CN101475696A - Process for preparing high viscosity sodium carboxymethylcellulose - Google Patents
Process for preparing high viscosity sodium carboxymethylcellulose Download PDFInfo
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- CN101475696A CN101475696A CNA200810177216XA CN200810177216A CN101475696A CN 101475696 A CN101475696 A CN 101475696A CN A200810177216X A CNA200810177216X A CN A200810177216XA CN 200810177216 A CN200810177216 A CN 200810177216A CN 101475696 A CN101475696 A CN 101475696A
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 11
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 title claims abstract description 11
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000742 Cotton Polymers 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000006266 etherification reaction Methods 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract 9
- 238000006243 chemical reaction Methods 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 22
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 7
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 2
- 229940106681 chloroacetic acid Drugs 0.000 claims 2
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000004898 kneading Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- 235000021050 feed intake Nutrition 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 hydroxyl hydrogen Chemical compound 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 125000002353 D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a method having simple and flexible operation for preparing ultra-high viscidity sodium carboxymethyl cellulose through a method of adding a crosslinking agent in the production process of a common kneading method. The method comprises the following steps: (1) mixing a certain amount of sodium hydroxide aqueous solution with ethanol aqueous solution in proportion in advance, cooling the mixed solution to room temperature and loosening purified cotton to flocculation; (2) adding the purified cotton and the mixed solution in a kneader to carry out basification reaction; (3) carrying out etherification reaction when the basification reaction is finished, wherein the step (3) has the characteristics that the crosslinking agent is added during adding etherifying agent and the weight of the crosslinking agent is 0.1 to 1.0 percent of that of the purified cotton; and (4), carrying out neutralization, washing, rake alcohol reclaiming, drying, crushing and sieving to obtain the product of ultra-high viscidity sodium carboxymethyl cellulose. The method has simple and flexible operation and the obtained product has ultra-high viscidity.
Description
Technical field
The present invention relates to a kind of method for preparing the technical grade high viscosity sodium carboxymethylcellulose.
Background technology
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 is a kind of macromolecular chemistry material, can water-swelling, in water, during swelling, can form transparent thickness glue, and aspect potential of hydrogen, show as neutrality.The Na-CMC aqueous solution has performances such as good bonding, thickening, emulsification, suspension, film forming, protective colloid, maintenance moisture, resistance to enzymolysis and metabolism inertia.When carboxymethylcellulose sodium solution concentration increased, viscosity rose sharp, and the logarithm of viscosity and concentration is proportionlity slightly, and high viscosity is more obvious, when content 2～3% the time, solution almost presents the jelly shape.High viscosity sodium carboxymethylcellulose has the advantageous property of many uniquenesses, has obtained widespread use in industrial production such as daily washing composition, building, coating.
When using the kneading method to produce Na-CMC, methods such as the polymerization degree of main employing raising cellulosic material or nitrogen protection improve the viscosity of Xylo-Mucine, can improve the viscosity of product to a certain extent.Adopt the polymerization degree that improves cellulosic material, mainly be subjected to the influence of Mierocrystalline cellulose quality, in case the material quality fluctuation will have influence on the final viscosity of whole Na-CMC product, when for example using the highest M1000 purified cotton of the polymerization degree to produce the product of 6H type usually, use Brookfield (Brookfield) viscometer to measure the viscosity of 1%B type at most at 4000-5000cps, and along with the increase of substitution value, viscosity reduces gradually.And utilize the measure of nitrogen protection, and then make production stage loaded down with trivial details, wayward, potential safety hazard is arranged, increase unnecessary risk to enterprise.
Summary of the invention
The technical issues that need to address of the present invention are: with provide a kind of simple to operate flexibly, by mediating the method that the method for adding linking agent in the method production technique prepares high viscosity sodium carboxymethylcellulose in routine.
For addressing the above problem, the preparation method of high viscosity sodium carboxymethylcellulose of the present invention 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 the purified cotton shredding is become cotton-shaped, the mol ratio of purified cotton and sodium hydroxide is controlled at 1: 2.2～6.0, and the amount of aqueous ethanolic solution is 1～10 times of purified cotton;
2. in order purified cotton and mixed solution are joined in the kneader and alkalize, feed intake and close the kneader dog-house after finishing, alkalization temperature is controlled between 20～28 ℃, and the reaction times is 30～60 minutes;
3. alkalization is carried out etherification reaction after finishing, and the mol ratio of purified cotton and etherifying agent is controlled at 1: 1.0～2.8; Be characterized in: add linking agent during with etherifying agent, the weight of linking agent is 0.1～1.0% of purified cotton, and the time was controlled at 30～60 minutes, and temperature is controlled between 30～50 ℃; After adding, linking agent was warming up to 75～80 ℃ of etherification reactions 40～80 minutes;
4. to finish post neutralization to pH value be 6.5～8.5 to etherification reaction, after washing, by rake formula alcohol recovery device recovered alcohol, again drying, pulverize and sieve, obtain the high viscosity sodium carboxymethylcellulose product.
Linking agent recited above is selected from any in chloropropane, propylene glycol of chlorine, the epoxy chloropropane, and linking agent adopts and ethanol blended way is added, and linking agent and alcoholic acid weight ratio are 1: 20～30.
Etherifying agent recited above is chloroacetic spirituous solution, and wherein chloroacetic weight accounts for 50～80%.
The invention has the beneficial effects as follows: method of the present invention does not change the basic technology that original kneading method is produced, simple to operate flexible, the product that adopts this method production to obtain has ultra-high viscidity, particularly when substitution value during in 0.8 left and right sides, thickening effectiveness is obvious especially, the viscosity of using Brookfield (Brookfield) viscometer to measure the 1%B type can reach or near 8000cps, amount of increase reaches 40-50%.
Embodiment
The invention will be further described below in conjunction with specific embodiment.The umber of raw material and ratio are all by weight among the embodiment.
Embodiment 1:
In advance 2 parts of 48% aqueous sodium hydroxide solutions with 2.5 parts of mixing of aqueous ethanolic solution of 84.5%, mixed solution is cooled to room temperature, again 1 part of purified cotton shredding is become cotton-shaped, in order purified cotton and mixed solution are joined in the kneader and alkalize, feed intake and close the kneader dog-house after finishing, alkalization temperature is controlled between 20-28 ℃, and the reaction times is 30-60 minute.Alkalization is carried out etherification reaction after finishing, 1 part of the Mono Chloro Acetic Acid spirituous solution of etherifying agent employing 50-80%; Add the linking agent chloropropane during with etherifying agent, the weight of linking agent is 0.2% of purified cotton.Linking agent adopts and ethanol blended way is added, and linking agent and alcoholic acid weight ratio are 1: 22, and the time was controlled at 30-60 minute, and temperature is controlled between 30-50 ℃; High temperature (75-80 ℃) is etherification reaction 40-80 minute then.Being neutralized to pH value is 7.0, and through washing, alcohol reclaims (rake formula), and dry and pulverizing is sieved, and obtains the sticking cross-linking type Xylo-Mucine product of final extra-high-speed.Substitution value 0.652 purity 98.0%, the viscosity 2540cps of 1%B type.
Embodiment 2:
In advance 2.5 parts of 48% aqueous sodium hydroxide solutions with 3.0 parts of mixing of aqueous ethanolic solution of 90%, mixed solution is cooled to room temperature, again 1 part of purified cotton shredding is become cotton-shaped, in order purified cotton and mixed solution are joined in the kneader and alkalize, feed intake and close the kneader dog-house after finishing, alkalization temperature is controlled between 20-28 ℃, and the reaction times is 30-60 minute.Alkalization is carried out etherification reaction after finishing, 1.2 parts of the Mono Chloro Acetic Acid spirituous solutions of etherifying agent employing 50-80%; Add the linking agent propylene glycol of chlorine during with etherifying agent, the weight of linking agent is 0.25% of purified cotton; Linking agent adopts and ethanol blended way is added, and linking agent and alcoholic acid weight ratio are 1: 25, and the time was controlled at 30-60 minute, and temperature is controlled between 30-50 ℃; High temperature (75-80 ℃) is etherification reaction 40-80 minute then.Being neutralized to pH value is 6.5, washing, and alcohol reclaims (rake formula), and dry and pulverizing is sieved, and obtains the sticking cross-linking type Xylo-Mucine product of final extra-high-speed.Substitution value 0.736 purity 97.6%, the viscosity 3460cps of 1%B type.
Embodiment 3:
In advance 2.5 parts of 50% aqueous sodium hydroxide solutions with 2.8 parts of mixing of aqueous ethanolic solution of 92%, mixed solution is cooled to room temperature, again 1 part of purified cotton shredding is become cotton-shaped, in order purified cotton and mixed solution are joined in the kneader and alkalize, feed intake and close the kneader dog-house after finishing, alkalization temperature is controlled between 20-28 ℃, and the reaction times is 30-60 minute.Alkalization is carried out etherification reaction after finishing, and 1.3 parts of the Mono Chloro Acetic Acid spirituous solutions of etherifying agent employing 50-80% add the linking agent epoxy chloropropane during with etherifying agent, and the weight of linking agent is 0.3% of purified cotton; Linking agent adopts and ethanol blended way is added, and linking agent and alcoholic acid weight ratio are 1: 30, and the time was controlled at 30-60 minute, and temperature is controlled between 30-50 ℃.High temperature (75-80 ℃) is etherification reaction 40-80 minute then.Being neutralized to pH value is 8.0, washing, and alcohol reclaims (rake formula), and dry and pulverizing is sieved, and obtains the sticking cross-linking type Xylo-Mucine product of final extra-high-speed.Substitution value 0.835 purity 97.2%, the viscosity 7860cps of 1%B type.
Embodiment 4:
In advance 3.3 parts of 49% aqueous sodium hydroxide solutions with 3.2 parts of mixing of aqueous ethanolic solution of 93%, mixed solution is cooled to room temperature, again 1 part of purified cotton shredding is become cotton-shaped, in order purified cotton and mixed solution are joined in the kneader and alkalize, feed intake and close the kneader dog-house after finishing, alkalization temperature is controlled between 20-28 ℃, and the reaction times is 30-60 minute.Alkalization is carried out etherification reaction after finishing, and 1.6 parts of the Mono Chloro Acetic Acid spirituous solutions of etherifying agent employing 50-80% add the linking agent chloropropane during with etherifying agent, and the weight of linking agent is 0.5% of purified cotton; Linking agent adopts and ethanol blended way is added, and linking agent and alcoholic acid weight ratio are 1: 20, and the time was controlled at 30-60 minute, and temperature is controlled between 30-50 ℃.High temperature (75-80 ℃) is etherification reaction 40-80 minute then.Being neutralized to pH value is 7.2, washing, and alcohol reclaims (rake formula), and dry and pulverizing is sieved, and obtains the sticking cross-linking type Xylo-Mucine product of final extra-high-speed.Substitution value 0.996 purity 98.4%, the viscosity 4326cps. of 1%B type
Embodiment 5:
In advance 4.6 parts of 48.5% aqueous sodium hydroxide solutions with 3.3 parts of mixing of aqueous ethanolic solution of 94.5%, mixed solution is cooled to room temperature, again 1 part of purified cotton shredding is become cotton-shaped, in order purified cotton and mixed solution are joined in the kneader and alkalize, feed intake and close the kneader dog-house after finishing, alkalization temperature is controlled between 20-28 ℃, and the reaction times is 30-60 minute.Alkalization is carried out etherification reaction after finishing, 2.5 parts of the Mono Chloro Acetic Acid spirituous solutions of etherifying agent employing 50-80%.During with etherifying agent, add the linking agent chloropropane, the weight of linking agent is 1.0% of purified cotton, and linking agent adopts and ethanol blended way is added, and linking agent and alcoholic acid weight ratio are 1: 23, time was controlled at 30-60 minute, and temperature is controlled between 30-50 ℃.High temperature (75-80 ℃) is etherification reaction 40-80 minute then.Being neutralized to pH value is 6.8, washing, and alcohol reclaims (rake formula), and dry and pulverizing is sieved, and obtains the sticking cross-linking type Xylo-Mucine product of final extra-high-speed.Substitution value 1.324 purity 96.1%, the viscosity 3126cps. of 1%B type
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
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| CNA200810177216XA CN101475696A (en) | 2008-12-09 | 2008-12-09 | Process for preparing high viscosity sodium carboxymethylcellulose |
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| CNA200810177216XA CN101475696A (en) | 2008-12-09 | 2008-12-09 | Process for preparing high viscosity sodium carboxymethylcellulose |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967231A (en) * | 2010-09-30 | 2011-02-09 | 华南理工大学 | Production method of sodium carboxymethyl cellulose with low sodium content |
| CN102093579A (en) * | 2009-12-10 | 2011-06-15 | 上海长光企业发展有限公司 | Method for preparing sodium carboxymethylcellulose with extra-high viscosity |
| CN102295831A (en) * | 2010-06-23 | 2011-12-28 | 深圳市意可曼生物科技有限公司 | Special material for fully biodegradable rigid sheet and preparation method thereof |
| 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 |
| CN102775503A (en) * | 2012-08-14 | 2012-11-14 | 常熟威怡科技有限公司 | Preparation method of high-salt resistance high-viscosity sodium carboxymethylcellulose |
| CN102887956A (en) * | 2012-10-22 | 2013-01-23 | 河北业之源化工有限公司 | Method for preparing technical grade sodium carboxymethylcellulose with high viscosity and high salt resistance |
| CN103059321A (en) * | 2013-01-25 | 2013-04-24 | 湖北葛店人福药用辅料有限责任公司 | Preparation method of cross-linking sodium carboxymethylcellulose pharmaceutical adjuvant |
| CN103224565A (en) * | 2013-04-27 | 2013-07-31 | 甘肃圣大方舟马铃薯变性淀粉有限公司 | Method for preparing carboxymethyl cellulose used in printing paste by using straws |
| CN104072621A (en) * | 2014-06-30 | 2014-10-01 | 泸州北方化学工业有限公司 | Method for preparing ultrahigh-viscosity sodium carboxymethyl cellulose |
| CN104560247A (en) * | 2014-12-29 | 2015-04-29 | 福建清源科技有限公司 | Composite coal water slurry additive and preparation method thereof |
| IT201700102009A1 (en) * | 2017-09-12 | 2019-03-12 | Promoitalia Group Spa | REGENERATING AND SMOOTHING COMPOSITION FOR THE TREATMENT OF SKIN INESTETISIS AND ITS PREPARATION PROCEDURE |
-
2008
- 2008-12-09 CN CNA200810177216XA patent/CN101475696A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093579A (en) * | 2009-12-10 | 2011-06-15 | 上海长光企业发展有限公司 | Method for preparing sodium carboxymethylcellulose with extra-high viscosity |
| CN102093579B (en) * | 2009-12-10 | 2014-04-30 | 上海长光企业发展有限公司 | Method for preparing sodium carboxymethylcellulose with extra-high viscosity |
| CN102295831A (en) * | 2010-06-23 | 2011-12-28 | 深圳市意可曼生物科技有限公司 | Special material for fully biodegradable rigid sheet and preparation method thereof |
| CN101967231B (en) * | 2010-09-30 | 2012-06-20 | 华南理工大学 | Production method of sodium carboxymethyl cellulose with low sodium content |
| CN101967231A (en) * | 2010-09-30 | 2011-02-09 | 华南理工大学 | Production method of sodium carboxymethyl cellulose with low sodium content |
| 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 |
| CN102775503A (en) * | 2012-08-14 | 2012-11-14 | 常熟威怡科技有限公司 | Preparation method of high-salt resistance high-viscosity sodium carboxymethylcellulose |
| CN102775503B (en) * | 2012-08-14 | 2014-06-18 | 常熟威怡科技有限公司 | Preparation method of high-salt resistance high-viscosity sodium carboxymethylcellulose |
| CN102887956B (en) * | 2012-10-22 | 2015-06-03 | 河北业之源化工有限公司 | Method for preparing technical grade sodium carboxymethylcellulose with high viscosity and high salt resistance |
| CN102887956A (en) * | 2012-10-22 | 2013-01-23 | 河北业之源化工有限公司 | Method for preparing technical grade sodium carboxymethylcellulose with high viscosity and high salt resistance |
| CN103059321A (en) * | 2013-01-25 | 2013-04-24 | 湖北葛店人福药用辅料有限责任公司 | Preparation method of cross-linking sodium carboxymethylcellulose pharmaceutical adjuvant |
| CN103059321B (en) * | 2013-01-25 | 2015-11-18 | 湖北葛店人福药用辅料有限责任公司 | A kind of preparation method of croscarmellose sodium pharmaceutical excipient |
| CN103224565A (en) * | 2013-04-27 | 2013-07-31 | 甘肃圣大方舟马铃薯变性淀粉有限公司 | Method for preparing carboxymethyl cellulose used in printing paste by using straws |
| CN103224565B (en) * | 2013-04-27 | 2016-01-20 | 甘肃圣大方舟马铃薯变性淀粉有限公司 | Utilize straw for the method for the carboxymethyl cellulose of printing gum |
| CN104072621A (en) * | 2014-06-30 | 2014-10-01 | 泸州北方化学工业有限公司 | Method for preparing ultrahigh-viscosity sodium carboxymethyl cellulose |
| CN104560247A (en) * | 2014-12-29 | 2015-04-29 | 福建清源科技有限公司 | Composite coal water slurry additive and preparation method thereof |
| IT201700102009A1 (en) * | 2017-09-12 | 2019-03-12 | Promoitalia Group Spa | REGENERATING AND SMOOTHING COMPOSITION FOR THE TREATMENT OF SKIN INESTETISIS AND ITS PREPARATION PROCEDURE |
| WO2019053606A1 (en) * | 2017-09-12 | 2019-03-21 | Promoitalia Group S.P.A. | Regenerating composition with smoothing action for treating skin imperfections and process for preparation thereof |
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