CN106432515A - Preparation method of high substitution degree carboxymethyl cellulose sodium and application thereof - Google Patents
Preparation method of high substitution degree carboxymethyl cellulose sodium and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
- D06P1/48—Derivatives of carbohydrates
- D06P1/50—Derivatives of cellulose
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Abstract
The invention relates to a preparation method of high substitution degree carboxymethyl cellulose sodium. The method comprises the steps of: (1) preparing an alkali wine mixed solution in advance for stand-by use; (2) taking carboxymethyl cellulose sodium as the raw material to conduct alkalization again; (3) carrying out etherification reaction; (4) performing washing centrifugation and recovering the solvent; and (5) conducting drying, crushing, mixing and packaging. The invention also provides application of the preparation method in reactive printing paste. The preparation method provided by the invention has the characteristics of simple and effective process, high etherification efficiency, high salt removal rate, and easy drying and crushing, and the production capacity of the production line is brought into maximum play. The prepared carboxymethyl cellulose sodium has ultrahigh substitution degree (DS1.7-2.2), high viscosity (3000-15000mpas for a 2% aqueous solution of Brookfield) and purity (90-98%), and is applicable to reactive printing paste.
Description
Technical field
The invention belongs to the production field of sodium carboxymethyl cellulose, and in particular to a kind of carboxymethyl cellulose with high degree sodium
Preparation method and its application in reactive printing gum.
Background technology
Sodium carboxymethyl cellulose（Na-CMC）Be native cellulose chemically modified obtain a kind of with ethers structure
Derivant.It is a kind of important water for industrial use soluble polymer, traditionally referred to as CMC.CMC is formed after being dissolved in water to be had necessarily
The colloid solution of viscosity, with thickening, bonding, film forming, Protection glue, keeps the effect such as moisture, emulsifying and suspension, is widely used in many
Plant industrial circle.
Printing gum is the macromolecular compound for playing thickening power in print paste, and traditional printing gum is mainly using sea
Sodium alginate, but sodium alginate electrolyte resistance is poor, easily goes mouldy, and Storage period is short, and paste making rate is low, use cost height；High in recent years
Replacement degree, high-viscosity sodium carboxymethyl cellulose replace sodium alginate to be widely used as reactive printing gum, mesh
Before be commonly used in reactive printing gum the substitution value of CMC be about 1.1-1.7.With the continuous development of dyeing, especially
It is that the aspects such as fabric feeling, color yield, definition are required to improve, the CMC of this substitution value can not meet reactive printing
The needs of thickener.Higher replacement degree, the sodium carboxymethyl cellulose product of such as DS1.7-2.4 is developed.
The method for preparing the CMC product of high degree of substitution and high viscosity has a lot, such as with the wadding fibrous element after shredding as original
Material, by the kneading method technique of the repeatedly low range solvent of alkalization etherificate, substep improves substitution value and obtains the CMC compared with high substituted degree
Product；Or with the cellulose powder body of certain fineness as raw material, using the aq slurry process of big multiplying power solvent, be etherified by improving
Efficiency, obtains the CMC product compared with high substituted degree.
The CMC product for high substituted degree being prepared using these processes is usually constructed with some drawbacks：Repeatedly alkalization is etherified
The technical process of kneading method is unfavorable for improving the viscosity of product, while the intensification down cycles of continuous several times are tight to device damage
Weight；The easy aquation caking of product in washing process, salinity is difficult removing；After ethanol is reclaimed and dried, CMC caking is serious, crushes tired
Difficult；Particularly repeatedly the kneading method technique of alkalization etherificate is subject to consersion unit, washing centrifugation apparatus, distillation equipment and freezing to set
Standby restriction, when extra-high substitution value CMC product (DS1.7-2.2) is produced, the production capacity of production line is reduced to conventional replacement
Degree CMC product（DS0.8-1.0）The 35 ~ 45% of product, cause the cost of product to improve by a larger margin.Aq slurry process is using different
Propanol is solvent, and the ratio of fibril and isopropanol is about 1:8 ~ 30, therefore solvent-oil ratio is big, and the process time is long, and production capacity is low,
Valuable product；Most importantly, due to aq slurry process does not possess cost performance in manufacture routine CMC product, therefore slurry
Method technique is not yet popularized at home, and aq slurry process is not general with the equipment of kneading method technique, sets for existing kneading method
For standby, aq slurry process is not applied to.
Patent 201210582442.2 is to prepare extra low viscose degree carboxymethyl cellulose using low-viscosity sodium carboxymethyl cellulose
Sodium, the later stage for belonging to CMC is processed, and changes the viscosity of CMC by adding thinner, due to not carrying out alkalization etherification reaction, no
The substitution value for being related to CMC changes；But the method involved by the patent can not be carried out using existing equipment, extra increase instead is needed
Equipment is answered, production cost is higher.
Content of the invention
Problem to be solved by this invention be overcome extra-high substitution value CMC at present become to produce during to be etherified efficiency low, viscous
Spend that low, desalination is difficult, the inexpensive high shortcoming of production capacity, a kind of high replace and substitution value is stable, high viscosity, purity are high, de- is provided
Salt effect is good, low production cost, can be widely applied for the preparation method of industrial carboxymethyl cellulose with high degree sodium,
Present invention simultaneously provides its application in reactive printing gum.
The technical solution used in the present invention is：
A kind of preparation method of carboxymethyl cellulose with high degree sodium, including alkalization etherificate, washing centrifugation, dries pulverizing and batch mixing
Packaging process, is raw material using sodium carboxymethyl cellulose；Specifically include following steps：
（1）The sodium hydrate aqueous solution that 80-150 weight portion mass fraction is 50% with 160-250 weight portion volume fraction is
The ethanol water mixing of 85-93%, is cooled to 18-30 DEG C, obtains alkali wine；
（2）100 weight portion substitution values are the sodium carboxymethyl cellulose raw material of 0.6-1.4 and step（1）Gained alkali wine is uniformly mixed
Conjunction carries out quaternization；
（3）Will be water-soluble for the monoxone ethanol of 70-75% to 0-0.5 parts by weight epoxy chloropropane and 100-200 weight portion mass fraction
Liquid mix, then with step（2）Product uniformly mix, controlling reaction temperature 20-40 DEG C；Then stirring mixing 20-30 minute, control
Reaction temperature 25-40 DEG C processed；Mixture is delivered to methyltertiarvbutyl ether reactor, controlling reaction temperature 75-80 DEG C, the response time, 60-120 divided
Clock；
（4）Step（3）After end, by gains 1800-2500 weight portion volume fraction for 75-85% ethanol aqueous wash
Wash, centrifugation, reclaim ethanol；
（5）Dry, crush, packaging, obtain final product.
Further improvement, step（2）The quaternization is carried out in reactor is mediated；
Step（2）Quaternization is specially：Sodium carboxymethyl cellulose raw material and alkali wine are uniformly added in kneading reactor, carboxylic first
The joining day of base sodium cellulosate raw material is 15-25 minute, and alkali wine mixed solution sprays minute time 20-30；Alkali wine has been sprayed
Bi Hou, adds 0-35 parts by weight solids sodium hydroxide, uniform stirring 30-40 minute, carries out quaternization, quaternization temperature control
System is at 15-25 DEG C.
Further improvement, step（2）Middle sodium carboxymethyl cellulose raw material is powdery or cotton-shaped, preferably cotton-shaped.
Further improvement, step（2）The substitution value of middle sodium carboxymethyl cellulose raw material is 0.8-1.2, preferably 0.9-
1.0.
Further improvement, step（2）The moisture of middle sodium carboxymethyl cellulose raw material is 3-12%, preferably 5-10%,
More preferably 6-8%.
Further improvement, step（2）The input quality of middle sodium carboxymethyl cellulose raw material and the ratio of kneader volume
For 1.6-15, preferably 1:8-12, more preferably 1:9-11.
Further improvement, when being consersion unit from kneader, step（3）Specially：After the completion of alkalization, by 0-
0.5 parts by weight epoxy chloropropane and 100-200 weight portion mass fraction mix for the monoxone ethanol water of 70-75%, and all
Even it is sprayed to containing step（2）In the kneading reactor of reactant, spray time 30-40 minute, controlling reaction temperature 20-40
℃；After the completion of spray, stirring mixing 20-30 minute, controlling reaction temperature 25-40 DEG C；Mixture is delivered to methyltertiarvbutyl ether reactor, control
Reaction temperature 75-80 DEG C processed, minute in response time 60-120；
Further improvement, the concentration of the washing ethanol solution in step (4) is 78-85%, more preferably 78-82%.
Further improvement, step（4）The material that centrifugation is completed reclaims ethanol by steam stripper.
Invention also provides application of the preparation method in reactive printing gum.
The present invention is reaction raw materials using the carboxymethyl cellulose raw material of fixing substitution value, in later basification and etherification procedure
In greatly reduce the side reaction of reaction and by-product is produced, and improve the efficiency of quaternization and etherification reaction, only pass through
The operation of finite number of time, so that it may reach high substituted degree and high viscosity, with the properties of product that prior art is incomparable.
Conventionally employed cellulosic material is carried out in alkalization etherification procedure, and repeatedly alkalization can produce substantial amounts of by-product and pair is anti-
Answer product（It is referred to as by-product salt）, with gathering for by-product salt, the etherificate efficiency of reaction can decline.It is typically repeated operation 3-4
Secondary, replacement degree can just reach the replacement degree of the application, but etherificate efficiency only has 30-40%, and the application is equivalent to repeating alkalization
Etherificate 2 times, etherificate efficiency is up to 55-65%, and this can bring to production a series of favourable in the very high efficiency of this area meaning
Condition.
The application is raw material using the CMC of replacement degree 0.6-1.4, mainly take into account etherificate efficiency, viscosity and product
The equalization problem of energy.The substitution value of raw material is too low, and viscosity is easily improved, but substitution value is difficult to improve；Raw material substitution value is too high, takes
Easily improve for degree, viscosity is not easy to improve；Meanwhile, can both be related to the problem of yield, only pass through creative work,
Trial dare to be challenged, the substitution value scope in could selecting preferably, just easily using existing equipment, production capacity is improved to highest.
The preparation method of the present invention does not need specific process equipment, mainly relies on existing kneader to can achieve, and
Loss to production equipment is low, reduces production cost.
In quaternization, spraying alkali carries out the addition of solid sodium hydroxide after drinking again, is conducive to improving the replacement of product
Degree.
Any chemical manufacturing process can run into new problem in commercial production is applied to, all.The preparation of the present invention
Method is particularly directed to commercial production, it is contemplated that the problems such as efficiency in production, production capacity, cost, is optimized from parameters,
The program of suitable commercial production popularization is finally given, has been that inventor is tested repeatedly in one line of commercial production for many years, is created
The result for drawing after the property made work, significant in actual production.
In the industrial production, the final substitution value that obtains is 1.7-2.2 to the present invention, purity 90-95%, 2%Brookfield water
The sodium carboxymethyl cellulose product of the extra-high degree of substitution and high viscosity of solution viscosity 3000-15000mpas, so superior performance is
Prior art is incomparable.
The preparation method of the present invention is applied in reactive printing gum, is conducive to improving feel, the color yield of dyeing and printing products
And definition.
Specific embodiment
Embodiment 1
(1) liquid caustic soda of 80 part of 50% mass fraction is mixed with 160 part of 93% volume fraction ethanol, and is cooled to 20 DEG C of alkali wine
Mixed solution is stand-by；
(2) the cotton-shaped sodium carboxymethyl cellulose of 100 parts of substitution values 0.9 and above-mentioned alkali wine mixed solution are uniformly added into kneading anti-
Answer in device, 15 minutes joining days of sodium carboxymethyl cellulose raw material, alkali wine mixed solution sprays 20 minutes time；Alkali wine is sprayed
35 parts of solid sodium hydroxide stirrings are added to carry out within 40 minutes quaternization after finishing, quaternization controls 25 DEG C of temperature；
(3), after the completion of alkalizing, the monoxone ethanol water of 120 part of 70% mass fraction is uniformly sprayed to mediate reactor
In, spray time 40 minutes, 30 DEG C of controlling reaction temperature；After the completion of monoxone ethanol water spray, continue mixing 20 minutes,
30 DEG C of controlling reaction temperature；
(4) said mixture being delivered in methyltertiarvbutyl ether reactor carries out etherification reaction, 78 DEG C of controlling reaction temperature, the response time
100 minutes；
(5), after etherification reaction terminates, will be washed twice in ethanol solution of the reaction mass with 2000 part of 82% volume fraction
And be centrifuged, it is centrifuged the material for completing and ethanol is reclaimed by steam stripper；
(6) ethanol carries out dries pulverizing and packaging after the completion of reclaiming, and the final substitution value that obtains is 1.75, purity 95%, and 2%
The sodium carboxymethyl cellulose product of the extra-high degree of substitution and high viscosity of Brookfield solution viscosity 10000mpas.
Embodiment 2
(1) liquid caustic soda of 85 part of 50% mass fraction is mixed with 200 part of 93% volume fraction ethanol, and is cooled to 25 DEG C of alkali wine
Mixed solution is stand-by；
(2) the powdery sodium carboxymethyl cellulose of 100 parts of substitution values 1.0 and above-mentioned alkali wine mixed solution are uniformly added into kneading anti-
Answer in device, 20 minutes joining days of sodium carboxymethyl cellulose raw material, alkali wine mixed solution sprays 30 minutes time；Alkali wine is sprayed
20 parts of solid sodium hydroxide stirrings are added to carry out within 35 minutes quaternization after finishing, quaternization controls 25 DEG C of temperature；
(3), after the completion of alkalizing, 0.5 part of epoxychloropropane is mixed with the monoxone ethanol water of 100 part of 70% mass fraction,
And uniformly be sprayed to mediate in reactor, spray time 30 minutes, 40 DEG C of controlling reaction temperature；Monoxone ethanol water is sprayed
After the completion of, continue mixing 20 minutes, 30 DEG C of controlling reaction temperature；
(4) said mixture being delivered in methyltertiarvbutyl ether reactor carries out etherification reaction, 75 DEG C of controlling reaction temperature, the response time
100 minutes；
(5), after etherification reaction terminates, will be washed twice in ethanol solution of the reaction mass with 2100 part of 78% volume fraction
And be centrifuged, it is centrifuged the material for completing and ethanol is reclaimed by steam stripper；
(6) ethanol carries out dries pulverizing and packaging after the completion of reclaiming, and the final substitution value that obtains is 1.9 purity 92%, and 2%
The sodium carboxymethyl cellulose product of the extra-high degree of substitution and high viscosity of Brookfield solution viscosity 6700mpas.
Embodiment 3
(1) liquid caustic soda of 150 part of 50% mass fraction is mixed with 200 part of 90% volume fraction ethanol, and is cooled to 18 DEG C of alkali wine
Mixed solution is stand-by；
(2) sodium carboxymethyl cellulose that 100 parts of substitution values are 0.8 is uniformly added into kneading reaction with above-mentioned alkali wine mixed solution
In device, 20 minutes joining days of sodium carboxymethyl cellulose raw material, alkali wine mixed solution sprays 25 minutes time；Alkali wine has been sprayed
25 parts of solid sodium hydroxide stirrings are added to carry out within 30 minutes quaternization after finishing, quaternization controls 20 DEG C of temperature；
(3), after the completion of alkalizing, 0.1 part of epoxychloropropane is mixed with the monoxone ethanol water of 150 part of 75% mass fraction,
And uniformly be sprayed to mediate in reactor, spray time 30 minutes, 35 DEG C of controlling reaction temperature；Monoxone ethanol water is sprayed
After the completion of, continue mixing 20 minutes, 35 DEG C of controlling reaction temperature；
(4) said mixture being delivered in methyltertiarvbutyl ether reactor carries out etherification reaction, 78 DEG C of controlling reaction temperature, the response time
100 minutes；
(5), after etherification reaction terminates, will be washed twice in ethanol solution of the reaction mass with 1800 part of 80% volume fraction
And be centrifuged, it is centrifuged the material for completing and ethanol is reclaimed by steam stripper；
(6) ethanol carries out dries pulverizing and packaging after the completion of reclaiming, and the final substitution value that obtains is 1.75 purity 95%, and 2%
The sodium carboxymethyl cellulose product of the extra-high degree of substitution and high viscosity of Brookfield solution viscosity 8000mpas.
Embodiment 4
(1) liquid caustic soda of 100 part of 50% mass fraction is mixed with 250 part of 85% volume fraction ethanol, and is cooled to 30 DEG C of alkali wine
Mixed solution is stand-by；
(2) sodium carboxymethyl cellulose that 100 parts of substitution values are 1.2 is uniformly added into kneading reaction with above-mentioned alkali wine mixed solution
In device, 20 minutes joining days of sodium carboxymethyl cellulose raw material, alkali wine mixed solution sprays 25 minutes time；Alkali wine has been sprayed
15 parts of solid sodium hydroxide stirrings are added to carry out within 30 minutes quaternization after finishing, quaternization controls 20 DEG C of temperature；
(3), after the completion of alkalizing, monoxone ethanol water of 0.25 part of epoxychloropropane with 200 part of 72% mass fraction is mixed
Close, and be uniformly sprayed to mediate in reactor, spray time 30 minutes, 35 DEG C of controlling reaction temperature；Monoxone ethanol water
After the completion of spray, continue mixing 20 minutes, 35 DEG C of controlling reaction temperature；
(4) said mixture being delivered in methyltertiarvbutyl ether reactor carries out etherification reaction, 78 DEG C of controlling reaction temperature, the response time
100 minutes；
(5), after etherification reaction terminates, will be washed twice in ethanol solution of the reaction mass with 2500 part of 75% volume fraction
And be centrifuged, it is centrifuged the material for completing and ethanol is reclaimed by steam stripper；
(6) ethanol carries out dries pulverizing and packaging after the completion of reclaiming, and the final substitution value that obtains is 1.85, purity 93%, and 2%
The sodium carboxymethyl cellulose product of the extra-high degree of substitution and high viscosity of Brookfield solution viscosity 6500mpas.
Embodiment 5
(1) liquid caustic soda of 110 part of 50% mass fraction is mixed with 220 part of 87% volume fraction ethanol, and is cooled to 25 DEG C of alkali wine
Mixed solution is stand-by；
(2) sodium carboxymethyl cellulose that 100 parts of substitution values are 0.6 is uniformly added into kneading reaction with above-mentioned alkali wine mixed solution
In device, 15 minutes joining days of sodium carboxymethyl cellulose raw material, alkali wine mixed solution sprays 25 minutes time, carries out alkalizing instead
Should, quaternization controls 25 DEG C of temperature；
(3), after the completion of alkalizing, 0.2 part of epoxychloropropane is mixed with the monoxone ethanol water of 125 part of 70% mass fraction,
And uniformly be sprayed to mediate in reactor, spray time 40 minutes, 40 DEG C of controlling reaction temperature；Monoxone ethanol water is sprayed
After the completion of, continue mixing 20 minutes, 40 DEG C of controlling reaction temperature；
(4) said mixture being delivered in methyltertiarvbutyl ether reactor carries out etherification reaction, 75 DEG C of controlling reaction temperature, the response time
120 minutes；
(5), after etherification reaction terminates, will be washed twice in ethanol solution of the reaction mass with 2500 part of 82% volume fraction
And be centrifuged, it is centrifuged the material for completing and ethanol is reclaimed by steam stripper；
(6) ethanol carries out dries pulverizing and packaging after the completion of reclaiming, and the final substitution value that obtains is 2.15 purity 91%, and 2%
The sodium carboxymethyl cellulose product of the extra-high degree of substitution and high viscosity of Brookfield solution viscosity 5000mpas.
Embodiment 6
(1) liquid caustic soda of 100 part of 50% mass fraction is mixed with 250 part of 85% volume fraction ethanol, and is cooled to 30 DEG C of alkali wine
Mixed solution is stand-by；
(2) sodium carboxymethyl cellulose that 100 parts of substitution values are 1.4 is uniformly added into kneading reaction with above-mentioned alkali wine mixed solution
In device, 25 minutes joining days of sodium carboxymethyl cellulose raw material, alkali wine mixed solution sprays 25 minutes time；Alkali wine has been sprayed
35 parts of solid sodium hydroxide stirrings are added to carry out within 30 minutes quaternization after finishing, quaternization controls 15 DEG C of temperature；
(3), after the completion of alkalizing, the monoxone ethanol water of 173 part of 70% mass fraction is uniformly sprayed to mediate reactor
In, spray time 30 minutes, 20 DEG C of controlling reaction temperature；After the completion of monoxone ethanol water spray, continue mixing 30 minutes,
25 DEG C of controlling reaction temperature；
(4) said mixture being delivered in methyltertiarvbutyl ether reactor carries out etherification reaction, 80 DEG C of controlling reaction temperature, the response time
60 minutes；
(5), after etherification reaction terminates, will be washed twice in ethanol solution of the reaction mass with 2200 part of 85% volume fraction
And be centrifuged, it is centrifuged the material for completing and ethanol is reclaimed by steam stripper；
(6) ethanol carries out dries pulverizing and packaging after the completion of reclaiming, and the final substitution value that obtains is 2.0, purity 92%, and 2%
The sodium carboxymethyl cellulose product of the extra-high degree of substitution and high viscosity of Brookfield solution viscosity 6000mpas.
Comparative example 1
1 difference from Example 1 of comparative example is, sodium carboxymethyl cellulose raw material is replaced with purified cotton or Cotton Pulp, and
Repeat to alkalize, be etherified, other operating procedures are identical, specially：
(1) liquid caustic soda of 80 part of 50% mass fraction is mixed with 150 part of 93% volume fraction ethanol, and is cooled to 20 DEG C of alkali wine
Mixed solution is stand-by；
(2) 100 parts of purified cottons or Cotton Pulp and above-mentioned alkali wine mixed solution are uniformly added in kneading reactor, purified cotton or
15 minutes joining days of Cotton Pulp, alkali wine mixed solution sprays 25 minutes time；Alkali wine spray adds 35 parts of solids after finishing
Sodium hydroxide stirring carries out quaternization for 30 minutes, and quaternization controls 25 DEG C of temperature；
(3), after the completion of alkalizing, 0.1 part of epoxychloropropane is mixed with the monoxone ethanol water of 120 part of 70% mass fraction,
And uniformly be sprayed to mediate in reactor, spray time 40 minutes, 30 DEG C of controlling reaction temperature；Monoxone ethanol water is sprayed
After the completion of, continue mixing 20 minutes, 30 DEG C of controlling reaction temperature；
(4) said mixture being delivered in methyltertiarvbutyl ether reactor carries out etherification reaction, 78 DEG C of controlling reaction temperature, the response time
100 minutes；
Step（4）After end, repeat to carry out successively（2）、（3）、（4）Operation, is repeated twice.
(5) washed twice and be centrifuged in the ethanol solution by reaction mass with 2000 part of 80% volume fraction, centrifugation
The material for completing reclaims ethanol by steam stripper；
(6) ethanol carries out dries pulverizing and packaging after the completion of reclaiming, and the final substitution value that obtains is 1.5, purity 78%, and 2%
The sodium carboxymethyl cellulose product of Brookfield solution viscosity 3800mpas.
Comparative example 2
For the sodium carboxymethyl cellulose of commercially available substitution value 1.2, model IH-12,1%Brookfield solution viscosity 1200mpas.
Comparative example 3
For commercially available sodium alginate, model LY1, Qingdao bright moon.
Effect example
Embodiment 1-6 and comparative example 1-3 are carried out stamp applying detection, thickener proportioning is shown in Table 1.
1 thickener proportioning of table（Percentage by weight）
In table 1, thickening agent consumption and Parameter are shown in Table 2.
2 thickening agent consumption of table and parameter
In table 2, dyestuff is：3% reactive turquoise blue BNC or 3% reactive blue BNC P3R or 3% reactive black BNC.Divide equally per set product
Cai Yong not three of the above dyestuff.
Found out by table 2, the usage amount of sodium alginate is big, and sodium alginate price height in practice, therefore the application can have
Effect reduces production cost.
The said goods are carried out stamp to bafta and spun rayon, stamp process is：
90 DEG C of dryings of stamp, 2 minutes 102 DEG C of decatizes are rinsed 100 DEG C for 8 minutes and use detergent Z04 2g/
L soaps 10 minutes and rinses drying.
PRINTED FABRIC is detected, testing result is shown in Table 3.
3 testing result of table
Claims (9)
1. a kind of preparation method of carboxymethyl cellulose with high degree sodium, it is characterised in that including alkalization etherificate, washing centrifugation,
Dry and smash and batch mixing packaging process, be raw material using sodium carboxymethyl cellulose.
2. the preparation method of a kind of carboxymethyl cellulose with high degree sodium according to claim 1, it is characterised in that concrete
Comprise the steps：
（1）The sodium hydrate aqueous solution that 80-150 weight portion mass fraction is 50% with 160-250 weight portion volume fraction is
The ethanol water mixing of 85-93%, is cooled to 18-30 DEG C, obtains alkali wine；
（2）100 weight portion substitution values are the sodium carboxymethyl cellulose raw material of 0.6-1.4 and step（1）Gained alkali wine is uniformly mixed
Conjunction carries out quaternization；
（3）Will be water-soluble for the monoxone ethanol of 70-75% to 0-0.5 parts by weight epoxy chloropropane and 100-200 weight portion mass fraction
Liquid mix, then with step（2）Product uniformly mix, controlling reaction temperature 20-40 DEG C；Then stirring mixing 20-30 minute, control
Reaction temperature 25-40 DEG C processed；Mixture is delivered to methyltertiarvbutyl ether reactor, controlling reaction temperature 75-80 DEG C, the response time, 60-120 divided
Clock；
（4）Step（3）After end, by gains 1800-2500 weight portion volume fraction for 75-85% ethanol aqueous wash
Wash, centrifugation, reclaim ethanol；
（5）Dry, crush, packaging, obtain final product.
3. a kind of preparation method of carboxymethyl cellulose with high degree sodium according to claim 2, it is characterised in that step
（2）The quaternization is carried out in reactor is mediated.
4. a kind of preparation method of carboxymethyl cellulose with high degree sodium according to claim 3, it is characterised in that step
（2）Quaternization is specially：Sodium carboxymethyl cellulose raw material and alkali wine are uniformly added in kneading reactor, while adding carboxymethyl fibre
The plain sodium side spray alkali wine of dimension；After alkali wine spray is finished, 0-35 part solid sodium hydroxide is added, is stirred, quaternization is carried out,
Quaternization temperature control is at 15-25 DEG C.
5. a kind of preparation method of carboxymethyl cellulose with high degree sodium according to claim 2, it is characterised in that step
（2）Middle sodium carboxymethyl cellulose raw material is powdery or cotton-shaped, preferably cotton-shaped.
6. a kind of preparation method of carboxymethyl cellulose with high degree sodium according to claim 2, it is characterised in that step
（2）The substitution value of middle sodium carboxymethyl cellulose raw material is 0.8-1.2, preferably 0.9-1.0.
7. a kind of preparation method of carboxymethyl cellulose with high degree sodium according to claim 2, it is characterised in that step
（2）The moisture 3-12% of middle sodium carboxymethyl cellulose raw material.
8. a kind of preparation method of carboxymethyl cellulose with high degree sodium according to claim 3, it is characterised in that step
（2）The ratio of the input quality of middle sodium carboxymethyl cellulose raw material and kneader volume is 1：6-15.
9. the application of the preparation method of the carboxymethyl cellulose with high degree sodium described in any one of claim 1-8, which is used for making
Standby reactive printing gum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610620338.6A CN106432515B (en) | 2016-08-02 | 2016-08-02 | A kind of preparation method and applications of carboxymethyl cellulose with high degree sodium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610620338.6A CN106432515B (en) | 2016-08-02 | 2016-08-02 | A kind of preparation method and applications of carboxymethyl cellulose with high degree sodium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106432515A true CN106432515A (en) | 2017-02-22 |
| CN106432515B CN106432515B (en) | 2018-02-16 |
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| CN110093792A (en) * | 2019-05-23 | 2019-08-06 | 成都市山马生物科技有限公司 | A kind of high substituted carboxymethyl starch composite reactive printing gum and preparation method |
| CN111574637A (en) * | 2020-06-15 | 2020-08-25 | 昆山京昆油田化学科技有限公司 | Methyl carboxymethyl guar gum and preparation method and application thereof |
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