium salt, and etherifying under stirring in an organic solvent under inert gas protection; (3) adding an alkali, heating for second etherification, neutralizing, washing and drying to obtain carboxymethyl cellulose with carboxymethyl mol substituent degree not lower than 2.0.
Description
One, the technical field
The invention belongs to the preparation and synthesis of carboxymethyl cellulose ether with ultrahigh substitution degree, and belongs to the technical field of polymer chemistry.
Second, background Art
The cellulose ether is a high molecular polymerobtained by chemically modifying, alkalizing and etherifying natural cellulose. The water-soluble cellulose ether has good properties of thickening, suspending, dispersing, film forming, bonding, colloid keeping, microorganism stability and the like, so the water-soluble cellulose ether is applied to industrial departments such as petroleum drilling, food, medicine, coating, building, daily chemical industry, ceramics, paper making, electronic departments and the like, and has wide application.
Carboxymethyl cellulose ether is the most important ionic cellulose ether, is an ionic cellulose ether obtained by alkalization, carboxymethylation, intermediate washing and purification of natural cellulose, is one of the most important water-soluble polymers in industry, and has extremely wide application in industry. The substitution degree of carboxymethyl cellulose ether sold in the current market is about 0.60-1.20. With the continuous expansion of application fields, various complex and deteriorated application environments require that carboxymethyl cellulose ether with higher degree of substitution and more uniform substitution is a common trend at home and abroad in a use environment with high temperature, low pH value and high salt content. The carboxymethyl cellulose with ultrahigh substitution degree has wider substitution degree and viscosity range, higher storage stability and thermal stability, better acid and alkali resistance and salt resistance, good rheological property, smaller thixotropy and the like, and can be better applied to various industries such as toothpaste, alkaline batteries, oil exploitation, reactive dye printing and dyeing slurry and the like.
The development of carboxymethyl cellulose with ultrahigh substitution degree begins in countries such as the United states and Japan in the eighties and ninety years of the last century, and patents U.S. Pat. No. 4,426,206 and U.S. Pat. No. 5,455,341 report methods for synthesizingcarboxymethyl cellulose with ultrahigh substitution degree in multiple steps, but more methods have complex processes and high energy consumption and have the defects of reduced polymerization degree and viscosity of products, high process cost and the like; in order to obtain a carboxymethyl cellulose product with moderate degree of polymerization and ultrahigh degree of substitution, the research on a reasonable reaction mechanism and a preparation process is very meaningful, and the carboxymethyl cellulose has very wide market and application prospects.
The invention belongs to a preparation method of carboxymethyl cellulose ether with ultrahigh substitution degree.
Third, the invention
The invention provides measures of stepwise continuous alkali addition, control of acid-base ratio of each reaction stage and the like, develops a method for etherification in the continuous alkali addition stage, does not need repeated cooling and heating steps, and can ensure that the product has higher etherification degree to obtain the carboxymethyl cellulose ether with ultrahigh substitution degree.
The synthesis of the carboxymethyl cellulose with ultrahigh substitution degree belongs to heterogeneous liquid-solid reaction, and is a process for realizing alkali addition and staged etherification reaction in situ after an inert organic solvent is alkalized. The following preparation processes are expressed in parts by weight unless otherwise specified:
under the reaction condition of 10-30 ℃, adding 200 parts of cellulose into 1600-3000 parts of organic solvent dissolved with a proper amount of 40% NaOH aqueous solution, and alkalizing the cellulose for 0.5-2 hours; slowly adding 800-1200 parts of 45-75% chloroacetic acid-organic solvent solution, then adding a proper amount of alkali, and adding 350-500 parts of total alkali in one-time alkalization; heating to 50-65 ℃ and keeping the temperature for 0.5-4 hours; then adding 350-450 parts of 35-45% NaOH aqueous solution, heating to 70-80 ℃, and keeping the temperature for reaction for 0.5-5 hours; neutralizing the solution with acid until the pH value is 7, centrifuging the solution, washing the solution with 70 to 80 percent aqueous alcohol solution, and drying the solution for 2 to 5 hours in a vacuum oven at the temperature of between 60 and 85 ℃.
The preparation principle of the highly substituted sodium carboxymethylcellulose can be represented by the following chemical reaction equation:
alkalization of cellulose to alkali cellulose:
conversion of chloroacetic acid to sodium chloroacetate:
conversion of alkali cellulose and sodium chloroacetate to:
neutralizing and washing:
here, x is a number less than 3 and greater than 2; n is the number of carboxymethyl groups substituted on each cellulose glucose ring, Cell- (ONa)3-n(CH2COO-Na+)nAfter washing, the Cell becomes Cell- (OH)3-n(OCH2COO-Na+)n. In addition, the reaction system is alkaline, some side reactions are generated in the presence of water, and by-products such as sodium glycolate and glycolic acid are generated and expressed by chemical equationsComprises the following steps:
the control of the side reactions is key in the process of preparing the product with ultrahigh substitution degree, and on one hand, the side reactions consume alkali and etherifying agent, so that the etherification efficiency is reduced; on the other hand, sodium glycolate, sodium ethoxide and more salt impurities in the product cause difficulty in product purification, influence the service performance of the product, such as acid resistance, temperature resistance and salt resistance, and greatly reduce the predictability of the calculation amount of the neutralizing acid. The degree of the side reaction is firstly related to the amount of free (or free) alkali in the system, namely the excessive alkali which is not used for cellulose to form alkali cellulose, and the higher the amount of the free alkali is, the stronger the side reaction is; in addition, the side reaction is directly related to the water amount of the system. The water in the system is used for promoting the cellulose to be alkalized, but the excessive water can cause the generated alkali cellulose to be hydrolyzed to be increased, so that the amount of free alkali is increased, and the side reaction degree is increased. Therefore, in order to prepare the side reaction, alkali needs to be reasonably used, and the water quantity of the system is controlled at the same time, namely the concentration, the adding mode and the adding quantity of the alkali in the reaction process are controlled, so that the aim of fully alkalizing to generate more complete alkali cellulose is fulfilled. In addition, temperature has a direct influence on side reactions. The reasonable control of the temperature rise speed and the reaction temperature is beneficial to the uniform etherification of the cellulose, the etherification efficiency is improved, and the occurrence of side reactions is inhibited.
The organic solvent medium can be selected from isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol, ethanol, toluene, etc., and any one of their aqueous mixed organic solvents; the etherifying agent may be selected from chloroacetic acid, sodium chloroacetate, etc.; the activating agent is any one of sodium hydroxide or potassium hydroxide or a mixture thereof.
Description of the drawings
FIG. 1: a flow chart of a preparation process of carboxymethyl cellulose with ultrahigh substitution degree.
Fifth, the detailed description
Example 1
Preparing 2300 parts of mixed solution from 450 parts of 40% NaOH aqueous solution and 1850 parts of isopropanol/toluene (85/15) under the reaction condition of 20 ℃, adding 200 parts of cellulose, and alkalizing for 45 minutes; slowly adding 1050 parts of 65% chloroacetic acid-isopropanol/toluene solution in 1 hour, stirring for 30 minutes, and then adding 690 parts of 40% alkali liquor, wherein the reaction temperature can not exceed 40 ℃ all the time; heating to 60 ℃ and keeping the temperature to react for 1.5 hours; and adding 425 parts of 40% NaOH aqueous solution, heating to 72-74 ℃, and keeping the temperature for reacting for 1.5 hours. Then, the mixture was neutralized with glacial acetic acid to PH 7, centrifuged, and the filter cake was washed once with 72% and 75% aqueous ethanol solutions, respectively, and dried in a vacuum oven at 80 ℃ for 4 hours to obtain a product.
Example 2
Under the reaction condition of 35 ℃, 500 parts of 35% NaOH aqueous solution and 2050 parts of n-butanol are prepared into 2550 parts of mixed solution, 200 parts of cellulose is added, and alkalization is carried out for 1 hour; slowly adding 950 parts of 70% chloroacetic acid-n-butanol solution within 70 minutes, stirring for 20 minutes, and then additionally adding 190 parts of NaOH solid, wherein the reaction temperature can not exceed 40 ℃ all the time; heating to 65 ℃ and keeping the temperature to react for 2 hours; adding 400 parts of 45% NaOH aqueous solution, heating to 75 ℃, and keeping the temperature for reaction for 1 hour. Then, the mixture was neutralized with glacial acetic acid to pH 7, centrifuged, and the cake was washed once with 79% and 82% aqueous methanol solutions and dried in a vacuum oven at 70 ℃ for 6 hours to obtain a product.
Example 3
Under the reaction condition of 10 ℃, 350 parts of 40% KOH aqueous solution and 1650 parts of isopropanol/ethanol (86/14) are prepared into 2000 parts of mixed solution, 200 parts of cellulose is added, and alkalization is carried out for 30 minutes; slowly adding 995 parts of 60% chloroacetic acid-propanol/ethanol solution in 50 minutes, stirring for 40 minutes, and then adding 750 parts of 45% alkali liquor in a supplementing manner until the reaction temperature can not exceed 40 ℃ all the time; heating to 55 ℃ and keeping the temperature to react for 3 hours; then adding 180 parts of KOH solid, heating to 70 ℃, and keeping the temperature for reaction for 2.5 hours. Then, the mixture was neutralized with glacial acetic acid to PH 7, centrifuged, and the filter cake was washed once with 70% and 78% aqueous acetone solutions, and dried in a vacuum oven at 85 ℃ for 2 hours to obtain a product.
Example 4
Preparing 2200 parts of mixed solution of 450 parts of 40% NaOH aqueous solution and 1850 parts of isopropanol under the reaction condition of 20 ℃, adding 200 parts of cellulose, and alkalizing for 45 minutes; slowly adding 1050 parts of 55% chloroacetic acid-isopropanol solution within 1 hour, stirring for 30 minutes, and then adding 690 parts of 40% alkali liquor, wherein the reaction temperature is not more than 40 ℃ all the time; heating to 60 ℃ and keeping the temperature to react for 1.5 hours; then 425 parts of 40% NaOH aqueous solution is added, the temperature is increased to 72-74 ℃, and the temperature is kept for reaction for 1.5 hours. Then, the mixture was neutralized with glacial acetic acid to PH 7, centrifuged, and the filter cake was washed once with 72% and 75% aqueous ethanol solutions, respectively, and dried in a vacuum oven at 80 ℃ for 4 hours to obtain a product.
Claims (11)
1. The preparation method of the carboxymethyl cellulose ether with ultrahigh substitution degree comprises the following steps: alkalizing natural cellulose with 18-50% NaOH aqueous solution, adding chloroacetic acid or a compound thereof dissolved in an inert solvent in an inert organic solvent medium according to a certain proportion under the protection of inert gas under the conditions of heating and stirring for etherification, adding 30-50% NaOH aqueous solution, heating for secondary etherification, neutralizing, washing and drying to obtain the carboxymethyl cellulose ether with the substitution degree of not less than 2.0.
2. The method according to claim 1, characterized in that natural cotton and wood cellulose are used as raw materials.
3. The process according to claim 1, wherein the alkalization,the warming and the etherification are carried out continuously in at least two stages.
4. The method according to claim 1, wherein the etherifying agent is chloroacetic acid, sodium chloroacetate, chloroacetate or the like.
5. The method according to claim 1, characterized in that the first etherification is carried out at a temperature of 50-70 ℃ for 1-5 h, and the reaction is carried out under the protection of nitrogen.
6. The method according to claim 1, characterized in that a proper amount of alkali is added in the secondary etherification, the temperature is raised to 70-80 ℃ and the etherification is carried out for 1-3 h, and the reaction is carried out under the protection of nitrogen.
7. The method according to claim 1, wherein the alkali-acid ratio of the primary etherification reaction is within a range of 1.3 to 1.9, and the alkali-acid ratio of the secondary etherification reaction is within a range of 2.0 to 2.3.
8. The method according to claim 1, wherein the inert organic solvent medium is selected from the group consisting of organic solvents such as isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethyl alcohol, toluene, and aqueous mixed organic solvents thereof.
9. The method according to claim 1, characterized in that the temperature of the system is reduced to 40-55 ℃, and an aqueous solution of an alcohol such as hydrochloric acid, acetic acid and the like with a certain concentration is added for neutralization.
10. The method according to claim 1, wherein the detergent is selected from methanol/water solution, ethanol/water solution, isopropanol/water solution, methanol/isopropanol/water solution, isopropanol/ethanol/water solution, etc. with a certain concentration.
11. The method of claim 1, wherein the synthesized ultra-high substitution carboxymethyl cellulose ether has a general formula:
R＝-OCH2COONa or OH, and the product is characterized in that the molar substitution degree of carboxymethyl on cellulose molecules can be controlled to be not less than 2.3.
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| CN 200610078867 CN1916027A (en) | 2006-05-11 | 2006-05-11 | Method for preparing carboxymethyl cellulose in high degree of substitution |
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| CN101240035B (en) * | 2008-03-14 | 2010-05-12 | 山东一滕化工有限公司 | Ultra-high substitution carboxymethyl cellulose sodium and its preparation method and application |
| CN101445561B (en) * | 2008-06-20 | 2011-01-05 | 淄博宜龙化工有限公司 | Preparing method of carboxymethyl cellulose with high viscosity and obtained product |
| CN101602938B (en) * | 2009-07-13 | 2012-11-28 | 北京理工大学 | Preparation method of cellulose-based drilling fluid filtrate reducer |
| CN104119454A (en) * | 2013-12-02 | 2014-10-29 | 上海长光企业发展有限公司 | Preparation method of polyanionic cellulose |
| CN104302671A (en) * | 2012-09-05 | 2015-01-21 | Gl化学株式会社 | Binder for electrode composition and secondary battery comprising same |
| CN104372687A (en) * | 2014-11-29 | 2015-02-25 | 滁州惠智科技服务有限公司 | Production method of cotton fiber/modified cotton fiber yarn-dyed cloth |
| CN104592398A (en) * | 2015-02-03 | 2015-05-06 | 重庆力宏精细化工有限公司 | Method for preparing sodium carboxymethyl cellulose |
| CN104844715A (en) * | 2015-05-08 | 2015-08-19 | 郝军元 | Preparation method of carboxymethylcellulose |
| CN104877033A (en) * | 2015-06-03 | 2015-09-02 | 西南大学 | Preparation method of carboxymethyl modified nano-crystalline celluloses |
| CN104894185A (en) * | 2015-05-11 | 2015-09-09 | 王美岭 | Method for preparing sodium carboxymethyl cellulose from straw |
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| CN106117371A (en) * | 2016-06-28 | 2016-11-16 | 陈建峰 | A kind of preparation method of carboxymethyl cellulose with high degree sodium |
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- 2006-05-11 CN CN 200610078867 patent/CN1916027A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101240035B (en) * | 2008-03-14 | 2010-05-12 | 山东一滕化工有限公司 | Ultra-high substitution carboxymethyl cellulose sodium and its preparation method and application |
| CN101445561B (en) * | 2008-06-20 | 2011-01-05 | 淄博宜龙化工有限公司 | Preparing method of carboxymethyl cellulose with high viscosity and obtained product |
| CN101602938B (en) * | 2009-07-13 | 2012-11-28 | 北京理工大学 | Preparation method of cellulose-based drilling fluid filtrate reducer |
| CN104302671A (en) * | 2012-09-05 | 2015-01-21 | Gl化学株式会社 | Binder for electrode composition and secondary battery comprising same |
| CN104302671B (en) * | 2012-09-05 | 2017-07-14 | Gl化学株式会社 | Electrode composition binding agent and the secondary cell containing the binding agent |
| CN104119454A (en) * | 2013-12-02 | 2014-10-29 | 上海长光企业发展有限公司 | Preparation method of polyanionic cellulose |
| CN105316930A (en) * | 2014-11-29 | 2016-02-10 | 耿云花 | Preparation method of formaldehyde-removing cotton fabric |
| CN105316929A (en) * | 2014-11-29 | 2016-02-10 | 耿云花 | Preparation method of formaldehyde-removing cotton fabric |
| CN104372687A (en) * | 2014-11-29 | 2015-02-25 | 滁州惠智科技服务有限公司 | Production method of cotton fiber/modified cotton fiber yarn-dyed cloth |
| CN104592398A (en) * | 2015-02-03 | 2015-05-06 | 重庆力宏精细化工有限公司 | Method for preparing sodium carboxymethyl cellulose |
| CN104844715A (en) * | 2015-05-08 | 2015-08-19 | 郝军元 | Preparation method of carboxymethylcellulose |
| CN104894185A (en) * | 2015-05-11 | 2015-09-09 | 王美岭 | Method for preparing sodium carboxymethyl cellulose from straw |
| CN104894185B (en) * | 2015-05-11 | 2018-09-25 | 横琴桦硕环保科技有限公司 | A method of preparing sodium carboxymethylcellulose from stalk |
| CN104877033A (en) * | 2015-06-03 | 2015-09-02 | 西南大学 | Preparation method of carboxymethyl modified nano-crystalline celluloses |
| CN104877033B (en) * | 2015-06-03 | 2018-07-06 | 西南大学 | A kind of preparation method of carboxymethyl modified nano-cellulose |
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| CN106117371A (en) * | 2016-06-28 | 2016-11-16 | 陈建峰 | A kind of preparation method of carboxymethyl cellulose with high degree sodium |
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| CN106866828B (en) * | 2017-04-18 | 2019-02-05 | 傅兵 | A kind of method of secondary etherificate production cationic fiber cellulose fiber |
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