CN109898171B - Method for preparing modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber - Google Patents
Method for preparing modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber Download PDFInfo
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- CN109898171B CN109898171B CN201910194513.3A CN201910194513A CN109898171B CN 109898171 B CN109898171 B CN 109898171B CN 201910194513 A CN201910194513 A CN 201910194513A CN 109898171 B CN109898171 B CN 109898171B
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 27
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- 238000012986 modification Methods 0.000 claims abstract description 13
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- 238000002166 wet spinning Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 15
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- 238000001035 drying Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
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- 238000001914 filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
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- 238000001179 sorption measurement Methods 0.000 abstract description 46
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001431 copper ion Inorganic materials 0.000 abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 10
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for modifying microcrystalline cellulose/graphene oxide composite fibers of cotton stalk barks, and belongs to the technical field of waste biomass resource recycling and the field of heavy metal pollution reduction, water resource purification and environmental protection. The method takes the microcrystalline cellulose of the cotton stalk barks as a raw material, uses maleic anhydride for modification, adopts a [ Bmim ] Cl ionic liquid and dimethyl sulfoxide dissolving system for dissolution, compounds graphene oxide as a filler, and uses a wet spinning technology for spinning to prepare the modified composite fiber, wherein the adsorption capacity of the modified composite fiber on copper ions is 24.38mg/g, the linear density of the fiber is 18.02tex, and the breaking strength is 28.25 cN. The raw materials used by the invention have wide and cheap sources, the preparation process is simple and convenient, and the prepared modified composite fiber has better adsorption capacity to copper ions in aqueous solution.
Description
Technical Field
The invention relates to a method for preparing modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fibers by utilizing cotton stalk bark microcrystalline cellulose and graphene oxide.
Background
The problem of heavy metal pollution of water bodies in China is increasingly serious, the content of heavy metal ions exceeds the standard, and serious harm is caused to human health and social development, so that heavy metal pollution treatment is not slow at all. The cellulose material has the advantages of strong adsorption capacity, reproducibility, environmental protection and low price, so the cellulose material is very suitable to be used as an adsorbent for treating pollutants in wastewater. The cellulose not only exists widely in nature, but also can be obtained from various crops, and the cotton stalk cotton has abundant cotton stalk resources as a big country of the cotton industry in China, the annual output of the cotton stalks reaches 1530 ten thousand tons, and 400 ten thousand tons of cotton stalk barks exist, so that the cellulose can be changed into valuable things by reasonable development.
Currently, cellulose-based adsorption materials are roughly divided into nano cellulose materials, cellulose microsphere materials and cellulose membrane materials according to forms. Compared with the nano material, the adsorption fiber is convenient to recycle and has a simple preparation method. Compared with the microsphere membrane adsorbing material, the fiber has the advantages of large external specific surface, short mass transfer distance, higher adsorption selectivity, high adsorption and desorption speed, strong regeneration capacity, low energy consumption, small fluid resistance and the like. Meanwhile, the adsorption fiber has various application forms and can be made into multifilament, yarn, woven fabric, non-woven fabric and the like, so that the adsorption fiber can be widely applied to the fields of individual respiratory protection, gas purification, environmental protection, water treatment, recovery of precious metal ions, separation and extraction of medicines, biochemical engineering, wet metallurgy and the like. Although cellulose has a certain adsorption effect on heavy metals due to its structural characteristics. However, it has been found that the direct use of natural cellulose for substance adsorption has some disadvantages, such as low adsorption capacity and low selectivity. In order to enhance the adsorption capacity of the cellulose material to heavy metal ions, the cellulose is usually modified chemically or physically. The chemical treatment is mainly completed by the modification reaction of a large amount of hydroxyl in a fiber macromolecular structure, and functional groups with specific adsorption performance are introduced after the modification of the fiber hydroxyl, so that the adsorption performance of the cellulose material is greatly improved. The physical modification is to improve the performance of the cellulose by taking the cellulose as a matrix and adding other functional components. According to the invention, maleic anhydride is grafted to a cellulose skeleton chain after ring opening through a polymerization reaction, so that carboxyl and carbonyl groups are added on the surface of cellulose, and the adsorption performance of the cellulose material is greatly improved. Graphene oxide is an excellent filler capable of enhancing adsorption capacity because graphene oxide has characteristics of large specific surface area and good hydrophilicity, and has many anionic functional groups, which has strong electrostatic adsorption effect on heavy metal ions having cationic properties. However, Graphene Oxide (GO) has a small size, is easily agglomerated during use, and has a problem of being difficult to separate after use, which limits the development of graphene oxide, so how to overcome the problems becomes a main research direction of researchers in academia in recent years. According to the invention, a composite modification mode is adopted, and the nano graphene oxide is added into the fiber, so that the adsorption performance of the cellulose is improved, and the problem that the graphene oxide is easy to agglomerate and difficult to separate and recycle is solved.
Disclosure of Invention
In order to solve the problems of environmental pollution and resource waste, the invention provides a method for preparing novel adsorption fibers, aiming at removing heavy metals in polluted wastewater, reducing the pollution of the heavy metals to the environment, improving the utilization value of waste cotton stalks and increasing the social and economic benefits.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for preparing modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fibers comprises the following steps:
(1) modification: placing the microcrystalline cellulose of the cotton stalk bark in 10-20 wt% of alkaline solution, stirring for 1-3 hours at 50-70 ℃ for alkali treatment, repeatedly washing a product with deionized water, filtering and drying to obtain the microcrystalline cellulose of the cotton stalk bark after the alkali treatment; adding the cotton stalk bark microcrystalline cellulose subjected to alkali treatment into melted maleic anhydride, stirring for 2 hours at 65 ℃, dripping pyridine after stirring, continuously heating to 90 ℃, continuously stirring for 6 hours, repeatedly washing a product with deionized water, ethanol and acetone, filtering, and drying to obtain the modified cotton stalk bark microcrystalline cellulose;
wherein the mass ratio of the microcrystalline cellulose of the cotton stalk bark treated by alkali to the maleic anhydride is 1: 6; the mass of the pyridine accounts for 2-4% of that of the microcrystalline cellulose of the cotton stalk bark treated by the alkali, and the pyridine is preferably 3%.
(2) Dissolving: putting the modified cotton stalk bark microcrystalline cellulose obtained in the step (1) into a melted [ Bmim ] Cl ionic liquid to be dissolved for 2-3 hours under the heating condition of 70-90 ℃ to obtain a dissolved solution;
wherein the mass ratio of the microcrystalline cellulose of the modified cotton stalk bark to the ionic liquid is 1: 8-1: 15, preferably 1: 10;
(3) compounding: uniformly dispersing a certain amount of graphene oxide into dimethyl sulfoxide to obtain a mixed solution of the graphene oxide and the dimethyl sulfoxide; adding the mixed solution of graphene oxide and dimethyl sulfoxide into the dissolved solution obtained in the step (2) to obtain a modified cotton stalk bark microcrystalline cellulose composite spinning solution;
wherein the mass of the graphene oxide is 1-5% of the mass of the modified cotton stalk bark microcrystalline cellulose, and the mass of the dimethyl sulfoxide is 75-175% of the total mass of the modified cotton stalk bark microcrystalline cellulose and the ionic liquid;
(4) defoaming: continuously stirring the modified cotton stalk bark microcrystalline cellulose composite spinning solution obtained in the step (3) for 2-3 hours, taking out the spinning solution after the spinning solution is stable, carrying out vacuum defoaming, and standing for a period of time;
(5) spinning: carrying out wet spinning on the modified cotton stalk bark microcrystalline cellulose composite spinning solution treated in the step (4), wherein a coagulation bath is deionized water, and adjusting the coagulation time to obtain modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fibers;
according to the technical scheme, in a preferable case, in the step (1), the alkaline solution is a NaOH solution, a potassium hydroxide solution or a calcium hydroxide solution.
According to the technical scheme, in a preferable case, in the step (1), the temperature of the alkali treatment is 60 ℃ and the time is 2 hours.
According to the technical scheme, in a preferable case, in the step (1), the drying conditions are as follows: the temperature is 70-90 ℃, and the time is 3-4 hours.
According to the technical scheme, in a preferable case, in the step (2), the modified cotton stalk bark microcrystalline cellulose obtained in the step (1) is placed into a melted [ Bmim ] Cl ionic liquid to be dissolved for 2-3 hours under the heating condition of 80 ℃ to obtain a dissolved solution.
According to the technical scheme, in the step (4), the vacuum defoaming time is preferably 20 to 40 minutes, preferably 30 minutes, and the standing time is 12 to 48 hours, preferably 24 hours.
According to the technical scheme, in a preferable case, in the step (5), the solidification time is 30-150 seconds.
According to the technical scheme, the particle size of the graphene oxide is preferably 0.5-4 nm.
According to the technical scheme, the microcrystalline cellulose of the cotton stalk bark can be prepared by referring to the method of patent No. 201710847371.7 under the preferable condition.
According to the technical scheme, preferably, the method further comprises the following steps: (6) air drying: and (5) air-drying the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber obtained in the step (5).
The invention also relates to the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the method comprises the steps of taking cotton stalk bark microcrystalline cellulose as a raw material, carrying out graft modification on the cotton stalk bark microcrystalline cellulose by using maleic anhydride, dissolving the modified cotton stalk bark microcrystalline cellulose by using an ionic liquid and dimethyl sulfoxide dissolving system, adding graphene oxide as a filler into the dissolving solution, preparing a composite spinning solution, and finally spinning in a wet spinning mode to prepare the modified composite fiber with the copper ion adsorption capacity of 24.38mg/g, the fiber linear density of 18.02tex and the breaking strength of 28.25 cN. The raw materials used by the invention have wide and cheap sources, the preparation process is simple and convenient, and the prepared modified composite fiber has better adsorption capacity to copper ions in aqueous solution. In the invention, the microcrystalline cellulose of the cotton stalk bark is used as the raw material, so that the utilization value of the waste cotton stalks is improved, and the social and economic benefits are increased; the carboxyl which has the electrostatic adsorption effect on heavy metal ions is introduced to the microcrystalline cellulose of the cotton stalk bark by using a chemical modification method, so that the adsorption capacity is enhanced, and the modification method is simple to operate; the environment-friendly, safe and recyclable ionic liquid is used as a dissolving agent of microcrystalline cellulose of cotton stalk barks; the graphene oxide is added into the fibers by adopting an ultrasonic dispersion method, so that the adsorption capacity is enhanced, and the problem that the graphene oxide as an adsorption material is easy to agglomerate and is difficult to recover is solved. Compared with nano-cellulose materials, the adsorption fiber is convenient to recover and has a simple preparation method. Compared with the microsphere membrane cellulose adsorption material, the fiber has large external specific surface, short mass transfer distance and higher adsorption selectivity. Meanwhile, the application forms of the composite material are various, and the composite material can be made into multifilament, yarn, woven fabric, non-woven fabric and the like.
Drawings
FIG. 1 is a scanning electron micrograph of fibers at 500 times magnification. (a) Is the microcrystalline cellulose fiber of cotton stalk bark, (b) is the microcrystalline cellulose/GO composite fiber of modified cotton stalk bark in example 3, and the surface of the microcrystalline cellulose/GO composite fiber of modified cotton stalk bark can be seen to be rougher than the surface of the microcrystalline cellulose fiber of cotton stalk bark by comparison. The microcrystalline cellulose of the cotton stalk bark is subjected to grafting modification by maleic anhydride, carbonyl and carboxyl groups are added on the surface of the microcrystalline cellulose, and after the microcrystalline cellulose is dissolved and regenerated into fibers, the fiber surface forms a rough state with concave and convex parts; meanwhile, due to the addition of the graphene oxide, the surface of the fiber is in an irregular shape.
FIG. 2 is a Fourier infrared spectrum of a fiber. a is the modified cotton stalk bark microcrystalline cellulose/GO composite fiber of example 3, and b is modified cotton stalk bark microcrystalline cellulose. 1735cm in a-1Peak at (b), 1719cm in-1The peaks in (A) are all due to the stretching of C ═ O in COOH; and 1648cm in a-1Peak at (b) 1637cm-1The peaks are all assigned to C ═ C; 1159cm in a-1Peak at (b) 1162cm-1The peak is attributed to the ester bond formed after esterification of maleic anhydride and the bulk of cellulose. a. The existence of COOH, C ═ C and ester bonds in the b proves that maleic anhydride has successfully performed esterification reaction with the cotton stalk bark microcrystalline cellulose, and also shows that the modified structure of the cellulose is not damaged after the modified cotton stalk bark microcrystalline cellulose is spun into fibers.
FIG. 3 is a graph comparing the adsorption before and after fiber modification, with the modified cotton stalk bark microcrystalline cellulose/GO composite fiber being the fiber of example 3. Under the condition of room temperature, the pH value is 7, and the adsorption time is 150min, the adsorption capacity of the modified cotton stalk bark microcrystalline cellulose/GO composite fiber to copper ions is larger than that of the cotton stalk bark microcrystalline cellulose fiber to copper ions. The fiber surface is added with carboxyl and carbonyl groups through maleic anhydride modification, and the groups have strong adsorption function on cationic dyes such as methylene blue and the like; the added graphene oxide contains a large amount of-OH and-COOH on the surface, so that the graphene oxide can form a group with an anionic functional group and has an adsorption effect on copper ions with cationic properties.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Example 1
The preparation method of the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber comprises the following steps:
(1) modification: microcrystalline cellulose (prepared by the method of example 1 in patent application No. 201710847371.7) was treated with 15 wt% NaOH solution, magnetically stirred at 60 deg.C for 2 hours, repeatedly washed with deionized water, filtered and oven-dried at 80 deg.C for 3 hours. The alkali treated cotton stalk bark microcrystalline cellulose fiber was added to molten maleic anhydride in a mass ratio of 1:6, heated to 65 ℃ and continuously mechanically stirred for 2 hours. After stirring, dripping pyridine (accounting for 3 percent of the mass of the microcrystalline cellulose of the modified cotton stalk bark), continuously heating to 90 ℃, continuously stirring for 6 hours, repeatedly washing and filtering a product by deionized water, ethanol and acetone, and drying in an oven at 80 ℃ for 4 hours to obtain the microcrystalline cellulose of the modified cotton stalk bark;
(2) dissolving: putting the modified cotton stalk bark microcrystalline cellulose obtained in the step (1) into melted [ Bmim ] Cl ionic liquid, keeping the mass ratio of the modified cotton stalk bark microcrystalline cellulose to the ionic liquid at 1:10, and continuously stirring for 2 hours at the temperature of 80 ℃;
(3) compounding: uniformly dispersing a certain amount of graphene oxide with the specification of 0.5-4 nm into dimethyl sulfoxide by using an ultrasonic disperser, and adding a mixed solution of the graphene oxide and the dimethyl sulfoxide into the dissolved solution obtained in the step (2), wherein the mass of the graphene oxide is 1% of that of the microcrystalline cellulose of the modified cotton stalk bark, and the mass ratio of the dimethyl sulfoxide to the microcrystalline cellulose of the modified cotton stalk bark to the ionic liquid is 1: 1;
(4) defoaming: continuously stirring the modified cotton stalk bark microcrystalline cellulose composite spinning solution prepared in the step (3) for 3 hours, taking out the spinning solution after the spinning solution is stabilized, and performing vacuum defoaming for 30 minutes, wherein the standing time is 24 hours;
(5) spinning: and (3) putting the spinning solution obtained in the step (4) into a needle tube of a propelling device of a simple spinning machine, extruding the spinning solution by a propelling force provided by a motor, extruding the spinning solution from a 0.6(23G) type needle head, and forming in a coagulating bath, wherein the coagulating bath is deionized water, the drafting force is unchanged, and the coagulating time is 90 seconds.
(6) Air drying: and (5) placing the fiber spun in the step (5) in a fume hood for natural air drying.
(7) Adsorption: after drying the fiber obtained in (6), 0.1g of the dried fiber was put into a conical flask containing 100ml of a copper sulfate solution (copper ion concentration: 100mg/L), and the flask was put into a constant temperature shaking water tank to perform an adsorption test at a shaking speed of 150 r/min. Absorbing a certain amount of adsorption treatment solution through the filtration of a disposable filter head, diluting ten times, and detecting the concentration of copper ions in the solution by using an atomic absorption spectrophotometer.
The modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber is prepared by the method. The modified conjugate fiber obtained in the present example had an adsorption amount of copper ions of 17.77mg/g, a fiber linear density of 15.78tex and a breaking strength of 59.39 cN.
Example 2
The preparation method of the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber comprises the following steps:
(1) modification: microcrystalline cellulose (prepared by the method of example 1 in patent application No. 201710847371.7) was treated with 15 wt% NaOH solution, magnetically stirred at 60 deg.C for 2 hours, repeatedly washed with deionized water, filtered and oven-dried at 80 deg.C for 3 hours. The alkali treated cotton stalk bark microcrystalline cellulose fiber was added to molten maleic anhydride in a mass ratio of 1:6, heated to 65 ℃ and continuously mechanically stirred for 2 hours. After stirring, dripping pyridine (accounting for 3 percent of the mass of the microcrystalline cellulose of the cotton stalk bark), continuously heating to 90 ℃, continuously stirring for 6 hours, repeatedly washing and filtering a product by deionized water, ethanol and acetone, and drying in an oven at 80 ℃ for 4 hours to obtain the microcrystalline cellulose of the modified cotton stalk bark;
(2) dissolving: putting the modified cotton stalk bark microcrystalline cellulose obtained in the step (1) into melted [ Bmim ] Cl ionic liquid, keeping the mass ratio of the modified cotton stalk bark microcrystalline cellulose to the ionic liquid at 1:10, and continuously stirring for 2 hours at the temperature of 80 ℃;
(3) compounding: uniformly dispersing a certain amount of graphene oxide into dimethyl sulfoxide by using an ultrasonic disperser, and adding a mixed solution of the graphene oxide and the dimethyl sulfoxide into the dissolved solution obtained in the step (2), wherein the mass of the graphene oxide is 3% of that of the microcrystalline cellulose of the modified cotton stalk bark, and the mass ratio of the dimethyl sulfoxide to the microcrystalline cellulose of the modified cotton stalk bark to the ionic liquid is 1: 1;
(4) defoaming: continuously stirring the modified cotton stalk bark microcrystalline cellulose composite spinning solution prepared in the step (3) for 3 hours, taking out the spinning solution after the spinning solution is stabilized, and performing vacuum defoaming for 30 minutes, wherein the standing time is 24 hours;
(5) spinning: and (3) putting the spinning solution obtained in the step (4) into a needle tube of a propelling device of a simple spinning machine, extruding the spinning solution by a propelling force provided by a motor, extruding the spinning solution from a 0.6(23G) type needle head, and forming in a coagulating bath, wherein the coagulating bath is deionized water, the drafting force is unchanged, and the coagulating time is 90 seconds.
(6) Air drying: and (5) placing the fiber spun in the step (5) in a fume hood for natural air drying.
(7) Adsorption: after drying the fiber obtained in (6), 0.1g of the dried fiber was put into a conical flask containing 100ml of a copper sulfate solution (copper ion concentration: 100mg/L), and the flask was put into a constant temperature shaking water tank to perform an adsorption test at a shaking speed of 150 r/min. Absorbing a certain amount of adsorption treatment solution through the filtration of a disposable filter head, diluting ten times, and detecting the concentration of copper ions in the solution by using an atomic absorption spectrophotometer.
The modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber is prepared by the method. The modified conjugate fiber obtained in the present example had an adsorption amount of copper ions of 20.87mg/g, a fiber linear density of 13.05tex and a breaking strength of 39.42 cN.
Example 3
The preparation method of the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber comprises the following steps:
(1) modification: microcrystalline cellulose (prepared by the method of example 1 in patent application No. 201710847371.7) was treated with 15 wt% NaOH solution, magnetically stirred at 60 deg.C for 2 hours, repeatedly washed with deionized water, filtered and oven-dried at 80 deg.C for 3 hours. The alkali treated cotton stalk bark microcrystalline cellulose fiber was added to molten maleic anhydride in a mass ratio of 1:6, heated to 65 ℃ and continuously mechanically stirred for 2 hours. After stirring, dripping pyridine (accounting for 3 percent of the mass of the microcrystalline cellulose of the cotton stalk bark), continuously heating to 90 ℃, continuously stirring for 6 hours, repeatedly washing and filtering a product by deionized water, ethanol and acetone, and drying in an oven at 80 ℃ for 4 hours to obtain the microcrystalline cellulose of the modified cotton stalk bark;
(2) dissolving: putting the modified cotton stalk bark microcrystalline cellulose obtained in the step (1) into melted [ Bmim ] Cl ionic liquid, keeping the mass ratio of the modified cotton stalk bark microcrystalline cellulose to the ionic liquid at 1:10, and continuously stirring for 2 hours at the temperature of 80 ℃;
(3) compounding: uniformly dispersing a certain amount of graphene oxide into dimethyl sulfoxide by using an ultrasonic disperser, and adding a mixed solution of the graphene oxide and the dimethyl sulfoxide into the dissolved solution obtained in the step (2), wherein the mass of the graphene oxide is 5% of that of the microcrystalline cellulose of the modified cotton stalk bark, and the mass ratio of the dimethyl sulfoxide to the microcrystalline cellulose of the modified cotton stalk bark to the ionic liquid is 1: 1;
(4) defoaming: continuously stirring the modified cotton stalk bark microcrystalline cellulose composite spinning solution prepared in the step (3) for 3 hours, taking out the spinning solution after the spinning solution is stabilized, and performing vacuum defoaming for 30 minutes, wherein the standing time is 24 hours;
(5) spinning: and (3) putting the spinning solution obtained in the step (4) into a needle tube of a propelling device of a simple spinning machine, extruding the spinning solution by a propelling force provided by a motor, extruding the spinning solution from a 0.6(23G) type needle head, and forming in a coagulating bath, wherein the coagulating bath is deionized water, the drafting force is unchanged, and the coagulating time is 90 seconds.
(6) Air drying: and (5) placing the fiber spun in the step (5) in a fume hood for natural air drying.
(7) Adsorption: after drying the fiber obtained in (6), 0.1g of the dried fiber was put into a conical flask containing 100ml of a copper sulfate solution (copper ion concentration: 100mg/L), and the flask was put into a constant temperature shaking water tank to perform an adsorption test at a shaking speed of 150 r/min. Absorbing a certain amount of adsorption treatment solution through the filtration of a disposable filter head, diluting ten times, and detecting the concentration of copper ions in the solution by using an atomic absorption spectrophotometer.
The modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber is prepared by the method. The modified conjugate fiber obtained in the present example had an adsorption amount of copper ions of 24.38mg/g, a fiber linear density of 18.02tex and a breaking strength of 28.25 cN.
Claims (8)
1. The method for preparing the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber is characterized by comprising the following steps of:
(1) modification: placing the microcrystalline cellulose of the cotton stalk bark in 10-20 wt% of alkaline solution, stirring for 1-3 hours at 50-70 ℃ for alkali treatment, washing a product with deionized water, filtering and drying to obtain the microcrystalline cellulose of the cotton stalk bark after the alkali treatment; adding the cotton stalk bark microcrystalline cellulose subjected to alkali treatment into molten maleic anhydride, stirring for 2 hours at 65 ℃, then dripping pyridine, heating to 90 ℃, continuing stirring for 6 hours, washing a product with deionized water, ethanol and acetone, filtering, and drying to obtain modified cotton stalk bark microcrystalline cellulose;
wherein the mass ratio of the microcrystalline cellulose of the cotton stalk bark treated by alkali to the maleic anhydride is 1: 6; the pyridine accounts for 2-4% of the mass of the microcrystalline cellulose of the cotton stalk bark treated by the alkali;
(2) dissolving: putting the modified cotton stalk bark microcrystalline cellulose obtained in the step (1) into a molten [ Bmim ] Cl ionic liquid, and dissolving for 2-3 hours under a heating condition of 70-90 ℃ to obtain a dissolved solution;
wherein the mass ratio of the microcrystalline cellulose of the modified cotton stalk bark to the ionic liquid is 1: 8-1: 15;
(3) compounding: dispersing graphene oxide into dimethyl sulfoxide by using an ultrasonic disperser to obtain a mixed solution of graphene oxide and dimethyl sulfoxide; adding the mixed solution of graphene oxide and dimethyl sulfoxide into the dissolved solution obtained in the step (2) to obtain a modified cotton stalk bark microcrystalline cellulose composite spinning solution;
wherein the particle size of the graphene oxide is 0.5-4 nm; the mass of the graphene oxide is 1-5% of that of the microcrystalline cellulose of the modified cotton stalk bark, and the mass of the dimethyl sulfoxide is 75-175% of the total mass of the microcrystalline cellulose of the modified cotton stalk bark and the ionic liquid;
(4) defoaming: stirring the modified cotton stalk bark microcrystalline cellulose composite spinning solution obtained in the step (3) for 2-3 hours, then carrying out vacuum defoaming, and standing;
(5) spinning: carrying out wet spinning on the modified cotton stalk bark microcrystalline cellulose composite spinning solution treated in the step (4) to obtain modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fibers;
wherein the coagulating bath is deionized water.
2. The method for preparing the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber according to claim 1, wherein in the step (5), the setting time is 30-150 seconds.
3. The method for preparing the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber according to claim 1, wherein in the step (1), the alkaline solution is NaOH solution, potassium hydroxide solution or calcium hydroxide solution.
4. The method for preparing the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber according to claim 1, wherein in the step (1), the drying conditions are as follows: the temperature is 70-90 ℃, and the time is 3-4 hours.
5. The method for preparing the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber according to claim 1, wherein in the step (4), the vacuum defoaming time is 20-40 minutes, and the standing time is 12-48 hours.
6. The method for preparing the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber according to claim 1, further comprising: (6) air drying: and (5) air-drying the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber obtained in the step (5).
7. The method for preparing the modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber according to claim 1, wherein in the step (1), the temperature of the alkali treatment is 60 ℃ and the time is 2 hours.
8. The modified cotton stalk bark microcrystalline cellulose/graphene oxide composite fiber prepared by the method of any one of claims 1 to 7.
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