CN102093481A - Method for preparing instant carboxymethylcellulose - Google Patents
Method for preparing instant carboxymethylcellulose Download PDFInfo
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- CN102093481A CN102093481A CN2009102002922A CN200910200292A CN102093481A CN 102093481 A CN102093481 A CN 102093481A CN 2009102002922 A CN2009102002922 A CN 2009102002922A CN 200910200292 A CN200910200292 A CN 200910200292A CN 102093481 A CN102093481 A CN 102093481A
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Abstract
The invention discloses a method for preparing instant carboxymethylcellulose. The preparation method comprises the following steps of: a) alkalifying cellulose, wherein refined cotton serves as a raw material of the cellulose; b) etherifying alkali cellulose; c) neutralizing and washing; d) drying; and e) performing aftertreatment on a product. The preparation method of the carboxymethylcellulose also comprises the step of performing a crosslinking reaction, wherein the crosslinking reaction is performed in the drying process in the step d); and in the crosslinking reaction, a crosslinking agent is oxalaldehyde in an amount which is 0.8 to 2 percent of the weight of the refined cotton. By the method, the problems that the dissolving speed of the conventional carboxymethylcellulose is low and a 'core wrapping' phenomenon easily occurs when the product is dissolved can be solved; on the premise of not increasing production time and not changing the original appearance and properties of the product, the dissolving speed of the carboxymethylcellulose can be greatly increased; and the method is simple and convenient and is low in cost.
Description
Technical field
The present invention relates to technical field of macromolecules, particularly a kind of preparation method of carboxymethyl cellulose.
Background technology
Xylo-Mucine claims carboxymethyl cellulose again, is called for short CMC, is to be basic raw material with a kind of natural cellulose, a kind of water miscible ionic ether of cellulose that obtains through chemical modification.It has characteristics such as thickening, emulsification dispersion, figuration, protective colloid, water conservation, film forming, acidproof, salt tolerant, and physiology is harmless, therefore is used widely in fields such as oil, food, medicine, papermaking, daily use chemicals, weaving, building produce.It is output maximum in the cellulose ethers, purposes the widest, use product the most easily, be commonly called as and be " industrial monosodium glutamate ".
But having a practical problems in the CMC use, is exactly that its complete dissolution time is long, and it is too slow that product discharges the viscosity time, and user's use has been caused certain difficulty.As in coating industry, use CMC to adopt the nature dissolving, and common CMC product dissolves fully and needs a very long time, very easily occurring " the bag heart " phenomenon in the dissolved process (is CMC surface beginning gel film forming, make water be difficult to infiltration and enter, and then form bulk CMC), thus the dissolved homogeneity influenced, influence the quality and the use of coating products, also have similar situation in other industry.At present, the manufacturer that has is in order to quicken the dissolution rate of Xylo-Mucine, adopt process for granulating, but this method needs to increase in addition granulating equipment, and make the product appearance flavescence easily, dissolution rate neither be very desirable, also prolonged the production time in process of production simultaneously, caused production capacity decline.
Publication number is CN1451687A, and the Chinese invention patent application that open day is on October 29th, 2003 discloses a kind of method (this method abbreviates immediate prior art hereinafter as) for preparing instant Xylo-Mucine.The technical scheme of this method is:
Raw material is by the quick-dissolving agent of making of following weight proportion:
Oxalic dialdehyde 10-40%
Water 60%-90%
The weight proportion of quick-dissolving agent and Xylo-Mucine is: quick-dissolving agent: Xylo-Mucine=1: 20-50, quick-dissolving agent evenly is sprayed on the Xylo-Mucine by above consumption, and be drying to obtain instant type Xylo-Mucine then.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of instant carboxymethyl cellulose, carboxymethyl cellulose according to this preparation method's preparation can be instant, slow with the carboxymethyl cellulose dissolving that the preparation method who solves existing carboxymethyl cellulose obtains, the technical problem of " the bag heart " phenomenon that can occur in the dissolution process.
The present invention solves the problems of the technologies described above by the following technical programs, reaches purpose of the present invention.
A kind of preparation method of instant carboxymethyl cellulose, this preparation method is cellulosic raw material with purified cotton, the step that comprises has:
A) cellulosic alkalization;
B) etherificate of soda cellulose;
C) neutralization washing;
D) oven dry;
The preparation method of described carboxymethyl cellulose also comprises the crosslinking reaction step, described crosslinking reaction step is carried out in described step d) drying course, the linking agent that described crosslinking reaction step is used is oxalic dialdehyde, described oxalic dialdehyde consumption be the 0.8%-2% of described purified cotton weight.
Because oxalic dialdehyde belongs to unsaturated hydrocarbons, there is a two key in intramolecule, and reactive behavior is bigger, and is fast with cellulosic hydroxyl reaction speed, so oxalic dialdehyde carries out little crosslinked more effective as linking agent to Mierocrystalline cellulose.This case contriver finds, adopts oxalic dialdehyde as linking agent, has made the carboxymethyl cellulose with instant effect.Under comparing, the complete dissolution time of the carboxymethyl cellulose that the present invention makes can shorten 5min-15min than the complete dissolution time of carboxymethyl cellulose that immediate prior art makes.The carboxymethyl cellulose dissolution rate that the present invention prepares is faster, can be applied to industry-by-industries such as coating, pottery processing, daily-use chemical industry better.The present invention carries out the crosslinking reaction step simultaneously in drying course, need not increases the extra production time, simple to operate, with low cost, does not influence preparation cycle.In addition, present method does not change original outward appearance of product and performance.
The optimized technical scheme of technique scheme is, described oxalic dialdehyde consumption be the 0.8%-2% of described purified cotton weight, described crosslinking reaction step has also been used described oxalic dialdehyde acidifying souring agent, described souring agent is a citric acid, and the consumption of described citric acid is the 0.1%-1.0% of purified cotton weight.
The present invention has selected oxalic dialdehyde as linking agent, and citric acid is as souring agent, and oxalic dialdehyde can react with Xylo-Mucine under the acidifying condition more fully, so the present invention has selected for use this nontoxic weak acid of citric acid as souring agent.
The preferred version of above-mentioned any one technical scheme is, described crosslinking reaction step is with described oxalic dialdehyde, described citric acid and alcohol mix and form mixing solutions and join and contain wine carboxymethyl cellulose wet feed (what is called contains wine carboxymethyl cellulose wet feed, promptly be through cellulosic alkalization, the product that the etherificate of soda cellulose and neutralization washing obtain) carries out crosslinking reaction in, this preferred version is with oxalic dialdehyde, citric acid and alcohol blend thorough mixing are even, be to be carrier with alcohol, fully oxalic dialdehyde and citric acid are penetrated in the material, make that reaction is more abundant, fully.In order to make the infiltration of oxalic dialdehyde and citric acid fully, describedly contain that the water capacity ratio is 30%-60% in the wine carboxymethyl cellulose wet feed, the carboxymethyl cellulose ratio is 70%-40%, and described alcohol consumption is the 5%-30% of carboxymethyl cellulose weight, and the volumetric concentration of alcohol is controlled to be 60%-95%.
The preferred version of above-mentioned any one technical scheme is, the temperature of described crosslinking reaction is controlled at 45 ℃-90 ℃, and the time of described crosslinking reaction is controlled at 30min-100min.
The preferred version of above-mentioned any one technical scheme is that vacuum rake dryer is adopted in described oven dry.The present invention finishes crosslinking reaction simultaneously in rake formula dried recovered alcohol process.
The preferred version of above-mentioned any one technical scheme is that the preparation method of described instant carboxymethyl cellulose is the kneading method.
Embodiment
Further specify technical scheme of the present invention below in conjunction with embodiment, but the present invention is not limited to embodiment.
A kind of preparation method of instant carboxymethyl cellulose, this preparation method is cellulosic raw material with purified cotton, the step that comprises has:
1), alkalization: liquid caustic soda and alcohol are joined in the kneader, the liquid caustic soda mass concentration is 45%-50%, the alcohol volumetric concentration is 90%-95%, stir 5min-10min, purified cotton put into carry out cellulosic alkalization in the kneader, charging time 5min-10min, alkalization time are 30min-60min, and temperature is controlled at 20 ℃-40 ℃.
2), etherificate: add a certain amount of chloroacetic spirituous solution, the weight ratio of Mono Chloro Acetic Acid and purified cotton is 0.5-0.9: 1, joining day is 20min-50min, chloroacetic quality accounts for 60%-70% in the chloroacetic spirituous solution, the alcohol that uses in the chloroacetic spirituous solution is that volumetric concentration is 95% alcohol, the temperature of etherification reaction is controlled at 70 ℃-80 ℃, and the time of etherification reaction is controlled at 30min-90min.
3), neutralization washing: etherification reaction is cooled to 45 ℃-55 ℃ after finishing, and material is joined in the alcohol that volumetric concentration is 60%-80%, adds hydrochloric acid or Glacial acetic acid adjusting pH to 6.5-8.5, and washing is centrifugal.
4), rake formula drying: through washing, centrifugal, the material that obtains enters the vacuum rake dryer drying, water capacity is the 30%-60% that accounts for centrifugal back material, evenly spray the spirituous solution of certain density oxalic dialdehyde and citric acid then, under agitation condition, finish crosslinking reaction, oxalic dialdehyde amount be controlled to be the 0.8%-2% of purified cotton weight, the amount of souring agent citric acid is controlled to be the 0.1%-1.0% of the weight of purified cotton, the alcohol consumption is the 0.1%-0.8% of purified cotton weight, the volumetric concentration of alcohol is controlled at 60%-95%, and the rake formula is controlled at 30min-100min time of drying, and temperature is controlled at 50 ℃-90 ℃.Simultaneously under negative pressure of vacuum, reclaim residual alcohol.
5), product aftertreatment:, be target product through obtaining white or micro-yellow powder after the processes such as product drying, pulverizing.
Generally speaking, this embodiment adopts the kneading legal system to be equipped with carboxymethyl cellulose sodium, in described step d) rake formula drying course, evenly spray the spirituous solution that contains certain density oxalic dialdehyde and citric acid containing in vacuum rake dryer in the wine carboxymethyl cellulose wet feed, finish crosslinking reaction simultaneously in rake formula dried recovered alcohol process, the negative pressure that vacuumizes is-0.01-0.04Mpa.
In this embodiment, the weight ratio that adds alcohol and purified cotton in the alkalization process is 1.5-2.5: 1.Liquid caustic soda is a sodium hydroxide solution, and the amount of substance of the sodium hydroxide in the liquid caustic soda is 2.0-2.15 with the ratio of chloroacetic amount of substance: 1.
The viscosity measurement of gained target product of the present invention is as follows: the massfraction of formulated product is 2% the aqueous solution, measures its viscosity with the NDJ-79 type rotational viscosimeter that dynamo-electric factory of Tongji University makes down at 25 ℃ ± 0.2 ℃.The substitution value of gained target product of the present invention, pH value, Cl
-Content, the sticking ratio of salt, moisture content are analyzed according to State Standard of the People's Republic of China GB 1904-2005 testing standard.
Dissolution time is tested according to following method: controlled temperature is 25 ℃ ± 0.2 ℃, in 30 seconds, equably the 0.5gCMC product is joined in the beaker that 100ml distilled water is housed of belt stirrer, and simultaneously rotating speed is controlled to be 100r/min, use manual time-keeping, then be considered as dissolving fully after being dissolved into complete transparent colloid Deng the CMC product, reading is the dissolution time of CMC product.
Embodiment 1
Under agitation condition, with the polymerization degree is that to join the 135kg mass concentration be that 49% liquid caustic soda and 200kg volumetric concentration are in the liquid caustic soda alcohol mixing solutions that forms of 95% alcohol for 2200 purified cotton 100kg, carry out quaternization, alkalization temperature is 35 ℃-25 ℃, and alkalization time is 50min.Adding the 110kg mass concentration is 70% chloroacetic spirituous solution, the employed alcohol of chloroacetic spirituous solution is that volumetric concentration is 95% alcohol, and the joining day is 40min, slowly is warming up to 80 ℃ and carries out etherification reaction, heating-up time is 15min, etherification reaction time 50min.Etherificate finishes postcooling to 45 ℃-55 ℃, and it is in 60% the alcohol that material is joined volumetric concentration, regulates pH to neutral with hydrochloric acid, through twice washing, and two times centrifugal, material enters the vacuum rake dryer drying, is 33% through surveying the material water capacity.Evenly spray adds the spirituous solution of 1.5kg oxalic dialdehyde and 18kg citric acid, contain citric acid 600g in the spirituous solution of citric acid, employed alcohol is that volumetric concentration is 65% alcohol, controlled temperature carries out crosslinking reaction 60min at 55 ℃-70 ℃, and (0.02Mpa) reclaim residual alcohol down,, obtain white powder in negative pressure of vacuum simultaneously through aftertreatments such as oven dry, pulverizing, be target product, detect and be Xylo-Mucine.
The correlation parameter detected result of the Xylo-Mucine that present embodiment obtains is as follows:
| Viscosity mpas | Substitution value | Cl -％ | pH | Moisture % | Dissolution time min |
| 1850 | 0.94 | 1.28 | 6.6 | 6.5 | 12 |
Embodiment 2
Under agitation condition, with the polymerization degree is that to join the 135kg mass concentration be that 49% liquid caustic soda and 200kg volumetric concentration are in the 95% alcohol mixing solutions for 2200 purified cotton 100kg, carry out quaternization, alkalization temperature is 35 ℃-25 ℃, alkalization time is 50min, adding the 110kg mass concentration is 70% chloroacetic spirituous solution, the employed alcohol of chloroacetic spirituous solution is that volumetric concentration is 95% alcohol, joining day is 40min, slowly be warming up to 80 ℃ and carry out etherification reaction, heating-up time is 15min, etherification reaction time 50min.Etherificate finishes postcooling to 45 ℃-55 ℃, and it is in 60% the alcohol that material is joined volumetric concentration, regulates pH to neutral with hydrochloric acid, through twice washing, and two times centrifugal, material enters the vacuum rake dryer drying, is 58% through surveying the material water capacity.Evenly spray adds the spirituous solution of 0.8kg oxalic dialdehyde and 6kg citric acid, contain the 100g citric acid in the spirituous solution of citric acid, employed alcohol is that volumetric concentration is 65% alcohol, controlled temperature carries out crosslinking reaction 30min at 75 ℃-90 ℃, and (0.02Mpa) reclaim residual alcohol down,, obtain white powder in negative pressure of vacuum simultaneously through aftertreatments such as oven dry, pulverizing, be target product, detect and be Xylo-Mucine.
Detected result is as follows:
The detected result of the target product of table 2: embodiment 2
| Viscosity mpas | Substitution value | Cl -％ | pH | Moisture % | Dissolution time min |
| 1700 | 0.95 | 1.36 | 7.35 | 8.2 | 16 |
Embodiment 3
Under agitation condition, with the polymerization degree is that to join the 135kg mass concentration be that 49% liquid caustic soda and 200kg volumetric concentration are in the 95% alcohol mixing solutions for 2200 purified cotton 100kg, carry out quaternization, alkalization temperature is 35 ℃-25 ℃, alkalization time is 50min, adding the 110kg mass concentration is 70% chloroacetic spirituous solution, the employed alcohol of chloroacetic spirituous solution is that volumetric concentration is 95% alcohol, joining day is 40min, slowly be warming up to 80 ℃ and carry out etherification reaction, the heating-up time is 15min.Etherification reaction time 50min.Etherificate finishes postcooling to 45 ℃-55 ℃, and it is in 60% the alcohol that material is joined volumetric concentration, regulates pH to neutral with hydrochloric acid, through twice washing, and two times centrifugal, material enters the vacuum rake dryer drying, is 45% through surveying the material water capacity.Evenly spray adds the spirituous solution of 2kg oxalic dialdehyde and 33kg citric acid, the citric acid that contains 1kg in the spirituous solution of citric acid, employed alcohol is that volumetric concentration is 65% alcohol, controlled temperature carries out crosslinking reaction 100min at 45 ℃-60 ℃, and (0.02Mpa) reclaim residual alcohol down,, obtain white powder in negative pressure of vacuum simultaneously through aftertreatments such as oven dry, pulverizing, be target product, detect and be Xylo-Mucine.
The detected result of the correlation parameter of the Xylo-Mucine that present embodiment obtains is as follows:
| Viscosity mpas | Substitution value | Cl -％ | pH | Moisture % | Dissolution time min |
| 1900 | 0.93 | 1.25 | 6.6 | 6.3 | 9 |
Comparative example
Under agitation condition, with the polymerization degree is that to join the 135kg mass concentration be that 49% liquid caustic soda and 200kg volumetric concentration are in the 95% alcohol mixing solutions for 2200 purified cotton 100kg, carry out quaternization, alkalization temperature is 35 ℃-25 ℃, alkalization time is 50min, adding the 110kg mass concentration is 70% chloroacetic spirituous solution, the employed alcohol of chloroacetic spirituous solution is that volumetric concentration is 95% alcohol, joining day is 40min, slowly be warming up to 80 ℃ and carry out etherification reaction, the heating-up time is 15min.Etherification reaction time 50min, regulate pH to neutral with hydrochloric acid, through twice washing, two times centrifugal, material enters the vacuum rake dryer drying, and (0.02Mpa) reclaim residual alcohol down, rake is done temperature at 55 ℃-70 ℃, and harrowing dried process time is 60min in negative pressure of vacuum simultaneously, material is again through aftertreatments such as oven dry, pulverizing, obtain white powder, the mixing solutions with 1.5kg oxalic dialdehyde and 3kg water evenly is sprayed on the material, mix 20min, the process oven dry obtains white powder again, is target product, detects to be Xylo-Mucine.
The detected result of the correlation parameter of the Xylo-Mucine that this Comparative Examples obtains is as follows:
| Viscosity mpas | Substitution value | Cl -％ | pH | Moisture % | Dissolution time min |
| 1800 | 0.93 | 1.16 | 7.2 | 7.6 | 22 |
Those of ordinary skill in the art will be appreciated that, above embodiment is used for illustrating the present invention, and be not to be used as limitation of the invention, as long as in connotation scope of the present invention, all will drop in claims scope of the present invention variation, the modification of the above embodiment.
Claims (8)
1. the preparation method of an instant carboxymethyl cellulose, this preparation method is cellulosic raw material with purified cotton, the step that comprises has:
A) cellulosic alkalization;
B) etherificate of soda cellulose;
C) neutralization washing;
D) oven dry;
It is characterized in that, the preparation method of described instant carboxymethyl cellulose also comprises the crosslinking reaction step, described crosslinking reaction step is carried out in described step d) drying course, the linking agent that described crosslinking reaction step is used is oxalic dialdehyde, described oxalic dialdehyde consumption be the 0.8%-2% of described purified cotton weight.
2. the preparation method of a kind of instant carboxymethyl cellulose according to claim 1, it is characterized in that: described crosslinking reaction step has also been used described oxalic dialdehyde acidifying souring agent, described souring agent is a citric acid, and the consumption of described citric acid is the 0.1%-1.0% of described purified cotton weight.
3. the preparation method of a kind of instant carboxymethyl cellulose according to claim 2 is characterized in that: described crosslinking reaction step be with described oxalic dialdehyde, described citric acid and alcohol mixes and forms mixing solutions and join to contain in the wine carboxymethyl cellulose wet feed and carry out crosslinking reaction.
4. the preparation method of a kind of instant carboxymethyl cellulose according to claim 3, it is characterized in that: the temperature of described crosslinking reaction is controlled at 50 ℃-90 ℃, and the time of described crosslinking reaction is controlled at 30min-100min.
5. the preparation method of a kind of instant carboxymethyl cellulose according to claim 3 is characterized in that: describedly contain that the water capacity ratio is 30%-60% in the wine carboxymethyl cellulose wet feed, the carboxymethyl cellulose ratio is 70%-40%.
6. the preparation method of a kind of instant carboxymethyl cellulose according to claim 3, it is characterized in that: described alcohol consumption is the 5%-30% of described purified cotton weight, and the volumetric concentration of described alcohol is controlled to be 60%-95%.
7. according to the preparation method of each described a kind of instant carboxymethyl cellulose of claim 1-6, it is characterized in that: vacuum rake dryer is adopted in described oven dry.
8. according to the preparation method of each described a kind of instant carboxymethyl cellulose of claim 1-6, it is characterized in that: the preparation method of described instant carboxymethyl cellulose is the kneading method.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104024277A (en) * | 2011-12-02 | 2014-09-03 | 实验室维维西公司 | Method for simultaneously substituting and cross-linking a polysaccharide by means of the hydroxyl functions thereof |
| CN104262649A (en) * | 2014-09-28 | 2015-01-07 | 泸州北方化学工业有限公司 | Sodium croscarmellose and preparation method thereof |
| CN104761646A (en) * | 2015-04-02 | 2015-07-08 | 佛山市富实新高分子纤维有限公司 | Preparation method of sodium carboxymethylcellulose with long shelf life |
| CN110627916A (en) * | 2019-11-02 | 2019-12-31 | 宜兴市军达浆料科技有限公司 | Preparation method of instant carboxymethyl starch or carboxymethyl cellulose pulp |
| CN114276461A (en) * | 2021-12-27 | 2022-04-05 | 重庆力宏精细化工有限公司 | Sodium carboxymethylcellulose and preparation method thereof, and battery cathode slurry and preparation method thereof |
| CN114957492A (en) * | 2021-12-28 | 2022-08-30 | 常熟威怡科技有限公司 | Preparation method of low-insoluble substance fast-dispersing carboxymethyl cellulose ether |
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2009
- 2009-12-10 CN CN2009102002922A patent/CN102093481A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104024277A (en) * | 2011-12-02 | 2014-09-03 | 实验室维维西公司 | Method for simultaneously substituting and cross-linking a polysaccharide by means of the hydroxyl functions thereof |
| CN104024277B (en) * | 2011-12-02 | 2018-11-06 | 实验室维维西公司 | Replace the method with cross-linked polysaccharides simultaneously for the hydroxy functional group by polysaccharide |
| CN104262649A (en) * | 2014-09-28 | 2015-01-07 | 泸州北方化学工业有限公司 | Sodium croscarmellose and preparation method thereof |
| CN104761646A (en) * | 2015-04-02 | 2015-07-08 | 佛山市富实新高分子纤维有限公司 | Preparation method of sodium carboxymethylcellulose with long shelf life |
| CN110627916A (en) * | 2019-11-02 | 2019-12-31 | 宜兴市军达浆料科技有限公司 | Preparation method of instant carboxymethyl starch or carboxymethyl cellulose pulp |
| CN114276461A (en) * | 2021-12-27 | 2022-04-05 | 重庆力宏精细化工有限公司 | Sodium carboxymethylcellulose and preparation method thereof, and battery cathode slurry and preparation method thereof |
| CN114957492A (en) * | 2021-12-28 | 2022-08-30 | 常熟威怡科技有限公司 | Preparation method of low-insoluble substance fast-dispersing carboxymethyl cellulose ether |
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Application publication date: 20110615 |