CN114478809B - Preparation method of carboxymethyl cellulose fiber - Google Patents
Preparation method of carboxymethyl cellulose fiber Download PDFInfo
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- CN114478809B CN114478809B CN202210155059.2A CN202210155059A CN114478809B CN 114478809 B CN114478809 B CN 114478809B CN 202210155059 A CN202210155059 A CN 202210155059A CN 114478809 B CN114478809 B CN 114478809B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/28—Moving reactors, e.g. rotary drums
Abstract
The invention provides a preparation method of carboxymethyl cellulose fiber, which comprises the steps of alkalization, etherification and post-treatment. The cellulose fiber is used as raw material and is carried out in organic solvent, so that the initial structure of the cellulose fiber can be maintained, and the structure and the morphology of the fiber are not affected basically. The cetyl trimethyl ammonium bromide is added during etherification, so that the tension of the fiber surface is reduced, the hydrophilicity of the fiber is increased, and the reaction efficiency is improved; meanwhile, cetyl trimethyl ammonium bromide is used as a brominating agent, free bromide ions in the system directly participate in reaction during etherification, and new graft copolymer is formed after fibers are brominated, so that the wettability and adsorptivity of the fibers are improved, exudates can be quickly adsorbed after the medical dressing is made, wounds are kept dry, and bacterial breeding is reduced. The invention also improves the stirring reaction pot, and avoids the problems of fiber filament hanging, winding, agglomeration and the like during etherification from influencing the structure and the shape of the fiber.
Description
Technical Field
The invention relates to the technical field of carboxymethyl cellulose, in particular to a preparation method of carboxymethyl cellulose fiber.
Background
Cellulose is mainly present in wood and plant fibers, wherein the content of cellulose in wood is 40-50%, and the content of cellulose in cotton is extremely high, reaching 95-99%. Many plants can be produced annually on earth by photosynthesis, about 5000 million tons, of which about 2000 million tons can be utilized to produce natural cellulose.
Carboxymethyl cellulose is a cellulose ether derivative with a glucose polymerization degree of 100-2000, which is produced by alkalizing natural cellulose with sodium hydroxide and etherifying chloroacetic acid. The glucose unit of the cellulose molecule has 3 alcoholic hydroxyl groups: 1 primary hydroxyl group and 2 secondary hydroxyl groups. All of the 3 alcoholic hydroxyl groups can be subjected to etherification reaction with monochloroacetic acid, wherein the primary hydroxyl groups are the most reactive, so that the primary hydroxyl groups are replaced firstly during the etherification reaction. The carboxymethyl cellulose (CMC) is obtained after carboxymethyl cellulose, and the aqueous solution has the functions of thickening, film forming, adhesion, water retention, colloid protection, emulsification, suspension and the like, and is widely applied to industries such as petroleum, food, medicine, textile, papermaking and the like, and is one of the most important cellulose ethers.
The carboxymethyl cellulose can absorb water into the fiber when being contacted with water as a dressing, can be well maintained under pressure, and can be conveniently applied to and removed from a wound; the liquid medicine is directly and vertically absorbed on the dressing, and can not spread along the fabric to wet the skin around the wound. Meanwhile, the carboxymethyl cellulose has the characteristic of forming colloid after moisture absorption, has very high moisture absorption and moisture retention, is nontoxic and degradable, and has good biocompatibility.
The common carboxymethyl cellulose preparation process is usually carried out by a water-borne method, water is taken as a reaction medium, cellulose raw materials form suspension in a reactor to react with an alkalizing agent and an etherifying agent, and the preparation process has the advantages of simple equipment and low cost, but because the cellulose raw materials can be gelatinized in a large amount of water to form a micelle, the reaction reagent is difficult to penetrate into a crystal region of cellulose, so that the reaction is insufficient, the substitution degree of the obtained carboxymethyl product is low, the salt content is high, the water content is high, and the product quality is poor. Meanwhile, carboxymethyl cellulose belongs to anionic cellulose ether, is usually white or milky fibrous powder or particles, and is easy to disperse in water to form transparent colloidal solution. Because of the characteristic of water solubility of carboxymethyl cellulose, and the carboxymethyl cellulose cannot be dehydrated rapidly when meeting high-concentration electrolyte, the carboxymethyl cellulose is difficult to be dissolved into spinning solution for preparing fibers by a wet spinning process.
The patent number CN201610342421.1 is named as a method for preparing fibers by carrying out electrostatic spinning on carboxymethyl cellulose, and provides a method for preparing fibers by using carboxymethyl cellulose.
In the prior art, there are few methods for directly processing cellulose fibers to carboxymethyl cellulose fibers.
In the patent number CN201910101739.4 named as a preparation method of the carboxymethyl cellulose fiber mask, an alkaline fabric is added with a monochloroacetic acid solution for padding, and the carboxymethyl cellulose fiber is obtained after 48 to 120 hours of reaction, but the method has low efficiency and long reaction time and is not suitable for mass production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of carboxymethyl cellulose fiber, which realizes the following aims:
1. the method is carried out in a form of cellulose fiber post-treatment, and solves the problem that carboxymethyl cellulose is difficult to dissolve into spinning stock solution to be spun into fibers by wet spinning.
2. The preparation method takes cellulose fibers as raw materials and is carried out in an organic solvent, so that the fiber structure of the initial cellulose fibers can be reserved, namely, the carboxymethyl cellulose fibers are directly prepared by using the cellulose fibers with a certain length, the hydrophilic effect is good, the reaction efficiency is high, the process operation is simple and convenient, and the preparation method can be used as medical dressing.
3. The invention improves the stirring reaction pot adopted by etherification to a certain extent, and avoids the influence on the morphological structure of cellulose fibers due to the fact that the cellulose fibers have a certain length and are easy to be hung, wound and agglomerated during stirring.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of carboxymethyl cellulose fiber comprises the steps of alkalization, etherification and post-treatment.
S1, alkalization
And (3) carrying out an alkalization reaction on the cellulose fiber with sodium hydroxide by taking absolute ethyl alcohol and water as solvents to generate alkali cellulose fiber.
Preferably, the ratio of the absolute ethyl alcohol to the water is 55-60:1.2-1.7; the ratio of the cellulose fiber to the solvent is 12-13:59-60.
Preferably, the sodium hydroxide is added in an amount of 15-18% of the cellulose fibers.
Preferably, the cellulose fiber is one of viscose fiber, high wet modulus viscose fiber, strong viscose fiber, lyocell fiber and modal fiber, the fineness is 1.1-6.6 dtex, and the cutting length is 16-76 mm.
Preferably, the temperature of the alkalization reaction is 40-50 ℃ and the reaction time is 50-70min.
S2, etherification
Placing alkali cellulose fibers in a stirring reaction kettle, adding monochloroacetic acid and absolute ethyl alcohol, adding hexadecyl trimethyl ammonium bromide, starting the stirring reaction kettle, heating to 55-65 ℃, rotating the kettle body of the stirring reaction kettle leftwards for 0.5-10 min under the condition of 30-100 revolutions per minute, then rotating rightwards for 0.5-10 min under the condition of 30-100 revolutions per minute, and alternately rotating left and right until the etherification reaction is completed, thus obtaining crude carboxymethyl cellulose fibers.
Preferably, the left rotation time is optimally 2min, and the right rotation time is optimally 2min.
Preferably, the etherification reaction time is 50-70min.
Preferably, the addition amount of the monochloroacetic acid is 25-30% of the cellulose fiber; the addition amount of the absolute ethyl alcohol is 15-17% of the cellulose fiber; the addition amount of the cetyl trimethyl ammonium bromide is 0.02-0.03 per mill of the cellulose fiber.
Cetyl trimethyl ammonium bromide is added during etherification, so that the tension on the surface of the fiber is reduced, the hydrophilicity of the fiber is increased, and the reaction efficiency is improved; meanwhile, cetyl trimethyl ammonium bromide is used as a brominating agent, free bromide ions in the system directly participate in reaction during etherification, and new graft copolymer is formed after fibers are brominated, so that the wettability and adsorptivity of the fibers are improved, exudates can be quickly adsorbed after the medical dressing is made, wounds are kept dry, and bacterial breeding is reduced.
Because the cellulose fiber adopted by the invention has a certain length, and is easy to hang, wind and agglomerate during stirring, and the form of the fiber is influenced to a certain extent, the stirring reaction pot adopted by the etherification is improved to a certain extent.
Preferably, the stirring reaction pot is horizontal, no traditional stirring shaft or stirring paddle is arranged, and stirring teeth are arranged on the inner wall of the stirring reaction pot.
Preferably, the stirring teeth and the inner wall form an angle of 30-35 degrees; the shape of the stirring teeth is crescent.
Preferably, the stirring teeth are made of metal materials with the thickness of 0.1cm, the maximum width of the middle is 2.2cm, and the stirring teeth extend towards the two ends and tend to be 0cm.
Preferably, the stirring teeth at the front half end of the pot body of the stirring reaction pot are clockwise, and the stirring teeth at the rear half end of the pot body of the stirring reaction pot are anticlockwise.
When the stirring reaction pot is started, the pot body of the stirring reaction pot rotates leftwards, alkali cellulose fibers move centripetally and gather in the middle of the pot; when the pot rotates rightwards, alkali cellulose fibers disperse towards the front end and the rear end of the pot, so that the problems of wire hanging, winding, agglomeration and the like are avoided.
S3, post-treatment
The post-treatment includes elution and drying.
Preferably, the crude carboxymethyl cellulose fiber is eluted with 85-95% ethanol solution for 3-5 times.
Preferably, the carboxymethyl cellulose fiber is obtained by drying, eluting and then drying for 2-3 hours at 65-70 ℃ in a dryer.
By adopting the technical scheme, the invention has the following technical effects:
1. the method provided by the invention is carried out in a form of cellulose fiber post-treatment, and solves the problem that carboxymethyl cellulose is difficult to dissolve into spinning stock solution to be spun into fibers by wet spinning.
2. The method takes cellulose fiber as raw material and is carried out in organic solvent, so that the fiber structure of the initial cellulose fiber can be preserved, namely, the carboxymethyl cellulose fiber is directly prepared by using the cellulose fiber with a certain length, the structure and the shape of the fiber are not affected basically, the reaction efficiency is high, the process operation is simple and convenient, and the production cost is saved.
3. Cetyl trimethyl ammonium bromide is added during etherification, so that the tension on the surface of the fiber is reduced, the hydrophilicity of the fiber is increased, and the reaction efficiency is improved; meanwhile, cetyl trimethyl ammonium bromide is used as a brominating agent, free bromide ions in the system directly participate in reaction during etherification, and new graft copolymer is formed after fibers are brominated, so that the wettability and adsorptivity of the fibers are improved, the hydrophilic effect is good, exudates can be quickly adsorbed after the medical dressing is made, wounds are kept dry, and bacterial breeding is reduced.
4. Because the cellulose fiber adopted by the invention has a certain length, and is easy to hang, wind and agglomerate during stirring, and the morphological structure of the fiber can be influenced to a certain extent, the invention improves the stirring reaction pot adopted by etherification to a certain extent, abandons the traditional stirring shaft or stirring paddle, and arranges crescent-shaped stirring teeth on the inner wall of the stirring reaction pot, wherein the stirring teeth at the front end of the pot body are clockwise, and the stirring teeth at the rear end of the pot body are anticlockwise. When the stirring reaction pot is started, the pot body of the stirring reaction pot rotates leftwards, alkali cellulose fibers move centripetally and gather in the middle of the pot; when the pot rotates rightwards, alkali cellulose fibers disperse towards the front end and the rear end of the pot, so that the problems of wire hanging, winding, agglomeration and the like are avoided from influencing the structure and the shape of the fibers.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the drawings that are needed in the description of the process of the present invention will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view showing the internal structure of a stirred tank reactor used in the present invention.
FIG. 2 is a schematic diagram showing the distribution of stirring teeth in a stirring reaction kettle.
Detailed Description
The invention will be further described with reference to specific examples and figures.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Example 1 a process for the preparation of carboxymethyl cellulose fiber comprising the steps of:
a preparation method of carboxymethyl cellulose fiber comprises the steps of alkalization, etherification and post-treatment.
S1, alkalization
And (3) carrying out an alkalization reaction on the viscose fiber by taking absolute ethyl alcohol and water as solvents and sodium hydroxide to generate alkali cellulose fiber.
The ratio of the absolute ethyl alcohol to the water is 58:1.5; the ratio of the viscose fiber to the solvent is 12.5:59.5; the addition amount of the sodium hydroxide is 16% of that of the viscose fiber.
The titer of the viscose fiber is 3dtex, and the cutting length is 38mm.
Preferably, the temperature of the alkalization reaction is 45 ℃ and the reaction time is 60min.
S2, etherification
Placing alkali cellulose fibers in a stirring reaction kettle, adding monochloroacetic acid and absolute ethyl alcohol, adding cetyl trimethyl ammonium bromide, starting the stirring reaction kettle, heating to 60 ℃, rotating the kettle body of the stirring reaction kettle, rotating leftwards for 2min under the condition of 60 turns/min, rotating rightwards for 2min under the condition of 60 turns/min, and carrying out etherification reaction for 60min in turn alternately left and right to obtain crude carboxymethyl cellulose fibers.
The addition amount of the monochloroacetic acid is 28% of that of the cellulose fiber; the addition amount of the absolute ethyl alcohol is 16% of the cellulose fiber; the addition amount of the cetyl trimethyl ammonium bromide is 0.025 per mill of the cellulose fiber.
Cetyl trimethyl ammonium bromide is added during etherification, so that the tension on the surface of the fiber is reduced, the hydrophilicity of the fiber is increased, and the reaction efficiency is improved; meanwhile, cetyl trimethyl ammonium bromide is used as a brominating agent, free bromide ions in the system directly participate in reaction during etherification, and new graft copolymer is formed after fibers are brominated, so that the wettability and adsorptivity of the fibers are improved, exudates can be quickly adsorbed after the medical dressing is made, wounds are kept dry, and bacterial breeding is reduced.
Because the cellulose fiber adopted by the invention has a certain length, and is easy to hang, wind and agglomerate during stirring, and the form of the fiber is influenced to a certain extent, the stirring reaction pot adopted by the etherification is improved to a certain extent.
The stirring reaction pot is horizontal, a traditional stirring shaft or stirring paddle is not needed, and stirring teeth are arranged on the inner wall of the stirring reaction pot.
The stirring teeth and the inner wall form an angle of 30 degrees; the shape of the stirring teeth is crescent.
The stirring teeth are made of metal materials with the thickness of 0.1cm, the maximum width of the middle is 2.2cm, and the stirring teeth extend towards the two ends to be 0cm.
The stirring teeth at the front half end of the pot body of the stirring reaction pot are clockwise, and the stirring teeth at the rear half end of the pot body of the stirring reaction pot are anticlockwise.
When the stirring reaction pot is started, the pot body of the stirring reaction pot rotates leftwards, alkali cellulose fibers move centripetally and gather in the middle of the pot; when the pot rotates rightwards, alkali cellulose fibers disperse towards the front end and the rear end of the pot, so that the problems of wire hanging, winding, agglomeration and the like are avoided.
S3, post-treatment
The post-treatment includes elution and drying.
And eluting the crude carboxymethyl cellulose fiber product with an ethanol solution with the mass fraction of 90% for 3 times.
And (3) drying, eluting, and then sending into a dryer for drying for 3 hours at 65 ℃ to obtain the carboxymethyl cellulose fiber.
Example 2 a process for preparing carboxymethyl cellulose fiber comprising the steps of:
a preparation method of carboxymethyl cellulose fiber comprises the steps of alkalization, etherification and post-treatment.
S1, alkalization
And (3) carrying out an alkalization reaction on the viscose fiber by taking absolute ethyl alcohol and water as solvents and sodium hydroxide to generate alkali cellulose fiber.
The ratio of the absolute ethyl alcohol to the water is 55:1.2; the ratio of the viscose fiber to the solvent is 12:59; the addition amount of the sodium hydroxide is 15% of that of the viscose fiber.
The titer of the viscose fiber is 1.1dtex, and the cutting length is 16mm.
Preferably, the temperature of the alkalization reaction is 40 ℃ and the reaction time is 70min.
S2, etherification
Placing alkali cellulose fibers in a stirring reaction kettle, adding monochloroacetic acid and absolute ethyl alcohol, adding cetyl trimethyl ammonium bromide, starting the stirring reaction kettle, heating to 55 ℃, rotating the kettle body of the stirring reaction kettle leftwards under the condition of 30 revolutions per minute for 0.5min, then rotating rightwards under the condition of 30 revolutions per minute for 0.5min, and carrying out etherification reaction for 70min in turn alternately left and right to obtain crude carboxymethyl cellulose fibers.
The addition amount of the monochloroacetic acid is 25% of that of the cellulose fiber; the addition amount of the absolute ethyl alcohol is 15% of that of cellulose fibers; the addition amount of the cetyl trimethyl ammonium bromide is 0.02 per mill of the cellulose fiber.
Cetyl trimethyl ammonium bromide is added during etherification, so that the tension on the surface of the fiber is reduced, the hydrophilicity of the fiber is increased, and the reaction efficiency is improved; meanwhile, cetyl trimethyl ammonium bromide is used as a brominating agent, free bromide ions in the system directly participate in reaction during etherification, and new graft copolymer is formed after fibers are brominated, so that the wettability and adsorptivity of the fibers are improved, exudates can be quickly adsorbed after the medical dressing is made, wounds are kept dry, and bacterial breeding is reduced.
Because the cellulose fiber adopted by the invention has a certain length, and is easy to hang, wind and agglomerate during stirring, and the form of the fiber is influenced to a certain extent, the stirring reaction pot adopted by the etherification is improved to a certain extent.
The stirring reaction pot is horizontal, a traditional stirring shaft or stirring paddle is not needed, and stirring teeth are arranged on the inner wall of the stirring reaction pot.
The stirring teeth and the inner wall form an angle of 35 degrees; the shape of the stirring teeth is crescent.
The stirring teeth are made of metal materials with the thickness of 0.1cm, the maximum width of the middle is 2.2cm, and the stirring teeth extend towards the two ends to be 0cm.
The stirring teeth at the front half end of the pot body of the stirring reaction pot are clockwise, and the stirring teeth at the rear half end of the pot body of the stirring reaction pot are anticlockwise.
When the stirring reaction pot is started, the pot body of the stirring reaction pot rotates leftwards, alkali cellulose fibers move centripetally and gather in the middle of the pot; when the pot rotates rightwards, alkali cellulose fibers disperse towards the front end and the rear end of the pot, so that the problems of wire hanging, winding, agglomeration and the like are avoided.
S3, post-treatment
The post-treatment includes elution and drying.
And eluting the crude carboxymethyl cellulose fiber by using an ethanol solution with the mass fraction of 85% for 5 times.
And (3) drying, eluting, and then sending into a dryer for drying for 2 hours at 70 ℃ to obtain the carboxymethyl cellulose fiber.
Example 3 a process for preparing carboxymethyl cellulose fiber comprising the steps of:
a preparation method of carboxymethyl cellulose fiber comprises the steps of alkalization, etherification and post-treatment.
S1, alkalization
And (3) carrying out an alkalization reaction on the viscose fiber by taking absolute ethyl alcohol and water as solvents and sodium hydroxide to generate alkali cellulose fiber.
The ratio of the absolute ethyl alcohol to the water is 60:1.7; the ratio of the viscose fiber to the solvent is 13:60; the addition of the sodium hydroxide is 18% of the viscose fiber.
The titer of the viscose fiber is 6.6dtex, and the cutting length is 76mm.
Preferably, the temperature of the alkalization reaction is 50 ℃ and the reaction time is 50min.
S2, etherification
Placing alkali cellulose fibers in a stirring reaction kettle, adding monochloroacetic acid and absolute ethyl alcohol, adding cetyl trimethyl ammonium bromide, starting the stirring reaction kettle, heating to 65 ℃, rotating the kettle body of the stirring reaction kettle, rotating leftwards for 10min under the condition of 100 revolutions per minute, rotating rightwards for 10min under the condition of 100 revolutions per minute, and carrying out etherification reaction for 50min in turn alternately left and right to obtain crude carboxymethyl cellulose fibers.
The addition amount of the monochloroacetic acid is 30% of that of the cellulose fiber; the addition amount of the absolute ethyl alcohol is 17% of the cellulose fiber; the addition amount of the cetyl trimethyl ammonium bromide is 0.03 per mill of the cellulose fiber.
Cetyl trimethyl ammonium bromide is added during etherification, so that the tension on the surface of the fiber is reduced, the hydrophilicity of the fiber is increased, and the reaction efficiency is improved; meanwhile, cetyl trimethyl ammonium bromide is used as a brominating agent, free bromide ions in the system directly participate in reaction during etherification, and new graft copolymer is formed after fibers are brominated, so that the wettability and adsorptivity of the fibers are improved, exudates can be quickly adsorbed after the medical dressing is made, wounds are kept dry, and bacterial breeding is reduced.
Because the cellulose fiber adopted by the invention has a certain length, and is easy to hang, wind and agglomerate during stirring, and the form of the fiber is influenced to a certain extent, the stirring reaction pot adopted by the etherification is improved to a certain extent.
The stirring reaction pot is horizontal, a traditional stirring shaft or stirring paddle is not needed, and stirring teeth are arranged on the inner wall of the stirring reaction pot.
The stirring teeth and the inner wall form an angle of 30 degrees; the shape of the stirring teeth is crescent.
The stirring teeth are made of metal materials with the thickness of 0.1cm, the maximum width of the middle is 2.2cm, and the stirring teeth extend towards the two ends to be 0cm.
The stirring teeth at the front half end of the pot body of the stirring reaction pot are clockwise, and the stirring teeth at the rear half end of the pot body of the stirring reaction pot are anticlockwise.
When the stirring reaction pot is started, the pot body of the stirring reaction pot rotates leftwards, alkali cellulose fibers move centripetally and gather in the middle of the pot; when the pot rotates rightwards, alkali cellulose fibers disperse towards the front end and the rear end of the pot, so that the problems of wire hanging, winding, agglomeration and the like are avoided.
S3, post-treatment
The post-treatment includes elution and drying.
And eluting the crude carboxymethyl cellulose fiber product with 95% ethanol solution for 3 times.
And (3) drying, eluting, and then sending into a dryer for drying for 3 hours at 65 ℃ to obtain the carboxymethyl cellulose fiber.
Comparative example 1
Representative example 1 was selected, with no cetyltrimethylammonium bromide added during the etherification step, and the remainder was identical to example 1 as comparative example 1. The carboxymethyl cellulose fiber prepared in comparative example 1 not only has reduced etherification reaction efficiency, but also has poor hydrophilic effect.
The hydrophilic effect detection method comprises the following steps:
according to the test method for sinking time of 5.9 in YY 0331-2006, water (water temperature 20 ℃) was added to a beaker having a diameter of 110mm to 120mm to a depth of 100mm, and approximately 1g of the carboxymethyl cellulose fibers of examples 1 to 3 and the unbrominated carboxymethyl cellulose fibers of comparative example 1 were each placed on a water surface gently with tweezers to gradually sink. The time taken for the gauze to sink completely into the liquid surface was measured with a stopwatch, and the average of three tests was calculated as the test result.
The carboxymethyl cellulose fiber produced in example 1 took 0.2 seconds on average to sink.
The carboxymethyl cellulose fiber produced in example 2 took 0.26 seconds on average to sink.
The carboxymethyl cellulose fiber produced in example 3 took 0.3 seconds on average to sink.
In comparative example 1, cetyltrimethylammonium bromide was not added in the etherification step, and the average time taken for the produced carboxymethyl cellulose fiber to sink was 4 seconds.
Cetyl trimethyl ammonium bromide is added during etherification, so that the tension on the surface of the fiber is reduced, the hydrophilicity of the fiber is increased, and the reaction efficiency is improved; meanwhile, cetyl trimethyl ammonium bromide is used as a brominating agent, free bromide ions in the system directly participate in reaction during etherification, and new graft copolymer is formed after fibers are brominated, so that the wettability and adsorptivity of the fibers are improved, the hydrophilic effect is better, exudates can be quickly adsorbed after the medical dressing is made, wounds are kept dry, and bacterial breeding is reduced.
The proportions are mass proportions, and the percentages are mass percentages, unless otherwise specified; the raw materials are all commercially available.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A process for the preparation of carboxymethyl cellulose fiber, characterized in that the process comprises the steps of alkalization, etherification and post-treatment;
the alkalization is carried out on cellulose fiber by taking absolute ethyl alcohol and water as solvents to carry out alkalization reaction with sodium hydroxide to generate alkali cellulose fiber;
the etherification is carried out, alkali cellulose fibers are placed in a stirring reaction pot, monochloroacetic acid and absolute ethyl alcohol are added, cetyl trimethyl ammonium bromide is added, the stirring reaction pot is started, the temperature is raised to 55-65 ℃, the stirring reaction pot body rotates leftwards under the condition of 30-100 revolutions per minute for 0.5-10 min, then the stirring reaction pot body rotates rightwards under the condition of 30-100 revolutions per minute for 0.5-10 min, and the stirring reaction pot body alternately rotates left and right until the etherification reaction is completed, so that a crude carboxymethyl cellulose fiber product is obtained;
the stirring teeth at the front half end of the pot body of the stirring reaction pot are clockwise, and the stirring teeth at the rear half end of the pot body of the stirring reaction pot are anticlockwise;
the addition amount of the cetyl trimethyl ammonium bromide is 0.02-0.03 per mill of the cellulose fiber.
2. A method of preparing carboxymethyl cellulose fiber according to claim 1, wherein the post-treatment comprises eluting and drying;
eluting the crude carboxymethyl cellulose fiber product with ethanol solution with the mass fraction of 85-95% for 3-5 times;
and (3) drying, eluting, and then sending into a dryer for drying at 65-70 ℃ for 2-3 hours to obtain the carboxymethyl cellulose fiber.
3. The method for preparing carboxymethyl cellulose fiber according to claim 1, wherein the ratio of the absolute ethyl alcohol to the water is 55-60:1.2-1.7; the ratio of the cellulose fiber to the solvent is 12-13:59-60; the addition amount of the sodium hydroxide is 15-18% of the cellulose fiber;
the temperature of the alkalization reaction is 40-50 ℃ and the reaction time is 50-70min.
4. The method for preparing carboxymethyl cellulose fiber according to claim 1, wherein the addition amount of monochloroacetic acid is 25-30% of the cellulose fiber; the addition amount of the absolute ethyl alcohol is 15-17% of the cellulose fiber.
5. The method for producing a carboxymethyl cellulose fiber according to claim 1, wherein the etherification reaction is carried out for 50 to 70 minutes.
6. The method for preparing carboxymethyl cellulose fiber according to claim 1, wherein the stirring reaction pot is horizontal, no conventional stirring shaft or stirring paddle is provided, and stirring teeth are arranged on the inner wall of the stirring reaction pot;
the stirring teeth and the inner wall form an angle of 30-35 degrees; the shape of the stirring teeth is crescent.
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