CN102286108B - Method for preparing potassium carboxymethylcellulose - Google Patents
Method for preparing potassium carboxymethylcellulose Download PDFInfo
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Abstract
The invention provides a method for producing potassium carboxymethylcellulose by a kneading method, which comprises the following steps of: alkalizing cellulose by high-concentration potassium hydroxide liquid and industrial potassium hydroxide solid to generate alkali cellulose; after the generated alkali cellulose is subjected to carboxymethylation of chloroacetic acid, adding the potassium hydroxide liquid and the industrial potassium hydroxide solid again to carry out secondary alkalization; then adding chloroacetic acid to carry out secondary carboxymethylation treatment; and washing, neutralizing, centrifuging, drying and grinding to obtain the potassium carboxymethylcellulose product. The product not only has good dissolubility, but also has simple production process, short reaction period, low equipment investment and low raw material consumption.
Description
Technical field
The present invention relates to a kind of preparation method of CMC 99.5 potassium, belong to natural macromolecular material chemical modification field.
Technical background
CMC 99.5 potassium is that purified cotton and Pottasium Hydroxide, Mono Chloro Acetic Acid alkalize under alkaline condition, etherification reaction and the water miscible fiber derivative that makes.In foodstuffs industry; CMC-Na uses as foodstuff additive commonly used; Yet the excessive absorption of discovering sodium ion can cause diseases such as mellitus, hypertension, cardiovascular diseases; So will reduce the amount of sodium in daily life, can also replace sodium salt with part sylvite simultaneously; In petroleum industry, down hole problems such as well slough, bit freezing appear in regular meeting in the water-based drilling process, this is because when getting into mud shale stratum mostly, the hydration swelling of clay with disperse to be caused.Therefore; Adopt chemical agent control drilling fluid medium to get into the stratum, the inhibition shale hydration expands and disperses, and is a kind of stabilizing borehole, the important means that guarantees normal drilling well; Research is illustrated in the suppressor factor use, and the effect suppressing the ground hydration swelling of CMC-K will obviously be better than CMC-Na.
Domestic less to CMC-K research at present, from document " the Different Alkali metal hydroxides is to the influence of a carboxymethyl celluloseization " literary composition, sum up and drawn some about CMC-Na and the correlated related conclusions of CMC-K, specific as follows:
(1) the NaOH massfraction is 25%, and Mierocrystalline cellulose reaches maximum swollen, is below or above this massfraction, and cellulosic moisture expansivity reduces; The KOH massfraction is 20% to 35%, and platform appears in cellulosic moisture expansivity, is lower than 20% or be higher than 35%, and the Mierocrystalline cellulose moisture expansivity increases with the increase of KOH massfraction.
(2) under the equal in quality mark, the absorption alkali number of Mierocrystalline cellulose in NaOH is higher than the adsorptive capacity in KOH.
(3) along with the increase of alkali number, the substitution value of product increases gradually, but the substitution value of CMC-Na increases rapidly, and the trend that the CMC-K substitution value increases is more slow.Within the specific limits, the consumption of alkali is big more, and Mierocrystalline cellulose is big more to the adsorptive capacity of alkali; The Mierocrystalline cellulose swollen is just good more, and cellulosic percent crystallinity descends, thereby has improved the reactive behavior of hydroxyl on the unit loop; Help the diffusion of etherifying agent, the utilization ratio of etherifying agent improves, and substitution value is also high more.In addition, because Na
+Compare K
+Reactive behavior higher, the former is better to cellulosic swollen, in etherification reaction, the utilization ratio of etherifying agent is much higher relatively, thereby causes the intensity of variation of same alkali number, the former sharply increases by substitution value, and the trend that the latter increases is more slow.
Because the substitution value of the CMC 99.5 potassium that above factors have caused under equal processing condition, producing will be far below Xylo-Mucine.
The chemical reaction of preparation CMC 99.5 potassium mainly contains two kinds at present: a kind of is that Mierocrystalline cellulose and potassium hydroxide base solution reaction generate soda cellulose; Soda cellulose carries out etherification reaction with Mono Chloro Acetic Acid again.Because this method substitution value is lower, so few people adopt the preparation of this kind method.Another kind is earlier CMC to be carried out acidifying, lets H
+Na among the replacement CMC
+, and then, making CMC 99.5 potassium with material after the acidifying and KOH liquid reactions, this method adopts many.Both compare, and the latter's operation will bother manyly than the former, and cost also will be higher than the former far away, but advantage is that the product substitution value that obtains is higher.
Summary of the invention
The present invention just is based on above background, obtains a kind of method that has than the CMC 99.5 potassium of high substitution value through process modification.
Technical scheme of the present invention is following:
A kind of preparation method of CMC 99.5 potassium may further comprise the steps:
A, with purified cotton and potassium hydroxide aqueous solution and the Pottasium Hydroxide solid pulverized, drop into together with aqueous ethanolic solution and to carry out a quaternization in the kneader;
After b, alkalization finish, carry out etherification reaction, in 40 minutes, equably etherifying agent is sprayed in the material to the kneader, carry out etherification reaction one time;
E, last material obtain CMC 99.5 potassium after pulverizing through washing.
After step b, further carry out following two steps, and then carry out step e, through after alkalization once and the etherificate, carry out double alkalisation and secondary etherificate more like this, mainly be to let react more abundant, it is higher to work it out the product substitution value.
After c, etherification reaction finish,, drop into together with aqueous ethanolic solution and to carry out double alkalisation in the material in the kneader and react once more with potassium hydroxide aqueous solution and Pottasium Hydroxide solid;
Add etherifying agent once more after d, the double alkalisation reaction, carry out the secondary etherification reaction;
The mass percent concentration of said potassium hydroxide aqueous solution is 40～55%, is reaction medium with the aqueous ethanolic solution, and the mass percentage concentration of aqueous ethanolic solution is 70～98%; Said etherifying agent is chloroacetic ethanolic soln, and its mass percent concentration is 50～80%.
Wherein, a quaternization time is 50～80 minutes among the step a, and one time the quaternization temperature is 10～40 ℃.
An etherification reaction temperature is 80 ℃ ± 2 ℃ among the step a, and an etherification reaction time is 40～50 minutes.
Among the step c, the double alkalisation reaction times is 20～40 minutes, and the double alkalisation temperature of reaction is 20～40 ℃.
The secondary etherification reaction temperature is 80 ℃ ± 2 ℃ in the steps d, and the secondary etherification reaction time is 40～70 minutes.
The time that step e continues reaction is 40-50 minute.
Said Pottasium Hydroxide solid adopts technical grade Pottasium Hydroxide solid.
Said etherification reaction will carry out in 40 minutes after quaternization, mainly contains two purposes like this, and one is that etherifying agent Mono Chloro Acetic Acid and sodium hydroxide fully react formation sodium salt participation etherification reaction; The secondth, let etherifying agent fully in soda cellulose, disperse infiltration, form parcel shape material to prevent local reaction, cause reaction inhomogeneous, cause the product inner quality poor.
The inventive method production process technology is simple, and reaction time is short, and facility investment is few, and raw material consumption is low, and the CMC 99.5 potassium that adopts this method to produce not only has good solubility, and it has higher substitution degree simultaneously.Especially adopting the double alkalisation etherificate, mainly is to consider that in the production process of CMC 99.5 potassium, potassium atom is not easy to replace on the products molecule chain, and adopts the double alkalisation etherificate can improve the product substitution value greatly, and then improves performance of products.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
With a certain amount of purified cotton that tears to shreds; 2.0 48% potassium hydroxide aqueous solution doubly, 0.05 times Pottasium Hydroxide solid and 1.8 times of ethanolic solns drop in the kneader simultaneously; Stir alkalization after 80 minutes; 1.1 times of chloroacetic ethanolic solns are sprayed equably to kneader, carry out carboxymethylation reaction.Temperature is increased to 60-90 ℃; Continue reaction 40 minutes; Obtain rough modified carboxy methyl cellulose potassium; Through washing, neutralization, centrifugal, dry, obtain refining CMC 99.5 potassium finished product after pulverizing, substitution value is 0.65,1% solution viscosity of NDJ-79 type viscometer measurement is 600mPas.Above multiple all is that the amount with purified cotton is the basis.
Embodiment 2:
With a certain amount of purified cotton that tears to shreds; 1.9 48% potassium hydroxide aqueous solution doubly, 0.1 times Pottasium Hydroxide solid and 1.8 times of ethanolic solns drop in the kneader simultaneously; Stir alkalization after 80 minutes; 1.1 times of chloroacetic ethanolic solns are sprayed equably to kneader, carry out carboxymethylation reaction.Temperature is increased to 60-90 ℃; Continue reaction 40 minutes; Obtain rough modified carboxy methyl cellulose potassium; Through washing, neutralization, centrifugal, dry, obtain refining CMC 99.5 potassium finished product after pulverizing, substitution value is 0.68,1% solution viscosity of NDJ-79 type viscometer measurement is 620mPas.Above multiple all is that the amount with purified cotton is the basis.
Embodiment 3:
With a certain amount of purified cotton that tears to shreds; 2.7 doubly 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.8 times of ethanolic solns of 0.1 times drop in the kneader simultaneously; Stir alkalization after 80 minutes, 1.5 times of chloroacetic ethanolic solns are sprayed equably to kneader, carry out carboxymethylation reaction.Temperature is increased to 60-90 ℃; Continue reaction 40 minutes; Obtain rough modified carboxy methyl cellulose potassium; Through washing, neutralization, centrifugal, dry, obtain refining CMC 99.5 potassium finished product after pulverizing, substitution value is 0.70,1% solution viscosity of NDJ-79 type viscometer measurement is 310mPas.Above multiple all is that the amount with purified cotton is the basis.
Embodiment 4:
With a certain amount of purified cotton that tears to shreds; 1.9 doubly 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.8 times of ethanolic solns of 0.3 times drop in the kneader simultaneously; Stir alkalization after 80 minutes, 1.4 times of chloroacetic ethanolic solns are sprayed equably to kneader, carry out carboxymethylation reaction.Temperature is increased to 60-90 ℃; Continue reaction 40 minutes; Obtain rough modified carboxy methyl cellulose potassium; Through washing, neutralization, centrifugal, dry, obtain refining CMC 99.5 potassium finished product after pulverizing, substitution value is 0.80,1% solution viscosity of NDJ-79 type viscometer measurement is 530 mPas.Above multiple all is that the amount with purified cotton is the basis.
Embodiment 5:
With a certain amount of purified cotton that tears to shreds; Earlier 1.5 times of 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.5 times of ethanolic solns of 0.15 times are dropped in the kneader simultaneously, stir alkalization after 60 minutes, 0.9 times of chloroacetic ethanolic soln is sprayed equably to kneader; Stirring reaction 40min; And then 0.5 times of 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.5 times of ethanolic solns of 0.15 times are dropped in the kneader simultaneously, after alkalizing once more 30 minutes, again 0.5 times of chloroacetic ethanolic soln is sprayed equably to kneader; Temperature is increased to 60-90 ℃; Continue reaction 40 minutes, obtain rough modified carboxy methyl cellulose potassium, through washing, neutralization, centrifugal, dry, obtain making with extra care CMC 99.5 potassium finished product after pulverizing; Substitution value is 0.84, and 1% solution viscosity that NDJ-79 type viscometer is measured is 1015mPas.Above multiple all is that the amount with purified cotton is the basis.
Embodiment 6:
With a certain amount of purified cotton that tears to shreds; Earlier 1.4 times of 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.5 times of ethanolic solns of 0.20 times are dropped in the kneader simultaneously, stir alkalization after 60 minutes, 0.9 times of chloroacetic ethanolic soln is sprayed equably to kneader; Stirring reaction 40min; And then 0.5 times of 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.5 times of ethanolic solns of 0.15 times are dropped in the kneader simultaneously, after alkalizing once more 30 minutes, again 0.5 times of chloroacetic ethanolic soln is sprayed equably to kneader; Temperature is increased to 60-90 ℃; Continue reaction 40 minutes, obtain rough modified carboxy methyl cellulose potassium, through washing, neutralization, centrifugal, dry, obtain making with extra care CMC 99.5 potassium finished product after pulverizing; Substitution value is 0.85, and 1% solution viscosity that NDJ-79 type viscometer is measured is 890mPas.Above multiple all is that the amount with purified cotton is the basis.
Embodiment 7:
With a certain amount of purified cotton that tears to shreds; Earlier 1.4 times of 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.5 times of ethanolic solns of 0.20 times are dropped in the kneader simultaneously, stir alkalization after 60 minutes, 1.0 times of chloroacetic ethanolic solns are sprayed equably to kneader; Stirring reaction 40min; And then 0.5 times of 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.5 times of ethanolic solns of 0.15 times are dropped in the kneader simultaneously, after alkalizing once more 30 minutes, again 0.5 times of chloroacetic ethanolic soln is sprayed equably to kneader; Temperature is increased to 60-90 ℃; Continue reaction 40 minutes, obtain rough modified carboxy methyl cellulose potassium, through washing, neutralization, centrifugal, dry, obtain making with extra care CMC 99.5 potassium finished product after pulverizing; Substitution value is 0.87, and 1% solution viscosity that NDJ-79 type viscometer is measured is 780mPas.Above multiple all is that the amount with purified cotton is the basis.
Embodiment 8:
With a certain amount of purified cotton that tears to shreds; Earlier 1.4 times of 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.5 times of ethanolic solns of 0.20 times are dropped in the kneader simultaneously, stir alkalization after 60 minutes, 1.1 times of chloroacetic ethanolic solns are sprayed equably to kneader; Stirring reaction 40min; And then 0.5 times of 48% potassium hydroxide aqueous solution, Pottasium Hydroxide solid and 1.5 times of ethanolic solns of 0.15 times are dropped in the kneader simultaneously, after alkalizing once more 30 minutes, again 0.6 times of chloroacetic ethanolic soln is sprayed equably to kneader; Temperature is increased to 60-90 ℃; Continue reaction 40 minutes, obtain rough modified carboxy methyl cellulose potassium, through washing, neutralization, centrifugal, dry, obtain making with extra care CMC 99.5 potassium finished product after pulverizing; Substitution value is 0.89, and 1% solution viscosity that NDJ-79 type viscometer is measured is 760mPas.Above multiple all is that the amount with purified cotton is the basis.
Term:
viscosity: 1% aqueous solution, NDJ-79 type rotary viscometer detects under 25 ℃ of conditions.
substitution value (D.S): detect according to 5.5 methods among the GB 1904-2005 " foodstuff additive Xylo-Mucine ", wherein in the substitution value calculation formula numerical value 0.08 to change numerical value be 0.096.
Claims (8)
1. the preparation method of a CMC 99.5 potassium is characterized in that may further comprise the steps:
A, with purified cotton and potassium hydroxide aqueous solution and the Pottasium Hydroxide solid pulverized, drop into together with aqueous ethanolic solution and to carry out a quaternization in the kneader;
After b, alkalization finish, etherifying agent is sprayed in the material to the kneader, carry out etherification reaction one time;
After c, etherification reaction finish,, drop into together with aqueous ethanolic solution and to carry out double alkalisation in the material in the kneader and react once more with potassium hydroxide aqueous solution and technical grade Pottasium Hydroxide solid;
Add etherifying agent once more after d, the double alkalisation reaction, carry out the secondary etherification reaction;
E, temperature are increased to 60-90 ℃, continue reaction, obtain rough modified carboxy methyl cellulose potassium, through washing, neutralization, centrifugal, dry, obtain making with extra care CMC 99.5 potassium finished product after pulverizing;
The mass percent concentration of said potassium hydroxide aqueous solution is 40～55%, is reaction medium with the aqueous ethanolic solution, and the mass percentage concentration of aqueous ethanolic solution is 70～98%; Said etherifying agent is chloroacetic ethanolic soln, and its mass percent concentration is 50～80%;
Pottasium Hydroxide solid and purified cotton mass ratio 0.05～0.3:1;
Mass ratio 1.8～3.0:1 of potassium hydroxide solution and purified cotton;
Mass ratio 1.5～3.0:1 of aqueous ethanolic solution and purified cotton;
Mass ratio 1.0～1.7:1 of etherifying agent and purified cotton.
2. the method for preparing CMC 99.5 potassium according to claim 1 is characterized in that: a quaternization time is 50～80 minutes among the step a, and one time the quaternization temperature is 10～40 ℃.
3. the method for preparing CMC 99.5 potassium according to claim 1 and 2 is characterized in that: an etherification reaction temperature is 80 ℃ ± 2 ℃ among the step b, and an etherification reaction time is 40～50 minutes.
4. the method for preparing CMC 99.5 potassium according to claim 1 is characterized in that: among the step c, the double alkalisation reaction times is 20～40 minutes, and the double alkalisation temperature of reaction is 20～40 ℃.
5. the method for preparing CMC 99.5 potassium according to claim 1 is characterized in that: the secondary etherification reaction temperature is 80 ℃ ± 2 ℃ in the steps d, and the secondary etherification reaction time is 40～70 minutes.
6. the method for preparing CMC 99.5 potassium according to claim 1 and 2 is characterized in that: the time that step e continues reaction is 40～50 minutes.
7. the method for preparing CMC 99.5 potassium according to claim 1 and 2 is characterized in that: said etherification reaction will carry out in 40 minutes after quaternization.
8. the method for preparing CMC 99.5 potassium according to claim 1 and 2 is characterized in that: said Pottasium Hydroxide solid adopts technical grade Pottasium Hydroxide solid.
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| CN104119454B (en) * | 2013-12-02 | 2017-07-14 | 上海长光企业发展有限公司 | The preparation method of polyanion cellulose |
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| CN104098781B (en) * | 2014-06-20 | 2016-08-17 | 华中农业大学 | A kind of method utilizing Concretio silicea Bambusae seu schizostachyi waste material to produce degradable liquid mulch film |
| CN104592398B (en) * | 2015-02-03 | 2016-08-24 | 重庆力宏精细化工有限公司 | A kind of preparation method of sodium carboxymethyl cellulose |
| CN104592399B (en) * | 2015-02-03 | 2017-03-15 | 重庆力宏精细化工有限公司 | A kind of preparation method for improving sodium carboxymethyl cellulose solution wandering fibre silk |
| CN105330752B (en) * | 2015-11-24 | 2018-06-15 | 泸州北方化学工业有限公司 | A kind of method for preparing carboxymethyl cellulose with high degree sodium |
| CN105254769B (en) * | 2015-11-24 | 2019-03-01 | 泸州北方化学工业有限公司 | A kind of method of technology of preparing level sodium carboxymethylcellulose |
| CN106336461B (en) * | 2016-08-22 | 2018-09-11 | 四川北方硝化棉股份有限公司 | A kind of preparation method of carboxymethyl cellulose lithium |
| CN112707969A (en) * | 2020-12-28 | 2021-04-27 | 常熟威怡科技有限公司 | Production process of sodium carboxymethylcellulose by self-esterification reaction |
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| CN1459464A (en) * | 2002-05-23 | 2003-12-03 | 武汉理工大学 | Preparation method of water soluble hydroxyethyl carboxymethyl cellulose thickener |
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| WO2007123974A2 (en) * | 2006-04-21 | 2007-11-01 | Hercules Incorporated | Decolorized raw cotton linters and preparation of ether derivatives therefrom |
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| CN1459464A (en) * | 2002-05-23 | 2003-12-03 | 武汉理工大学 | Preparation method of water soluble hydroxyethyl carboxymethyl cellulose thickener |
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