CN104558206A - Method for preparing sodium carboxymethylcellulose - Google Patents
Method for preparing sodium carboxymethylcellulose Download PDFInfo
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- CN104558206A CN104558206A CN201410810504.XA CN201410810504A CN104558206A CN 104558206 A CN104558206 A CN 104558206A CN 201410810504 A CN201410810504 A CN 201410810504A CN 104558206 A CN104558206 A CN 104558206A
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Abstract
The invention relates to a method for preparing sodium carboxymethylcellulose, and belongs to the field of chemical synthesis. The low-cost and high-yield method for preparing the sodium carboxymethylcellulose provided by the invention specifically comprises the following steps: feeding powdery cellulose with the particle sizes being 10-100microns, feeding to a reaction container of a solvent, and stirring for 10 minutes; adding NaOH for the first time, controlling the temperature in the reactor to be 10-70 DEG C and reacting for 0.2-0.5 hour, adding monochloroacetic acid and NaOH, controlling the reaction temperature to be 20-50 DEG C, and evenly stirring and reacting for 1-2 hours; adding NaOH, stirring and controlling the reaction temperature to be 20-50 DEG C, reacting for 0.2-0.8 hour to obtain a crude product; and washing the crude product with ethanol, and decolorizing with activated carbon to obtain a product. The preparation method disclosed by the invention is mild in condition; and the product obtained by reaction is high in purity and good in transparency.
Description
Technical field
The invention provides a kind of preparation method of Xylo-Mucine, belong to chemical industry synthesis field.
Background technology
Xylo-Mucine is generally pulverous solid, sometimes also particulate state or threadiness can be presented, color is white or faint yellow, there is no special smell, it is a kind of macromolecular chemistry material, CMC have very strong draw moist, can be soluble in water, in water, form the viscous solution that transparency is very high.CMC is insoluble to general organic solution, such as ethanol, ether, chloroform and benzene etc., but can be water-soluble, and the direct speed soluble in water of CMC is comparatively slow, but solubleness is still very large, and the aqueous solution of CMC has certain viscosity.Solid CMC is more stable under general environment, because have certain water-absorbent and draw moist, under the environment of drying, can preserve for a long time.
Refining Xylo-Mucine product, this product is recognized as safe foodstuff additive.Last century, the seventies China started to adopt, and was the Mierocrystalline cellulose kind that in the world today, use range is the widest, consumption is maximum.
The sodium salt of carboxymethyl cellulose ether, belongs to anionic ether of cellulose, is white or oyster white fibrous powder or particle, density 0.5-0.7g/cm
3, almost odorless, tasteless, tool water absorbability.Be easy to be dispersed in water into clear gum solution, insoluble in the organic solvents such as ethanol.1% aqueous solution pH is 6.5 ~ 8.5, and as pH>10 or <5, cement viscosity significantly reduces, and when pH=7, performance is best.To thermally-stabilised, below 20 DEG C, viscosity rises rapidly, and when 45 DEG C, change is comparatively slow, and more than 80 DEG C long-time heating can make its colloid sex change and viscosity and performance obviously decline.Soluble in water, solution is transparent; Very stable in basic solution, meet acid then facile hydrolysis, when pH value is 2-3, there will be precipitation, meet polyvalent metal salt and also can react appearance precipitation.
Xylo-Mucine (be called for short CMC) is for raw material and a kind of anionic macromolecular compound of synthesizing with refining short cotton.Molecular weight is 6400 ± 1000, has excellent water-soluble and film-forming properties, is widely used in the industry such as oil, daily use chemicals, light industry, food, medicine, is described as " monosodium glutamate of industry ".The synthetic method of CMC-Na, one is water coal direct method (spray alkaline process), and two 1 kinds is the solvent method adopting organic molten coal, and due to the latter, to have alkali charge few, and etherification time is short, etherifying agent utilization ratio high, is therefore widely adopted at present.
The leading indicator weighing CMC-Na quality is substitution value (DS) and viscosity, and in general, DS is different, then the character of CMC-Na is also different; Substitution value increases, and the transparency of solution and stability are also better.It is reported, CMC-Na substitution value transparency when 0.7-1.2 is better, its solution viscosity is maximum when pH is 6-9, for ensureing its quality, except selection etherifying agent, also must consider some factors affecting substitution value and viscosity, such as, use magnitude relation, etherification time, content of water in system, temperature, pH value, strength of solution etc. between alkali and etherifying agent.
Mierocrystalline cellulose is macromolecular polysaccharide, and from 50000 to 2500000 not etc., namely the content of glucosyl group is not from 300 to 15000 etc. for molecular weight. be the product of raw material is widely used in food, weaving, plastics, electrician and medical aspect with Mierocrystalline cellulose.Because there is hydrogen bond between its molecule in Mierocrystalline cellulose, very stable at normal temperatures, water insoluble and be insoluble to general organic solvent, such as ethanol, acetone, benzene etc.Mierocrystalline cellulose in a heated condition, to coking of dewatering gradually when 150 DEG C.The biosynthetic process of its complexity of natural fiber procatarxis, makes a part of molecular chain crystallization cannot become non-crystalline region in crystalline region, so Mierocrystalline cellulose has crystalline region and non-crystalline region two macrostructure.
Summary of the invention
The invention provides that a kind of cost is low, the high method preparing Xylo-Mucine of productive rate, it is realized by following technical scheme:
First time adds alkali: being added to by powdery end Mierocrystalline cellulose in the reaction vessel dropping into solvent and stirring 10min and add NaOH, controlling reactor temperature is 10 ~ 70 DEG C, reaction 0.2 ~ 0.5h;
Second time adds alkali: add monochloroacetic acid again and NaOH, control temperature of reaction are 20 ~ 50 DEG C, and uniform stirring reaction 1 ~ 2h;
Third time adds alkali: again add NaOH, and stirring and controlling temperature of reaction is that 20 ~ 50 DEG C of reaction 0.2 ~ 0.8h obtain crude product.
Mierocrystalline cellulose, NaOH and ClCH in above-mentioned steps
2the mol ratio of COOH is 1:0.3 ~ 0.7:1.7 ~ 2.5.
Above-mentioned solvent is the solution of second alcohol and water, isopropyl alcohol and water further; The weight adding solvent is 7 ~ 15 times of cellulose.
Further, the concentration of above-mentioned NaOH alkali lye is 10 ~ 30%.
Further, in above-mentioned reaction, alkali divides three times to add in batches, first time add that alkali content is alkali total amount 40 ~ 60%, second time add that alkali number is alkali total amount 20 ~ 35%, third time adds the alkali of surplus.
In above-mentioned reaction, the particle diameter of Mierocrystalline cellulose warp is 10 ~ 100um, and fiber dust is scattered in containing in solvent, then adds NaOH, and reaction is for becoming alkali fiber at the temperature disclosed above; Add in alkali step to react with monochloroacetic acid again in second time and generate CMC; Obtain CMC-Na finally by three-step reaction, crude product adds 20 ~ 90% (v/v) washing with alcohol, and activated carbon decolorizing obtains fine work.
Above-mentioned further, the crude product washing with alcohol of 40 ~ 60% (v/v), the consumption of ethanolic soln is 4 ~ 7 times of crude product quality.
In reaction system, organic solvent content is associated with water content, product substitution value, etherification method and mechanical means used.If organic solvent content is too many, reduces the concentration of product in reaction solution, be unfavorable for cellulosic alkalization; And organic solvent very little, in system, organic solvent equilibrium concentration is too low, and Mierocrystalline cellulose is swelling or generation gelinite likely.
At present, domestic molten coal method produces the process that CMC passes through alkalization-etherificate-neutralization washing-drying and crushing, also referred to as instantaneous injection.There is product in aforesaid method, to replace homogeneity inadequate, and transparency, solution hexagon, anti-corrupt ability are inadequate etc. and the ability of the resistance to divalent salts of product, are embodied in and are having Ca
2+and Mg
2+time, viscosity significantly reduces.
In the present invention, cellulosic particle diameter is 5 ~ 100um; During reaction, cellulose powder is all scattered in the reaction medium of organic solvent, and form very uniform soda cellulose after alkalization, during etherificate, etherifying agent can enter in soda cellulose molecule equably, makes etherification reaction very even.Mierocrystalline cellulose, alkali lye, etherifying agent and solvent form slurry, under constantly stirring, carry out alkalizing and etherification reaction, sufficient reacting and obtain that the purity of product is high, transparency good.
Because alkali lye point to add for three times, it is fewer to there is following hydrolytic side reactions in Monochloro Acetic Acid.The first step quaternization is reacted at fibrousness and certain density NaOH solution, and generate soda cellulose, the soda cellulose that its object is to obtain has hyperergy, for etherification reaction is thereafter prepared; Second step and the 3rd step add alkali to be made, in order to allow soda cellulose and Monochloro Acetic Acid generation etherification reaction, to its object is to the hydroxyl on the carboxymethyl substituted cellulose in Monochloro Acetic Acid.
The examination and test of products:
1, qualitative reaction:
(1) outward appearance is white or micro-yellow fibers sprills.
(2) get 3 ~ 3g product and be placed in 100ml, 50 ~ 70 DEG C of water, stir, do flame reaction after being cooled to room temperature, flame is aureus.
(3) get above-mentioned 20ml sample solution, add 20% (wt%) hydrochloric acid 2ml, produce white precipitate.
(4) get 10ml sample liquid, add 2ml CuSO
4liquid, produces the light blue precipitation of fine hair shape.
2, viscosimetric analysis: high viscosity is 1000 ~ 2000cP; Medium viscosity is 500 ~ 1000cP; Low viscosity 100 ~ 500cP; Viscosimetric analysis be finished product is made into 2% the aqueous solution, with Ai meter La rotational viscosimeter 25 DEG C of mensuration.
3, replacement degree (D.S) measures
Mierocrystalline cellulose is natural high moleculer eompound, and with several structural units (glucosyl group) composition, CMC is a kind of derivatived cellulose (ether of cellulose), and he is with carboxymethyl group sodium (-CH
2cOONa) instead of the hydrogen of hydroxyl on original glucose unit and be worth.Because etherification reaction is not very even, therefore substitution value is a mean value.The present invention adopts grey alkaline process to measure.
4, transparency is with the CMC-Na solution configuring 1%, measures turbidity with turbidometer, converts by transparency-turbidity conversion table.
5, determination of moisture: accurately take a certain amount of product, is dried to constant weight at being placed in 105 DEG C, then moisture (%)=(m
lose/ m
sample) × 100%
The present invention adopts that the product purity that three of improvement times add alkaline methods prepares is high, transparency good; The simple and easy applicable huge construction program industrial production of preparation method simultaneously.
Embodiment
embodiment 1
By particle diameter be 50 ~ 100um powdery cellulose drop into containing 25%NaOH solution reactor in, stirring with 100 ~ 200r/min and controlling temperature of reaction is 30 ~ 50 DEG C, react 0.5h.And then add the NaOH solution of monochloroacetic acid and 25%, stirring with 150 ~ 400r/min, controlling temperature of reaction is 30 ~ 40 DEG C, after reaction 1.5h, again adding 25%NaOH solution in temperature is that 30 ~ 40 DEG C of reaction 0.5h obtain crude product, finally uses 50% (v/v) washing with alcohol of 2 of crude product quality times, with the activated carbon decolorizing of 0.07 times of crude product quality and dry fine work.Above-mentioned Mierocrystalline cellulose, NaOH and ClCH
2the mol ratio of COOH is 1 ︰ 0.5 ︰ 2, and the weight adding solvent is 7 times of cellulose.First time drop into alkali be alkali and total amount 50%, second time drop into alkali number be alkali total amount 35%, third time, to drop into alkali number be 15% of alkali total amount.Through qualitative analysis be micro-yellow fibers sprills, the flame of flame reaction is aureus, sample test solution adds hydrochloric acid and produces white precipitate, adds CuSO
4liquid, the light blue precipitation of villous shape, viscosity are that 1700cP, transparency are good, moisture content 4.5%.
embodiment 1
By particle diameter be 50 ~ 100um powdery cellulose drop into containing 20%NAOH solution reactor in, stirring with 150 ~ 300r/min and controlling temperature of reaction is 20 ~ 40 DEG C, react 0.3h.And then add the NaOH solution of monochloroacetic acid and 20%, stirring with 200 ~ 300r/min, controlling temperature of reaction is 40 ~ 50 DEG C, after reaction 1.5h, again adding 20%NaOH solution in temperature is that 40 ~ 50 DEG C of reaction 0.3h obtain crude product, finally uses 50% (v/v) washing with alcohol of 1.5 of crude product quality times, with the activated carbon decolorizing of 0.03 times of crude product quality and dry fine work.Above-mentioned Mierocrystalline cellulose, NaOH and ClCH
2the mol ratio of COOH is 1 ︰ 0.4 ︰ 2.5, and the weight adding solvent is 13 times of cellulose.First time drop into alkali be alkali and total amount 60%, second time drop into alkali number be alkali total amount 30%, third time, to drop into alkali number be 10% of alkali total amount.Through qualitative analysis be micro-yellow fibers sprills, the flame of flame reaction is aureus, sample test solution adds hydrochloric acid and produces white precipitate, adds CuSO
4liquid, the light blue precipitation of villous shape, viscosity are that 1800 cP, transparency are good, moisture content 3.7%.
Above-described embodiment is only in order to illustrate technical scheme of the present invention; but not design of the present invention and protection domain are limited; those of ordinary skill in the art modifies to technical scheme of the present invention or equivalent replacement; and not departing from aim and the scope of technical scheme, it all should be encompassed in right of the present invention.
Claims (8)
1. prepare the method for Xylo-Mucine for one kind, it is characterized in that: it comprises the following steps: by particle diameter be the powdery end Mierocrystalline cellulose of 10 ~ 100um be added to drop into solvent reaction vessel in and add NaOH with first time after stirring 10min, control reactor temperature and be 10 ~ 70 DEG C, react 0.2 ~ 0.5h; Add monochloroacetic acid again and NaOH, control temperature of reaction are 20 ~ 50 DEG C, and uniform stirring reaction 1 ~ 2h; And then add NaOH, stirring and controlling temperature of reaction is that 20 ~ 50 DEG C of reaction 0.2 ~ 0.8h obtain crude product; Above-mentioned crude product obtains product through the activated carbon decolorizing of 0.03 ~ 0.1 times of ethanolic soln washing, crude product quality.
2. a kind of method preparing Xylo-Mucine according to claim 1, is characterized in that: Mierocrystalline cellulose, NaOH and ClCH in described above-mentioned steps
2the mol ratio of COOH is 1:0.3 ~ 0.7:1.7 ~ 2.5.
3. a kind of method preparing Xylo-Mucine according to claim 1 or 3, is characterized in that: the concentration of described above-mentioned NaOH alkali lye is 10 ~ 30%.
4. a kind of method preparing Xylo-Mucine according to claim 1, is characterized in that: above-mentioned first time add that alkali content is alkali total amount 40 ~ 60%, second time add that alkali number is alkali total amount 20 ~ 35%, third time adds the alkali of surplus.
5. a kind of method preparing Xylo-Mucine according to claim 1, is characterized in that: described reaction solvent is the solution of second alcohol and water, isopropyl alcohol and water, the weight wherein adding solvent is 7 ~ 15 times of cellulose.
6. a kind of method preparing Xylo-Mucine according to claim 1, is characterized in that: described above-mentioned
The crude product washing with alcohol of 20 ~ 90% (v/v), the consumption of ethanolic soln is 2 ~ 11 times of crude product quality.
7. a kind of method preparing Xylo-Mucine according to claim 1 or 6, is characterized in that: described above-mentioned
The crude product washing with alcohol of 40 ~ 60% (v/v), the consumption of ethanolic soln is 4 ~ 7 times of crude product quality.
8. a kind of method preparing Xylo-Mucine according to claim 1, is characterized in that: the consumption of described activated carbon decolorizing is 0.03 ~ 0.1 times of crude product quality.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104892773A (en) * | 2015-07-10 | 2015-09-09 | 泸州北方化学工业有限公司 | Preparation method of high-substitution-degree sodium carboxymethylcellulose |
-
2014
- 2014-12-24 CN CN201410810504.XA patent/CN104558206A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104877033B (en) * | 2015-06-03 | 2018-07-06 | 西南大学 | A kind of preparation method of carboxymethyl modified nano-cellulose |
| CN104892773A (en) * | 2015-07-10 | 2015-09-09 | 泸州北方化学工业有限公司 | Preparation method of high-substitution-degree sodium carboxymethylcellulose |
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