CN115287780A - Lignocellulose-based intelligent color-changing composite fiber material and preparation method thereof - Google Patents
Lignocellulose-based intelligent color-changing composite fiber material and preparation method thereof Download PDFInfo
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- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/06—Dyes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a lignocellulose-based intelligent color-changing composite fiber material and a preparation method thereof, and the composite fiber material comprises an intelligent color-changing molecule and nanocellulose, wherein the intelligent color-changing molecule is one or more of lactamized rhodamine 6G, ethylenediamine salicylaldehyde Schiff base, methyl orange, bromothymol blue and phenolphthalein. The lignocellulose-based intelligent color-changing composite fiber material prepared by the preparation method has the advantages of environmental friendliness, high luminous efficiency and high stability, is simple in preparation process, high in yield and low in cost, is suitable for large-scale preparation of intelligent color-changing composite fiber materials with different functions, has higher practicability and research value, provides new theoretical research and technical support for research of novel intelligent color-changing composite fiber materials, and has very wide application prospect.
Description
Technical Field
The invention relates to the technical field of functional fibers, in particular to a lignocellulose-based intelligent color-changing composite fiber material and a preparation method thereof.
Background
The color change phenomenon refers to the change of color of a substance after physical or chemical reaction. Materials prepared using the color change properties of the material are referred to as color change materials. The materials are classified according to the mode of external stimulation on the materials, and mainly comprise photochromism, thermochromism, electrochromism, acid-induced discoloration and the like. The development and exploration of color-changing materials are always the hot research direction, and have corresponding applications in various fields, such as: can be used as an indicator to search cancer affected parts in the pharmaceutical industry, can also be used as sun-screening clothes paint to absorb ultraviolet rays, and can be used as fluorescent anti-counterfeiting paint and the like. The first fluorescence chemical sensor was prepared in 1867 and used for detecting Al forming a highly luminescent morin chelate 3+ Ions.
The nano-cellulose has the advantages of high specific surface area, excellent mechanical property, rich hydroxyl, easiness in modification and the like, and the hydroxyl or other introduced functional groups are utilized to combine a fluorophore with a cellulose main chain. The preparation of the fluorescent intelligent fiber composite material based on the nano-cellulose is a new field and has great research value.
In the prior patent CN202110425064.6, a alginate fiber with fluorescence characteristic, a sodium alginate solution and a fluorescent complex are mixed together by physical blending, and a spinning solution is spun into a sodium alginate fiber with fluorescence characteristic by a wet spinning technology. Fluorescent substances in the fiber can stably exist, through a soaking experiment, the fluorescent substances do not overflow from a soaking solution, and the change of the fluorescence intensity of the soaked fluorescent fiber is small; the fiber has no toxicity to biological cells, and can not cause death of the biological cells. But the fiber has small tensile strength, can only carry out photochromism, has single color change, is easily influenced by factors such as solvent, pH, illumination, temperature and the like, and reduces the fatigue resistance and the light stability.
In the prior patent CN202011338086.0, a photochromic fiber and a preparation method thereof, the fiber is prepared by mixing a photochromic dye into a polyvinyl alcohol or polyacrylonitrile raw material spinning solution for spinning. By using the organic photochromic agent, when visible light irradiates on the fiber, the pigment of the fiber is lightened, and the light transmission performance is increased, and when the visible light is reduced, the color of the fiber is darkened, and the light transmission performance is reduced, so that the heat insulation performance of the fiber is ensured. However, the fiber only has photochromism and single color change, and can only change from white to blue under the action of visible light, and the fluorescent substance has high cost and is not suitable for industrial production.
Therefore, in order to solve the above problems, the present invention provides a lignocellulose-based intelligent color-changing composite fiber material and a preparation method thereof.
Disclosure of Invention
The intelligent color-changing composite fiber material provided by the invention has the advantages of environmental friendliness, high luminous efficiency and high stability, provides new theoretical research and technical support for the research of novel intelligent color-changing composite fiber materials, and has a very wide application prospect.
In order to achieve the purpose, the invention provides a wood nano cellulose-based intelligent color-changing composite fiber material which comprises an intelligent color-changing molecule and nano cellulose, wherein the intelligent color-changing molecule is one or more of lactamized rhodamine 6G, ethylenediamine salicylaldehyde Schiff base, methyl orange, bromothymol blue and phenolphthalein.
The intelligent lignocellulose-based color-changing composite fiber material and the preparation method thereof comprise the following steps:
(1) Extraction of nanocellulose
Extracting cellulose in a wood-based raw material by using sodium chlorite, then performing heat treatment by using an ethanol water solution, then performing treatment by using a hydrogen peroxide solution, and finally performing ultrasonic crushing, freeze drying to prepare nano cellulose;
(2) Preparation of intelligent color-changing composite fiber material
Taking dimethyl sulfoxide as a solvent, the ratio of the nano-cellulose, the intelligent color-changing molecules, polyacrylonitrile and polyvinyl alcohol prepared in the step (1) is 5-20; the intelligent color-changing molecule is one or more of lactamized rhodamine 6G, ethylenediamine salicylaldehyde Schiff base, methyl orange, bromothymol blue and phenolphthalein.
Preferably, the wood-based raw material is one or more of wood flour, oak flour, fir flour, beech flour, birch flour, maple flour, straw powder, bagasse, bamboo powder, reed and cotton.
Further, extraction of nanocellulose with sodium chlorite: in order to remove lignin and hemicellulose in a wood-based raw material, 1-2 g of sodium chlorite is weighed and added into a beaker, then 100-200 mL of deionized water is added into the beaker, the solution is fully stirred and dissolved to form 1-2% sodium chlorite solution, then 300-400 mu L of glacial acetic acid is added to ensure that the pH value of the solution is 3-4, finally a magnetic stirrer is used for stirring for 6-7 h at the temperature of 80-85 ℃, 0.2-0.3 g of sodium hypochlorite and 300-350 mu L of glacial acetic acid are added every 1-1.5 h, and finally the wood flour with white color is obtained by filtering.
Further, ethanol water solution heat treatment: preparing 65% ethanol, adding 350-400 mu L of concentrated sulfuric acid, mixing and stirring, adding the wood flour treated in the step (1) into a reaction kettle according to the solid-to-liquid ratio of 1:8-10, heating at 180-190 ℃ for 75-85 min, taking out the reaction kettle after complete reaction, continuously washing with a small water flow until cooling, washing with 65% ethanol until the mixture is neutral after cooling, performing suction filtration with a funnel, and washing with deionized water to remove redundant reactants to obtain the high-purity cellulose.
Further, hydrogen peroxide solution post-treatment: reacting 4-6 wt% of aqueous hydrogen peroxide and 0.4-0.6 g of sodium hydroxide solid according to the proportion of 80-200.
Further, ultrasonic preparation: and adding 70-85 mL of ionized water into the treated substance to prepare cellulose dispersion, and then carrying out ultrasonic crushing for 30-40 min under an ultrasonic cell crusher to finally obtain the nano cellulose dispersion.
Preferably, the preparation of the lactamized rhodamine 6G: mixing rhodamine 6G, methanol and ethylenediamine, adding the mixture into a three-neck flask, reacting for 8-9 hours at 80-85 ℃ under the protection of nitrogen, then distilling and extracting the mixture under reduced pressure, washing the mixture with water and dichloromethane, drying the mixture with anhydrous sodium sulfate, distilling the mixture under reduced pressure to remove the dichloromethane, and drying the mixture at normal temperature to obtain the lactamized rhodamine 6G.
Further, 35-45 mL of methanol and 0.4-0.6G of rhodamine 6G are weighed, evenly mixed and added into a three-neck flask, in order to discharge air in the flask, nitrogen is introduced into the flask and heated, 1.3-1.5 mL of ethylenediamine is added into the flask when the temperature rises to 35-45 ℃, the temperature is continuously raised, the nitrogen is continuously introduced after the temperature rises to 80-90 ℃, the reaction is stopped after 7-9 h, the product is cooled, the solvent is removed by reduced pressure distillation, 95-105 mL of dichloromethane is added into the residue to be dissolved, and 195-205 mL of water is added for extraction. The organic layer was separated, extracted three more times with water and dried over anhydrous sodium sulfate (Na) 2 SO 4 ) Drying, vacuum filtering with Buchner funnel, collecting filtrate, and distilling under reduced pressure to remove CH 2 C1 2 Solvent to obtain pink powder. And repeatedly carrying out reduced pressure distillation, extraction and drying to remove impurities in the lactamized rhodamine 6G.
Preferably, the preparation of ethylenediamine salicylaldehyde schiff base: dissolving ethylenediamine in absolute ethyl alcohol, transferring the mixture into a three-neck flask, slowly dripping 4.5-5.5 mL of salicylaldehyde into the mixture when the mixture starts to flow back under the heating condition of 80-85 ℃, refluxing for 4-5 hours, stopping heating, standing, cooling to room temperature, filtering when a large number of light yellow crystals are separated out, washing with absolute ethyl alcohol for three times, and then recrystallizing to obtain the ethylenediamine salicylaldehyde Schiff base.
Furthermore, the dosage of the ethylenediamine is 10-15 mL, and the dosage of the absolute ethyl alcohol is 70-80 mL.
Preferably, the intelligent color-changing composite fiber material is prepared by slowly adding 0.7-0.9 g of polyacrylonitrile, 0.14-0.16 g of polyvinyl alcohol, 0.08-0.1 g of nano-cellulose and 0.01-0.03 g of pH intelligent response color-changing molecules into 3.9-4.0 g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 75-85 ℃ for 4-5 hours, adding 15-25 microliter of glutaraldehyde for crosslinking, continuing to heat in a water bath for 4-5 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2-3 hours, and finally drying in a freeze dryer for 20-24 hours to obtain the pH intelligent color-changing composite fiber.
Preferably, the temperature of the coagulation bath is 20 to 40 ℃, the solvent is water, and the curing time is 5 to 10 minutes.
Preferably, the aperture of a spinneret orifice for wet spinning is 0.17-1.5 mm, the extrusion rate of a nozzle is 5-20 mL/h, and the spinning temperature is 20-40 ℃.
The application of the intelligent lignocellulose-based color-changing composite fiber material can be applied to the fields of chemical sensing, intelligent packaging, safe printing, optoelectronic equipment, medical health care products and the like.
The invention has the beneficial effects that:
(1) The preparation method of the intelligent color-changing composite fiber material is simple, the preparation conditions are mild, no environmental pollution is caused, the yield is high, the cost is low, the prepared intelligent color-changing composite fiber material is environment-friendly, has a photochromic effect, is high in luminous color-changing efficiency and good in stability, is suitable for large-scale preparation of intelligent color-changing composite fiber materials with different colors, and has a good application prospect.
(2) The nano-cellulose is prepared from wood-based raw materials, has the advantages of wide source, high mechanical strength, environmental friendliness, biodegradability, easiness in processing, easiness in realizing industrial production and the like, and has high economic use value.
(3) The invention applies the wet spinning process to the intelligent color-changing composite fiber material, so that the prepared intelligent color-changing composite fiber material has better tensile strength, the tensile strength can reach 2.55MPa in a dry state, the tensile strength of the fiber can reach 5.1MPa in a wet state, the fiber material has excellent mechanical property and biocompatibility, the advantages of the wood nano-cellulose fiber and photochromic molecules caused by light and pH are comprehensively utilized, the fiber material can be applied to the fields of optical information storage, military camouflage, biological information molecule marking, fluorescence anti-counterfeiting, flexible electrical appliances and the like, and the application range of the fiber material is widened.
(4) The intelligent color-changing composite fiber material is prepared by modifying cellulose by adopting the rhodamine derivative, the Schiff base and the pH dye, and the intelligent color-changing composite fiber material with different colors can be prepared by selecting different color-changing dyes as modifiers, so that a new theoretical and technical support is provided for the research of the novel intelligent color-changing composite fiber material.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is an electron microscope image of composite fiber without intelligent color-changing molecules added in the embodiment of the invention with different magnifications;
FIG. 2 is an electron microscope image of different magnifications of the intelligent color-changing lignocellulose-based composite fiber added with lactamized rhodamine 6G in the embodiment of the invention;
FIG. 3 is an electron microscope image of different magnifications of the intelligent color-changing lignocellulose-based composite fiber added with ethylenediamine salicylaldehyde Schiff base in the embodiment of the invention;
FIG. 4 is an electron microscope image of different magnifications of the pH-responsive lignocellulose-based intelligent color-changing composite fiber in an embodiment of the invention;
FIG. 5 is an infrared spectrum of a lignocellulose-based smart color-changing composite fiber material of the present invention;
FIG. 6 is a schematic diagram of mechanical properties of a lignocellulose-based smart color-changing composite fiber material according to the invention;
FIG. 7 is a fluorescence spectrum of the lactamized rhodamine 6G added lignocellulose-based intelligent color-changing composite fiber under different metal ion conditions;
FIG. 8 is a fluorescence spectrum of the intelligent color-changing lignocellulose-based composite fiber added with lactamized rhodamine 6G under the condition of different concentrations of mercury ions;
FIG. 9 is a fluorescence spectrum of the intelligent color-changing lignocellulose-based composite fiber with added lactamized rhodamine 6G under different pH conditions;
FIG. 10 is a fluorescence spectrum of intelligent color-changing lignocellulose-based composite fibers with the addition of ethylenediamine salicylaldehyde Schiff base under different pH conditions;
FIG. 11 is a fluorescence change diagram of the intelligent color-changing composite fiber with the addition of lactamized rhodamine 6G lignocellulose base;
FIG. 12 is a graph of the fluorescence change of the intelligent color-changing composite fiber with the addition of ethylenediamine salicylaldehyde Schiff base lignocellulose.
Detailed Description
The present invention will be further described with reference to examples in which various chemicals and reagents are commercially available unless otherwise specified.
Example 1
1. Preparation of nanocellulose
Extraction of nanocellulose with sodium chlorite: in order to remove lignin and hemicellulose in the wood-based raw material, 1g of sodium chlorite is weighed and added into a beaker, then 100mL of deionized water is added into the beaker, the mixture is fully stirred and dissolved into a 1% sodium chlorite solution, 300 mu L of glacial acetic acid is added to ensure that the pH value of the solution is 3, finally a magnetic stirrer is used for stirring for 6 hours at the temperature of 85 ℃, 0.2g of sodium hypochlorite and 300 mu L of glacial acetic acid are added every 1.5 hours, and finally filtering is carried out to obtain the wood flour with the white color.
Ethanol water solution heat treatment: preparing 65% ethanol, adding 350 mu L of concentrated sulfuric acid, mixing and stirring, adding the wood powder treated in the step (1) into a reaction kettle according to a solid-to-liquid ratio of 1:8-10, heating at 180 ℃ for 80min, taking out the reaction kettle after complete reaction, cooling, washing with 65% ethanol to be neutral, performing suction filtration by using a funnel, and cleaning redundant unreacted substances by using deionized water to obtain the high-purity cellulose.
Hydrogen peroxide solution post-treatment: preparing 4wt% of aqueous hydrogen peroxide, adding 0.4g of sodium hydroxide into the aqueous hydrogen peroxide, reacting the hydrogen peroxide and the sodium hydroxide for about 25min until no bubbles are generated, mixing a cellulose sample according to a solid-to-liquid ratio of 1.
Ultrasonic preparation: and adding 70mL of ionized water into the treated substance to prepare cellulose dispersion, and then carrying out ultrasonic crushing for 35min under an ultrasonic cell crusher to finally obtain the nano cellulose dispersion.
2. Preparation of lactamized rhodamine 6G
35mL of methanol and 0.5G of rhodamine 6G are weighed, uniformly mixed and added into a three-neck flask, in order to discharge the air in the flask, nitrogen is introduced into the flask and heated, 1.3mL of ethylenediamine is added into the flask when the temperature rises to 40 ℃, the temperature is continuously raised, nitrogen is continuously introduced when the temperature rises to 85 ℃, the reaction is stopped after 8 hours, the product is cooled, the solvent is removed by reduced pressure distillation, 95mL of dichloromethane is added into the residue to be dissolved, and 195mL of water is added for extraction. The organic layer was separated, extracted three more times with water and dried over anhydrous sodium sulfate (Na) 2 SO 4 ) Drying, vacuum filtering with Buchner funnel, collecting filtrate, and distilling under reduced pressure to remove CH 2 C 12 Solvent to obtain pink powder. And repeatedly carrying out reduced pressure distillation, extraction and drying to remove impurities in the lactamized rhodamine 6G.
3. Preparation of ethylenediamine salicylaldehyde Schiff base
Weighing 10mL of ethylenediamine, dissolving the ethylenediamine in 70mL of absolute ethanol, transferring the ethylenediamine into a three-neck flask, slowly dripping 4.5mL of salicylaldehyde into the three-neck flask when refluxing is started under the heating condition of 80 ℃, refluxing for 4 hours, stopping heating, standing, cooling to room temperature, filtering when a large amount of light yellow crystals are separated out, washing with absolute ethanol for three times, and then recrystallizing to obtain the ethylenediamine salicylaldehyde Schiff base.
4. Preparation of intelligent color-changing composite fiber added with lactamized rhodamine 6G lignocellulose base
Slowly adding 0.7G of polyacrylonitrile, 0.14G of polyvinyl alcohol, 0.08G of nanocellulose and 0.01G of lactamized rhodamine 6G into 3.9G of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 15 mu L of glutaraldehyde after 4 hours, continuing to heat in a water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the pore diameter of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a sprayer is 15mL/h, the spinning temperature is 30 ℃, and finally drying in a freeze dryer for 22 hours to obtain the lactamized rhodamine 6G lignocellulose-based intelligent color-changing composite fiber.
5. Preparing intelligent color-changing composite fiber added with ethylenediamine salicylaldehyde Schiff base lignocellulose base
Slowly adding 0.7g of polyacrylonitrile, 0.14g of polyvinyl alcohol, 0.08g of nano-cellulose and 0.01g of ethylenediamine salicylaldehyde Schiff base into 3.9g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 15 mu L of glutaraldehyde after 4 hours, continuing to heat in a water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the aperture of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a sprayer is 15mL/h, the spinning temperature is 30 ℃, and finally drying in a freeze dryer for 22 hours to obtain the fiber to be prepared.
6. Preparation of pH-responsive lignocellulose-based intelligent color-changing fiber
Slowly adding 0.7g of polyacrylonitrile, 0.14g of polyvinyl alcohol, 0.08g of nano-cellulose, 0.01g of methyl orange, 0.01g of bromothymol blue and 0.01g of phenolphthalein into 3.9g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 15 mu L of glutaraldehyde after 4 hours, continuing to heat in the water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the aperture of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a sprayer is 15mL/h, the spinning temperature is 30 ℃, and finally drying for 22 hours in a freeze dryer to obtain the prepared fiber.
Example 2
1. Preparation of nanocellulose
Extraction of nanocellulose with sodium chlorite: in order to remove lignin and hemicellulose in the wood-based raw material, 1.5g of sodium chlorite is weighed and added into a beaker, then 150mL of deionized water is added into the beaker, the mixture is fully stirred and dissolved into 1.5% sodium chlorite solution, 350 uL of glacial acetic acid is added to ensure that the pH value of the solution is 3.5, finally a magnetic stirrer is used for stirring for 6 hours at 85 ℃, 0.25g of sodium hypochlorite and 330 uL of glacial acetic acid are added every 1.5 hours, and finally the mixture is filtered to obtain the wood flour with white color.
Ethanol water solution heat treatment: preparing 65% ethanol, adding 380 mu L of concentrated sulfuric acid, mixing and stirring, adding the wood powder treated in the step (1) into a reaction kettle according to a solid-to-liquid ratio of 1:8-10, heating at 180 ℃ for 80min, taking out the reaction kettle after complete reaction, continuously washing with a small water flow until cooling, washing with 60 ℃ 65% ethanol until the ethanol is neutral, performing suction filtration with a funnel, and washing with deionized water to remove redundant reactants to obtain the high-purity cellulose.
Hydrogen peroxide solution post-treatment: firstly, preparing 5wt% of aqueous hydrogen peroxide, adding 0.7g of sodium hydroxide into the aqueous hydrogen peroxide, reacting the hydrogen peroxide and the sodium hydroxide for about 25min until no bubbles are generated, then taking a cellulose sample according to a solid-to-liquid ratio of 1.
Ultrasonic preparation: and adding 70mL of ionized water into the treated substance to prepare cellulose dispersion, and then carrying out ultrasonic crushing for 35min under an ultrasonic cell crusher to finally obtain the nano cellulose dispersion.
2. Preparation of lactamized rhodamine 6G
Weighing 40mL of methanol and 0.5G of rhodamine 6G, uniformly mixing and adding the methanol and the rhodamine into a three-neck flask, introducing nitrogen into the flask and heating the nitrogen to discharge air in the flask, adding 1.4mL of ethylenediamine into the flask when the temperature rises to 40 ℃, continuously increasing the temperature, and continuously increasing the temperature when the temperature rises to 85 DEG CNitrogen was introduced, the reaction was stopped after 8 hours, after the product was cooled, the solvent was distilled off under reduced pressure, 100mL of methylene chloride was added to the residue to dissolve it, and 200mL of water was added for extraction. The organic layer was separated, extracted three more times with water and dried over anhydrous sodium sulfate (Na) 2 SO 4 ) Drying, vacuum filtering with Buchner funnel, collecting filtrate, and distilling under reduced pressure to remove CH 2 C1 2 Solvent to obtain pink powder. And repeatedly carrying out reduced pressure distillation, extraction and drying to remove impurities in the lactamized rhodamine 6G.
3. Preparation of ethylenediamine salicylaldehyde Schiff base
Dissolving 12mL of ethylenediamine in 75mL of absolute ethanol, transferring the mixture into a three-neck flask, slowly dripping 5mL of salicylaldehyde into the three-neck flask when the mixture starts to reflux under the heating condition of 80 ℃, refluxing for 4 hours, stopping heating, standing, cooling to room temperature, filtering when a large amount of light yellow crystals are separated out, washing with absolute ethanol for three times, and then recrystallizing to obtain the ethylenediamine salicylaldehyde Schiff base.
4. Preparation of intelligent color-changing composite fiber added with lactamized rhodamine 6G lignocellulose base
Slowly adding 0.8G of polyacrylonitrile, 0.15G of polyvinyl alcohol, 0.09G of nanocellulose and 0.02G of lactamized rhodamine 6G into 4.0G of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 20 mu L of glutaraldehyde after 4 hours, continuing to heat in a water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the pore diameter of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a sprayer is 15mL/h, the spinning temperature is 30 ℃, and finally drying in a freeze dryer for 22 hours to obtain the lactamized rhodamine 6G lignocellulose-based intelligent color-changing composite fiber.
5. Preparation of intelligent color-changing composite fiber added with ethylenediamine salicylaldehyde Schiff base lignocellulose base
Slowly adding 0.8g of polyacrylonitrile, 0.15g of polyvinyl alcohol, 0.09g of nano-cellulose and 0.13g of ethylenediamine salicylaldehyde Schiff base into 4.0g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 20 mu L of glutaraldehyde after 4 hours, continuing to heat in a water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the aperture of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a sprayer is 15mL/h, the spinning temperature is 30 ℃, and finally drying in a freeze dryer for 22 hours to obtain the fiber to be prepared.
6. Preparation of pH response lignocellulose-based intelligent color-changing fiber
Slowly adding 0.8g of polyacrylonitrile, 0.15g of polyvinyl alcohol, 0.09g of nano-cellulose, 0.02g of methyl orange, 0.02g of bromothymol blue and 0.02g of phenolphthalein into 4.0g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 20 mu L of glutaraldehyde after 4 hours, continuing to heat in a water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the aperture of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a nozzle is 15mL/h, the spinning temperature is 30 ℃, and finally drying for 22 hours in a freeze dryer to obtain the fiber to be prepared.
Example 3
1. Preparation of nanocellulose
Extraction of nanocellulose with sodium chlorite: in order to remove lignin and hemicellulose in the wood-based raw material, 2g of sodium chlorite is weighed and added into a beaker, 200mL of deionized water is added into the beaker, the mixture is fully stirred and dissolved into 2% sodium chlorite solution, 400 mu L of glacial acetic acid is added to keep the pH value of the solution at about 4, finally a magnetic stirrer is used for stirring for 7 hours at 85 ℃, 0.3g of sodium hypochlorite and 350 mu L of glacial acetic acid are added every 1.5 hours, and finally the mixture is filtered to obtain the wood flour with white color.
Ethanol water solution heat treatment: preparing 65% ethanol, adding 400 mu L of concentrated sulfuric acid, mixing and stirring, adding the wood powder treated in the step (1) into a reaction kettle according to a solid-to-liquid ratio of 1:8-10, heating at 180 ℃ for 80min, taking out the reaction kettle after complete reaction, continuously washing with a small water flow until cooling, washing with 60 ℃ 65% ethanol until the mixture is neutral, performing suction filtration with a funnel, and washing with deionized water to remove redundant reactants to obtain the high-purity cellulose.
Hydrogen peroxide solution post-treatment: firstly, preparing 6wt% of aqueous hydrogen peroxide, adding 1g of sodium hydroxide into the aqueous hydrogen peroxide, reacting the hydrogen peroxide and the sodium hydroxide for about 35min until no bubbles are generated, then taking a cellulose sample according to a solid-to-liquid ratio of 1.
Ultrasonic preparation: and adding 85mL of ionized water into the treated substance to prepare cellulose dispersion, and then carrying out ultrasonic crushing for 40min under an ultrasonic cell crusher to finally obtain the nano cellulose dispersion.
2. Preparation of lactamized rhodamine 6G
45mL of methanol and 0.6G of rhodamine 6G are weighed, mixed uniformly and added into a three-neck flask, in order to exhaust air in the flask, nitrogen is introduced into the flask and heated, 1.5mL of ethylenediamine is added into the flask when the temperature rises to 45 ℃, the temperature is continuously raised, nitrogen is continuously introduced when the temperature rises to 90 ℃, the reaction is stopped after 9h, after the product is cooled, the solvent is removed by distillation under reduced pressure, 105mL of dichloromethane is added into the residue to be dissolved, and 205mL of water is added for extraction. The organic layer was separated, extracted three more times with water and dried over anhydrous sodium sulfate (Na) 2 SO 4 ) Drying, vacuum filtering with Buchner funnel, collecting filtrate, and distilling under reduced pressure to remove CH 2 C1 2 Solvent to obtain pink powder. And repeatedly carrying out reduced pressure distillation, extraction and drying to remove impurities in the lactamized rhodamine 6G.
3. Preparation of Ethylenediamine salicylaldehyde Schiff base
Dissolving 15mL of ethylenediamine in 80mL of absolute ethanol, transferring the mixture into a three-neck flask, slowly dripping 5.5mL of salicylaldehyde into the three-neck flask when the mixture starts to reflux under the heating condition of 80 ℃, refluxing for 4 hours, stopping heating, standing, cooling to room temperature, filtering when a large amount of light yellow crystals are separated out, washing with absolute ethanol for three times, and then recrystallizing to obtain the ethylenediamine salicylaldehyde Schiff base.
4. Preparation of intelligent color-changing composite fiber added with lactamized rhodamine 6G lignocellulose base
Slowly adding 0.9G of polyacrylonitrile, 0.16G of polyvinyl alcohol, 0.1G of nanocellulose and 0.03G of lactamized rhodamine 6G into 4.0G of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 25 mu L of glutaraldehyde after 4 hours, continuing to heat in a water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the pore diameter of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a sprayer is 15mL/h, the spinning temperature is 30 ℃, and finally drying in a freeze dryer for 22 hours to obtain the lactamized rhodamine 6G lignocellulose-based intelligent color-changing composite fiber.
5. Preparation of intelligent color-changing composite fiber added with ethylenediamine salicylaldehyde Schiff base lignocellulose base
Slowly adding 0.9g of polyacrylonitrile, 0.16g of polyvinyl alcohol, 0.1g of nano-cellulose and 0.15g of ethylenediamine salicylaldehyde Schiff base into 4.0g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 20 mu L of glutaraldehyde after 4 hours, continuing to heat in a water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the pore diameter of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a sprayer is 15mL/h, the spinning temperature is 30 ℃, and finally drying in a freeze dryer for 22 hours to obtain the fiber to be prepared.
6. Preparation of pH-responsive lignocellulose-based intelligent color-changing fiber
Slowly adding 0.9g of polyacrylonitrile, 0.16g of polyvinyl alcohol, 0.1g of nano-cellulose, 0.02g of methyl orange, 0.02g of bromothymol blue and 0.02g of phenolphthalein into 4.0g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 85 ℃, adding 25 mu L of glutaraldehyde after 4 hours, continuing to heat in the water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 30 ℃, the solvent is water, the curing time is 10 minutes, the aperture of a spinneret orifice of the wet spinning is 0.55mm, the extrusion rate of a sprayer is 15mL/h, the spinning temperature is 30 ℃, and finally drying for 22 hours in a freeze dryer to obtain the fiber to be prepared.
Example 4
1. Preparation of nanocellulose
Extraction of nanocellulose with sodium chlorite: in order to remove lignin and hemicellulose in the wood-based raw material, 1.50g of sodium chlorite is weighed and added into a beaker, then 150mL of deionized water is added into the beaker, the mixture is fully stirred and dissolved into 1% sodium chlorite solution, 300 mu L of glacial acetic acid is added to ensure that the pH value of the solution is 3.38, finally a magnetic stirrer is used for stirring for 6 hours at the temperature of 80 ℃, 0.2g of sodium hypochlorite and 300 mu L of glacial acetic acid are added every 1 hour, and finally the mixture is filtered to obtain the wood flour with white color.
Ethanol water solution heat treatment: preparing 65% ethanol, adding 380 mu L of concentrated sulfuric acid, mixing and stirring, adding the wood powder treated in the step (1) into a reaction kettle according to a solid-to-liquid ratio of 1:8-10, heating at 185 ℃ for 80min, taking out the reaction kettle after complete reaction, continuously washing with a small water flow until cooling, washing with 60 ℃ 65% ethanol until the ethanol is neutral, performing suction filtration with a funnel, and washing with deionized water to remove redundant reactants to obtain the high-purity cellulose.
Hydrogen peroxide solution post-treatment: firstly, preparing 5wt% of aqueous hydrogen peroxide, adding 0.5g of sodium hydroxide into the aqueous hydrogen peroxide, reacting the hydrogen peroxide and the sodium hydroxide for about 30min until no bubbles are generated, then taking a cellulose sample according to a solid-to-liquid ratio of 1.
Ultrasonic preparation: and adding 80mL of ionized water into the treated substance to prepare cellulose dispersion, and then carrying out ultrasonic crushing for 40min under an ultrasonic cell crusher to finally obtain the nano cellulose dispersion.
2. Preparation of lactamized rhodamine 6G
Weighing 40mL of methanol and 0.5G of rhodamine 6G, uniformly mixing and adding the methanol and the rhodamine into a three-neck flask, in order to exhaust air in the flask, introducing nitrogen into the flask and heating the nitrogen, adding 1.4mL of ethylenediamine into the flask when the temperature rises to 40 ℃, continuously raising the temperature, continuously introducing nitrogen when the temperature rises to 85 ℃, stopping the reaction after 8 hours, removing the solvent by reduced pressure distillation after the product is cooled, adding 100mL of dichloromethane into the residue to dissolve the dichloromethane, and then adding 200mL of water for extraction. The organic layer was separated and further extracted three times with water, and then with anhydrous sodium sulfate (Na) 2 SO 4 ) Drying, vacuum filtering with Buchner funnel, collecting filtrate, and distilling under reduced pressure to remove CH 2 C1 2 Solvent to obtain pink powder. And repeatedly carrying out reduced pressure distillation, extraction and drying to remove impurities in the lactamized rhodamine 6G.
3. Preparation of ethylenediamine salicylaldehyde Schiff base
Weighing 15mL of ethylenediamine, dissolving the ethylenediamine in 80mL of absolute ethanol, transferring the ethylenediamine into a three-neck flask, slowly dripping 5.1mL of salicylaldehyde into the ethylenediamine under the heating condition of 80 ℃ when the reflux is started, refluxing for 4.5 hours, stopping heating, standing, cooling to room temperature, filtering when a large number of light yellow crystals are separated out, washing with absolute ethanol for three times, and then recrystallizing to obtain the ethylenediamine salicylaldehyde Schiff base.
4. Preparation of intelligent color-changing composite fiber added with lactamized rhodamine 6G lignocellulose base
Slowly adding 0.8G of polyacrylonitrile, 0.15G of polyvinyl alcohol, 0.09G of nano-cellulose and 0.02G of lactamized rhodamine 6G into 3.96G of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 20 mu L of glutaraldehyde after 4 hours, continuing heating in a water bath for 4 hours, standing for defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 25 ℃, the solvent is water, the curing time is 10 minutes, the pore diameter of a spinneret orifice of the wet spinning is 1mm, the extrusion rate of a sprayer is 10mL/h, the spinning temperature is 30 ℃, and finally carrying out freeze drying in a freeze dryer for 24 hours to obtain the lactamized rhodamine 6G wood nano-cellulose based intelligent color-changing composite fiber.
5. Preparing intelligent color-changing composite fiber added with ethylenediamine salicylaldehyde Schiff base lignocellulose base
Slowly adding 0.8g of polyacrylonitrile, 0.15g of polyvinyl alcohol, 0.09g of nano-cellulose and 0.1g of ethylenediamine salicylaldehyde Schiff base into 3.96g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 15 mu L of glutaraldehyde after 4 hours, continuing to heat in a water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 25 ℃, the solvent is water, the curing time is 10 minutes, the pore diameter of a spinneret orifice of the wet spinning is 1mm, the extrusion rate of a sprayer is 10mL/h, the spinning temperature is 30 ℃, and finally drying in a freeze dryer for 24 hours to obtain the prepared fiber.
6. Preparation of pH-responsive lignocellulose-based intelligent color-changing fiber
Slowly adding 0.8g of polyacrylonitrile, 0.15g of polyvinyl alcohol, 0.09g of nano-cellulose, 0.01g of methyl orange, 0.01g of bromothymol blue and 0.01g of phenolphthalein into 3.96g of dimethyl sulfoxide solvent to obtain high-concentration spinning solution, heating and stirring the spinning solution in a water bath kettle at 80 ℃, adding 15 mu L of glutaraldehyde after 4 hours, continuing to heat in the water bath for 4 hours, standing and defoaming, then carrying out wet spinning in a coagulating bath, soaking for 2 hours, wherein the temperature of the coagulating bath is 25 ℃, the solvent is water, the curing time is 10 minutes, the aperture of a spinneret orifice of the wet spinning is 1mm, the extrusion rate of a sprayer is 10mL/h, the spinning temperature is 30 ℃, and finally drying for 24 hours in a freeze dryer to obtain the fiber to be prepared.
Performance testing of the conjugate fiber prepared in example 4
(1) Mechanical property detection
The prepared intelligent color-changing composite fiber is detected in a dry state and a wet state respectively, the surface of the fiber is smooth and flexible, and the tensile strength is 2.55MPa in the dry state; the tensile strength in the wet state was 5.1MPa.
(2) Detection of color Change Performance
A. Effect of alkalinity and acidity on the color-changing Properties of fibers
The lactamized rhodamine 6G lignocellulose-based intelligent color-changing composite fiber is observed under sunlight, the fiber is white, and no fluorescence is found when the fiber is observed under ultraviolet light; the acid solution is dripped on the fiber, the fiber has no color change under sunlight, the fiber has orange yellow fluorescence under ultraviolet light, the color-changing fiber can recover the white and non-fluorescence state under the alkaline condition, and the fiber can be repeatedly used for a plurality of times. Adding ethylenediamine salicylaldehyde Schiff base lignocellulose-based intelligent color-changing composite fibers, observing the fibers in the sunlight, wherein the fibers are white, and observing the fibers in ultraviolet light to find that the fibers have no fluorescence; the alkaline solution is dripped on the fiber, the fiber has no color change under sunlight, the fiber shows blue fluorescence under ultraviolet light, the fiber can recover the non-fluorescence state under the acidic condition, and the fiber can be repeatedly used for a plurality of times. The intelligent color-changing composite fiber material has good fluorescence color-changing performance, can be repeatedly used, improves the utilization rate of the intelligent color-changing composite fiber material, and has higher economic use value.
Respectively dripping different pH aqueous solutions on the pH response lignocellulose-based intelligent color-changing fibers, and finding that the color of the fibers changes from red to yellow when the pH color-changing fibers are in a range from pH =3 to pH = 6; at pH =6 to pH =7.5, the fiber turned from yellow to blue; at pH =7.5 to pH =10, the fibers turned violet from blue. Namely, the intelligent color-changing composite fiber material can display different colors according to different pH values, so that the application range of the intelligent color-changing composite fiber material is expanded.
B. Effect of Metal ions on the color Change Properties of fibers
Taking the intelligent color-changing composite fiber added with the lactamized rhodamine 6G lignocellulose base as an experimental sample, and dripping Cu on the fiber 2+ The fiber of the solution is light pink and has no fluorescence under ultraviolet light; dropping Hg on the fiber 2+ The fiber of the solution is light pink and is light yellow fluorescence under ultraviolet light; dropping Al on the fiber 3+ The fiber of the solution is pink, and the fiber of the solution is yellow and fluorescent under ultraviolet light; dropwise adding Fe on the fiber 3+ The solution, fiber is pink, and under the ultraviolet light, the solution shows strong yellow fluorescence. Namely, the intelligent color-changing composite fiber material prepared by the invention has good ultravioletThe double-mode intelligent color-changing performance of visible light is realized, different colors are formed by dropping different metal ions, the requirements of the multifunctional color-changing fiber are met, and the application of the multifunctional color-changing fiber is further widened.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (10)
1. Wooden nano-cellulose based intelligent color-changing composite fiber material, which is characterized in that: the color-changing dye comprises intelligent color-changing molecules and nanocellulose, wherein the intelligent color-changing molecules are one or more of lactamized rhodamine 6G, ethylenediamine salicylaldehyde Schiff base, methyl orange, bromothymol blue and phenolphthalein.
2. The method for preparing the lignocellulose-based intelligent color-changing composite fiber material as recited in claim 1, comprising the steps of:
(1) Extraction of nanocellulose
Extracting cellulose in a wood-based raw material by using sodium chlorite, then performing heat treatment by using an ethanol water solution, then performing treatment by using a hydrogen peroxide solution, and finally performing ultrasonic crushing, freeze drying to prepare nano cellulose;
(2) Preparation of intelligent color-changing composite fiber material
Taking dimethyl sulfoxide as a solvent, the ratio of the nano-cellulose, the intelligent color-changing molecules, polyacrylonitrile and polyvinyl alcohol prepared in the step (1) is (5-20); the intelligent color-changing molecule is one or more of lactamized rhodamine 6G, ethylenediamine salicylaldehyde Schiff base, methyl orange, bromothymol blue and phenolphthalein.
3. The method for preparing the lignocellulose-based intelligent color-changing composite fiber material as recited in claim 2, wherein: the wood-based raw material in the step (1) is one or more of poplar wood powder, oak wood powder, fir wood powder, beech wood powder, birch wood powder, maple wood powder, straw powder, bagasse, bamboo powder, reed and cotton.
4. The method for preparing the lignocellulose-based intelligent color-changing composite fiber material as recited in claim 2, wherein: in the step (1), sodium chlorite and glacial acetic acid are added every 1-1.5 hours to extract cellulose by using sodium chlorite, so that the pH value of the solution is 3-4.
5. The method for preparing the lignocellulose-based intelligent color-changing composite fiber material as recited in claim 2, wherein: and (2) performing heat treatment on the ethanol water solution in the step (1), and adding wood powder treated by sodium chlorite, 65% ethanol water solution and 350-400 mu L concentrated sulfuric acid into a reaction kettle, wherein the solid-to-liquid ratio is 1:8-10.
6. The method for preparing the lignocellulose-based intelligent color-changing composite fiber material as recited in claim 2, wherein: in the step (1), hydrogen peroxide solution treatment, 5wt% of hydrogen peroxide solution and sodium hydroxide solid react for 15-30 minutes without bubbling according to the proportion of 80-200, and a cellulose sample is taken according to the solid-to-liquid ratio of 1.
7. The method for preparing the lignocellulose-based intelligent color-changing composite fiber material as recited in claim 2, wherein: and (2) carrying out ultrasonic treatment in the step (1), mixing the sample treated by the hydrogen peroxide solution with deionized water according to a solid-to-liquid ratio of 1.
8. The method for preparing the lignocellulose-based intelligent color-changing composite fiber material as recited in claim 2, wherein: in the step (2), the temperature of the coagulating bath is 20-40 ℃, the solvent is water, and the curing time is 5-10 minutes.
9. The method for preparing the lignocellulose-based intelligent color-changing composite fiber material as recited in claim 2, wherein: in the step (2), the aperture of a spinneret orifice for wet spinning is 0.17-1.5 mm, the extrusion rate of a nozzle is 5-20 mL/h, and the spinning temperature is 20-40 ℃.
10. The application of the intelligent color-changing lignocellulose-based composite fiber material is characterized in that: the method is applied to the fields of chemical sensing, intelligent packaging, safe printing, optoelectronic equipment and medical health care products.
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