CN114108314B - Preparation method and application of fluorescent viscose fiber - Google Patents
Preparation method and application of fluorescent viscose fiber Download PDFInfo
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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Abstract
The invention discloses a preparation method and application of fluorescent viscose fiber. The preparation method disclosed by the invention comprises the following steps: s1, preparing a rich amine quantum dot by using citric acid as a carbon source and branched polyethyleneimine as an amination reagent through a hydrothermal method; s2, carboxymethyl modification is carried out on the viscose fiber to obtain carboxymethyl modified viscose fiber; s3, taking the carboxymethyl modified viscose fiber obtained in the S2 as a matrix, taking the rich amine quantum dot obtained in the S1 as a functionalizing agent, and preparing the carbon quantum dot functionalized fluorescent viscose fiber by a hydrothermal method. The fluorescent viscose fiber obtained by the preparation method disclosed by the invention has wide application prospect in the aspect of preparing the circulating renewable adsorption material.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation method and application of fluorescent viscose fiber.
Background
The viscose fiber comprises a plurality of viscose fibers such as common viscose fiber, high wet modulus viscose fiber, high-strength viscose fiber and the like. The common viscose fiber is also called rayon, is the most common viscose fiber and is also the most widely used viscose fiber. The viscose fiber with high wet modulus has the advantages of high polymerization degree, high strength, high wet modulus, fatigue resistance and the like. The viscose fiber can prevent static electricity, resist ultraviolet, has better air permeability and hygroscopicity, is suitable for human skin, is mainly used for blending with cotton, wool and other textiles, and is a high-quality clothing material.
On the macromolecular chain of viscose fiber, every glucose unit has three active-OH groups, and these groups are respectively positioned on carbon atoms of second position, third position and sixth position, and because of different space positions and different chemical reactivity, three hydroxyl groups can be undergone a series of reactions, for example, the hydroxyl groups can be changed into carboxyl groups by means of oxidation, and etherification reaction and various graft copolymerization reactions.
In the crystallization area of viscose fiber, the number of hydrogen bonds is large due to molecular accumulation, the reagent is difficult to enter, the accessibility is low, and the reaction performance is poor; in the amorphous region, the molecules are loosely stacked, the number of hydrogen bonds is small, the reactant is easy to permeate, the accessibility is high, and the reaction performance is good.
The cellulose derivative can be obtained by chemically modifying the hydroxyl groups on the activated viscose fiber and introducing new functional groups onto cellulose molecules by selecting proper modifying reagents, thus imparting new physical and chemical properties to cellulose and obtaining cellulose derivatives with remarkable differences.
The method for performing physicochemical modification on the viscose fiber or compounding the viscose fiber with other materials is a main method for the performance of the functionalized viscose fiber at present. With the deep research, the development of a novel functionalized modified viscose fiber product can solve the practical problems in production and life, such as spectral antibacterial, dye and formaldehyde pollutant adsorption and degradation, flame retardant property, dyeing and fixation performance, and is a future development trend.
Disclosure of Invention
Therefore, the invention provides a preparation method and application of fluorescent viscose fiber. According to the invention, the carboxymethylation modified viscose fiber is subjected to composite modification by using the rich amine carbon quantum dots, so that the prepared fluorescent viscose fiber not only can realize selective adsorption and release of guest molecules under different pH conditions, but also can adsorb pollutants such as formaldehyde, carbon dioxide and bacteria in the air, and meanwhile, can realize sterilization and catalytic decomposition of the pollutants, has fluorescent property, is convenient to evaluate and track, and has wide application prospects in the fields of administration materials, catalysis, sewage treatment, air purification, wound medical materials and the like.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
in a first aspect, an embodiment of the present invention provides a method for preparing a fluorescent viscose fiber, including the following steps:
s1, preparing a rich amine quantum dot by using citric acid as a carbon source and branched polyethyleneimine as an amination reagent through a hydrothermal method;
s2, carboxymethyl modification is carried out on the viscose fiber to obtain carboxymethyl modified viscose fiber;
s3, taking the carboxymethyl modified viscose fiber obtained in the S2 as a matrix, taking the rich amine quantum dot obtained in the S1 as a functionalizing agent, and preparing the carbon quantum dot functionalized fluorescent viscose fiber by a hydrothermal method.
Preferably, the specific operation of S1 comprises the following procedure:
taking branched polyethyleneimine as an amination reagent and citric acid as a carbon source, mixing the branched polyethyleneimine and the citric acid according to a mass ratio of 2:1-3:1 to obtain a mixed material, mixing the mixed material and water according to a mass ratio of 1:5-1:6, and then reacting for 6-8 hours at 160-180 ℃; and cooling, filtering, washing and drying after the reaction is finished to obtain the rich amine quantum dot.
Further, the specific mode of drying is vacuum freeze drying.
Preferably, the specific operation of S2 includes the following procedure:
mixing the viscose fiber fibril dried to constant weight with 0.5mol/L NaOH aqueous solution according to a solid-to-liquid ratio of 0.02g/mL, immersing the viscose fiber fibril in the 0.5mol/L NaOH aqueous solution, and stirring for 0.5h at normal temperature to obtain a solution A; stirring chloroacetic acid and 1mol/L sodium hydroxide aqueous solution uniformly according to a solid-to-liquid ratio of 1-1.1 g/mL to obtain a solution B, adding the solution B into the solution A, stirring to uniformly mix the solutions, sealing, and heating in a water bath at 70 ℃ for reaction for 4-5 h; and cooling, filtering, washing and drying after the reaction is finished to obtain the carboxymethyl modified viscose fiber.
Preferably, the specific operation of S3 includes the following procedure:
after the amine-rich quantum dots prepared in the step S1 are cooled to room temperature, the amine-rich quantum dots and the carboxymethyl modified viscose fibers prepared in the step S2 are mixed according to the mass ratio of 1:10, then adding water until the carboxymethyl modified viscose fiber is completely immersed in water, then sealing a reaction container, and reacting for 6-8 hours at 120-140 ℃; filtering out the obtained fiber material after the reaction is finished, washing the fiber material with hot water at 60 ℃ for several times until the pH value is neutral, and drying the washed fiber material to obtain the fluorescent viscose fiber.
Further, the drying mode of the washed fiber material is specifically as follows: drying at 60deg.C under vacuum overnight.
In a second aspect, an embodiment of the present invention provides a fluorescent viscose fiber, which is obtained by the above preparation method.
In a third aspect, the present invention provides an application of the fluorescent viscose fiber in preparing a recyclable adsorbing material.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) Carbon quantum dots (CDs) have attracted extensive research interest by researchers in the last decade as a carbon-based zero-dimensional carbon material. It has the characteristics of unique luminescence property, low toxicity, biocompatibility, low cost, simple synthetic route and the like. These properties make it widely applicable in optoelectronic devices, biomarkers and sensors. In addition to the above application fields, CD has been developed in recent years as an important carbon nanomaterial for macromolecular functionalization. According to the invention, the modified viscose fiber is prepared by compounding the amine-rich carbon quantum dots and the carboxymethylation modified viscose fiber, so that the prepared modified viscose fiber has fluorescent property and contains micropores with nanometer size. The fluorescent viscose fiber obtained by the preparation method provided by the invention has the advantages that the surface is rich in amino carbon quantum dots and nanometer-sized pore diameters, and meanwhile, the fluorescent viscose fiber has a skeleton of fiber macromolecules, so that the fluorescent viscose fiber can selectively adsorb and release guest molecules under different pH conditions, can adsorb pollutants such as formaldehyde, carbon dioxide and bacteria in the air, can sterilize and catalyze the pollutants, has fluorescent property, is convenient to evaluate and track, and has wide application prospects in the fields of administration materials, catalysis, sewage treatment, air purification, wound medical materials and the like.
(2) The glucose ring of the viscose cellulose macromolecule has three hydroxyl groups with different activities, and the hydrogen atoms of the hydroxyl groups are easy to form a large number of intermolecular and intramolecular hydrogen bonds with the oxygen atoms of the other hydroxyl groups. The intermolecular force is large, and the molecules are closely arranged to form a crystal structure. The hydroxyl groups are blocked in the crystals, and the reaction solution is difficult to enter, so that cellulose molecules are difficult to react. Therefore, the invention uses sodium hydroxide solution with specific concentration to soak the viscose fiber to make it swell, the intermolecular hydrogen bond of the treated viscose fiber is destroyed, the crystallization area is partially dissolved, the amorphous area is further expanded, more active free hydroxyl groups are exposed, and the chemical reaction is facilitated. After the alkaline leaching pretreatment, the surface of the viscose fiber becomes rough, and the accessibility is obviously improved.
(3) In order to improve the adsorption performance of the viscose, chloroacetic acid is used as a carboxymethyl modifying reagent, so that the chloroacetic acid reacts with the viscose subjected to alkaline leaching pretreatment in a nucleophilic substitution manner, and carboxymethyl modification is carried out, so that the anion viscose is prepared; the carbon quantum dots are nano-scale particles, the specific surface area of the carbon quantum dots is very large, and the carbon quantum dots contain a large number of amine groups and can perform amidation reaction with carboxyl groups of carboxymethyl modified viscose fibers, so that the carbon quantum dots are grafted on the surfaces of the viscose fibers and are combined into the viscose fibers loaded by the carbon quantum dots, and the absorption and release performances of the viscose fibers are further improved.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings that are required to be used in the description of the embodiments of the present invention will be briefly described below. It will be apparent to those skilled in the art that the drawings in the following description are merely exemplary and that other drawings may be derived from the drawings provided without the inventive effort to those skilled in the art.
The following drawings are provided to enable those skilled in the art to understand and read the disclosure, and are not intended to limit the applicable scope of the present invention, and any modifications may be made without affecting the efficacy or reach of the invention.
FIG. 1 is a schematic diagram of the synthetic process of the fluorescent viscose fiber provided in example 1 of the present application;
FIG. 2 is a graph showing the time-dependent adsorption amount of methyl orange by the fluorescent viscose fiber according to example 1 of the present application;
FIG. 3 is a schematic diagram of the selective adsorption performance and the cyclic adsorption performance of the fluorescent viscose fiber according to example 1 of the present application;
FIG. 4 is a graph showing the effect of fluorescent properties of the fluorescent viscose fiber according to example 1 of the present application; fig. 4- (a) is a fluorescent performance of the fluorescent viscose fiber provided in embodiment 1 of the present application under the bright environment, the dark environment and the ultraviolet lamp irradiation, and fig. 4- (b) is a fluorescent performance of the fluorescent viscose fiber provided in embodiment 1 of the present application and a fluorescent performance of the common viscose fiber under the dark environment and the ultraviolet lamp irradiation, wherein the common viscose fiber is located on the left side, and the fluorescent viscose fiber provided in embodiment 1 of the present application is located on the right side.
Fig. 5 is a graph of the cyclic adsorption effect of fluorescent viscose fibers provided in example 1 of the present application on methyl orange; wherein, the effect under the ultraviolet lamp irradiation in the dark environment of the behavior of top, the effect under the bright environment of behavior of below.
Fig. 6 is a graph showing the effect of fluorescence property under an ultraviolet lamp of the amine-rich quantum dot prepared in example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, the terms "comprises," "comprising," and any variations thereof, if any, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements but may include other steps or elements not expressly listed but inherent to such process, method, article, or apparatus or steps or elements added based on further optimization of the inventive concept.
Example 1
The embodiment provides a preparation method of fluorescent viscose fiber, which takes Citric Acid (CA) as a carbon source, branched polyethyleneimine (HPEI) as an amination reagent, and prepares the carbon quantum dots of rich amine by adopting a hydrothermal method under the condition of 180 ℃; and then taking the viscose fiber as a matrix, and preparing the carbon quantum dot functionalized viscose fiber composite material (VF-g-CDs) under the hydrothermal condition of 120 ℃ by using a functionalizing agent of the rich amine, namely the fluorescent viscose fiber.
The preparation method can be roughly divided into three steps: firstly, preparing amine-rich carbon quantum dots; secondly, preparing anion viscose fiber; and thirdly, preparing the viscose fiber (namely the fluorescent fiber) loaded by the carbon quantum dots.
(1) Preparation principle of anion viscose fiber
The molecular chain of the viscose fiber has a plurality of reactive hydroxyl groups which are relatively easy to react, thus providing a relatively good reaction condition for modifying the viscose fiber. However, a large number of hydrogen bonds including intermolecular hydrogen bonds and intramolecular hydrogen bonds are formed between two hydroxyl groups, and the hydroxyl groups are aggregated into a crystalline fibril structure in a solid state, so that most of the hydroxyl groups are sealed in a crystal region, pretreatment of reaction is needed to be carried out on viscose fibril in advance, the viscose fibril is soaked in sodium hydroxide, swelling is carried out on the viscose fiber, the hydroxyl groups react with the sodium hydroxide bonds to produce an active center with a certain structure, then chloroacetic acid is used for treating the viscose fiber under an alkaline condition, so that the chloroacetic acid reacts with the viscose fiber again to carry out nucleophilic substitution reaction, and carboxymethyl modification is carried out, so that the anionic viscose fiber is prepared.
(2) Principle of synthesis of carbon quantum dots
And (3) taking branched polyethyleneimine (HPEI) as an amination reagent, and carrying out high-temperature pyrolysis on the polyethyleneimine by taking citric acid as a carbon source, so as to obtain the hydrophilic fluorescent carbon quantum dot.
(3) Synthesis principle of viscose fiber loaded by carbon quantum dots
The carbon quantum dots are nano-scale particles, the specific surface area of the carbon quantum dots is very large, and the carbon quantum dots contain a large number of amine groups and can perform amidation reaction with carboxyl groups of anion viscose fibers, so that the carbon quantum dots are grafted on the surfaces of the viscose fibers and are combined into a carbon quantum dot functionalized viscose fiber composite material (VF-g-CDs), namely the fluorescent viscose fibers.
The more detailed steps are as follows:
(1) And (3) synthesizing carbon quantum dot CD: the branched polyethyleneimine (HPEI) is used as an amination reagent, and citric acid is used as a carbon source, so that the carbon quantum dot CD is synthesized. The method comprises the following specific steps: HPEI 1.50g and 0.50g CA were mixed with 12 mL deionized water to form a clear solution, which was then transferred to a 25mL stainless steel autoclave with a corrosion resistant liner and reacted at 180℃for 6h. Cooling, filtering, washing with deionized water, and vacuum freeze-drying to obtain the amine-rich carbon quantum dots (CDs).
(2) Preparing carboxymethyl viscose: 3.0g of viscose fiber fibril dried to constant weight is weighed, put into a 250mL beaker A, added with 150mL of prepared 0.5mol/L sodium hydroxide aqueous solution, immersed in the fibril, and stirred for 0.5h at normal temperature. 160.0g of chloroacetic acid powder is weighed, 150mL of 1mol/L sodium hydroxide aqueous solution is added and stirred until the powder is completely dissolved, the solution is added into a beaker A after 0.5h, the solution is stirred and uniformly mixed, the mixture is sealed, the water bath heating is carried out to 70 ℃, and the water bath heating is carried out for 5 hours. And after the reaction is finished, cooling, filtering, washing and drying to obtain the carboxymethyl viscose fiber.
(3) Preparation of fluorescent viscose (VF-g-CDs): after the amine-rich carbon quantum dots obtained in the first step are cooled to room temperature, 0.04g of amine-rich carbon quantum dots and 0.40g of carboxymethyl viscose fiber are taken and put into an autoclave, and then 5 milliliters of deionized water is added to ensure that the fiber is immersed in the liquid. The autoclave was sealed and reacted at 140℃for 8 hours. After cooling, the fibers were filtered off and washed several times with hot water (-60 ℃) to neutrality. And drying the washed fiber overnight at 60 ℃ under vacuum to obtain the fluorescent viscose fiber composite material, namely the fluorescent viscose fiber.
The fluorescent viscose fiber prepared by the method provided by the embodiment 1 of the application has the advantages that the surface is rich in amino carbon quantum dots and the aperture with nanometer size, and meanwhile, the fluorescent viscose fiber has a skeleton of fiber macromolecules, so that not only can the selective adsorption and release of guest molecules be realized under different pH conditions, but also pollutants such as formaldehyde, carbon dioxide and bacteria in the air can be adsorbed, meanwhile, the sterilization and catalytic decomposition of the pollutants are realized, the fluorescent viscose fiber has fluorescent property, is convenient to evaluate and track, and has wide application prospects in the fields of administration materials, catalysis, sewage treatment, air purification, wound medical materials and the like.
Fig. 1 is a synthetic process route diagram of a fluorescent viscose fiber (VF-g-CDs) provided in this embodiment, where HPEI is branched polyethylenimine, CA is citric acid, and CD is a prepared rich amine carbon quantum dot.
Fig. 1 clearly shows the overall flow of the fluorescent viscose fiber prepared in this example, namely: preparation of rich amine carbon quantum dots, preparation of anion viscose fibers, and preparation of viscose fibers loaded by the carbon quantum dots (namely the fluorescent fibers).
Example 2
The present embodiment provides a method for preparing fluorescent viscose fiber, which has the same detailed operation steps as those of embodiment 1, except that:
in the step (1), the dosage of HPEI is 1.0g, the dosage of CA is 0.5g, the dosage of deionized water is 7.5g, and the reaction temperature and the reaction time are 160 ℃ and 8 hours respectively;
in the step (2), the hydrothermal reaction time is 4 hours;
in the step (3), the reaction temperature is 120 ℃ and the reaction time is 6 hours.
Example 3
The present embodiment provides a method for preparing fluorescent viscose fiber, which has the same detailed operation steps as those of embodiment 1, except that:
in the step (1), the dosage of HPEI is 1.25g, the dosage of CA is 0.5g, the dosage of deionized water is 6.875g, and the reaction temperature and the reaction time are 170 ℃ and 7 hours respectively;
in the step (2), the hydrothermal reaction time is 4.5 hours;
in the step (3), the reaction temperature is 130 ℃ and the reaction time is 7h.
Next, a series of experiments were performed on the fluorescent viscose fiber provided in example 1 to illustrate the advantageous effects of the present invention. The same experiment was performed on the fluorescent fibers provided in example 2 and example 3, and as a result, the technical effects to be achieved by the present invention could be achieved in the same manner as in example 1 as a whole.
A series of mixed solutions of methyl orange (anionic) and methylene blue (cationic) with different concentrations were prepared, adjusted to the required pH, and 20mg of fluorescent viscose was placed in 20mL of dye aqueous solution, and gently stirred at 25 ℃. The absorbance of the dye solution is tracked and detected by using a UV-Vis spectrometer, and then the dye concentration in the solution at different times is monitored by using the data, so that the adsorption capacity of the composite material is calculated, and the adsorption performance of the fluorescent viscose fiber is evaluated. A graph of the adsorption amount of methyl orange by the fluorescent viscose fiber provided in example 1 over time is shown in fig. 2.
According to the fig. 2, the fluorescent viscose fiber provided in example 1 of the present application adsorbs methyl orange, the adsorption amount is gradually increased with the increase of adsorption time, the adsorption efficiency is high just at the beginning, the adsorption efficiency is slowed down after 100min, the adsorption amount reaches saturation at 120 min, and the saturation amount is 22.02mg/g.
20mg of fluorescent viscose fiber pretreated by pH 5 solution is soaked in 20mL of 0.2mM Methyl Orange (MO) water solution, stirred for 2h at 25 ℃, taken out, put into another beaker with 20mL of buffer solution with a certain pH, and gently stirred. And tracking and monitoring the desorption process by adopting an ultraviolet-visible spectrometer, and evaluating the release performance of the fluorescent viscose fiber on dye guest molecules. Experimental data show that the release efficiency can reach more than 85%.
Fluorescent viscose (20 mg, pH 5) was added to an aqueous MO solution (100 mL,0.02 mM), stirred for 2 hours, and then removed, and the residual amount of MO in the solution was recorded by an ultraviolet-visible spectrometer. The fiber was then placed in 10mL fresh KHCO 3 /K 2 CO 3 The solution was stirred in buffer (pH 11.5,0.02M) for 0.5h, the MO concentration of the solution was recorded, the fibers were filtered off and dried in vacuo. The entire adsorption-desorption cycle was performed 7 times; the resolution efficiency can reach 89.94%, 86.3%, 85.2%, 84.31%, 83.67%, 85.58% and 82.4% respectively.
Through the above experiments, the fluorescent viscose fiber provided in embodiment 1 of the present application has cyclic adsorption performance and selective adsorption performance. Fig. 3 is a schematic diagram of the selective adsorption performance and the cyclic adsorption performance of the fluorescent viscose fiber (VF-g-CDs) provided in this embodiment, where MO refers to a typical anionic dye methyl orange, and MB refers to a typical cationic dye methylene blue.
As can be seen from fig. 3, first, the fluorescent viscose fiber provided in this embodiment has selective adsorption performance, namely, selective adsorption of anionic dye (methyl orange), but does not have adsorption effect on cationic dye (methylene blue), because amine groups of amine-rich quantum dots on the surface of the fluorescent viscose fiber exist in the form of quaternary ammonium groups under acidic condition, the adsorption capability on the anionic dye methyl orange is enhanced, and rejection effect on the cationic dye methylene blue is achieved; secondly, the fluorescent viscose fiber provided by the embodiment can adsorb anionic dye in an acidic environment, and can desorb in an alkaline environment, so that the cyclic adsorption performance is reflected, and the principle is that under the acidic condition, quaternary ammonium groups have stronger electrostatic attraction to the anionic dye methyl orange, so that the adsorption capacity is stronger; under alkaline conditions, the quaternary ammonium group is converted into an amino group, and the electrostatic attraction is weak, so that the release of the anionic dye methyl orange is realized.
FIG. 4 is a graph showing the effect of fluorescent properties of the fluorescent viscose fiber according to example 1 of the present application; fig. 4- (a) is a fluorescent performance of the fluorescent viscose fiber provided in embodiment 1 of the present application under normal light, a dark environment and an ultraviolet lamp, and fig. 4- (b) is a fluorescent performance of the fluorescent viscose fiber provided in embodiment 1 of the present application and a common viscose fiber under the dark environment and the ultraviolet lamp.
As can be seen from fig. 4, the fluorescent viscose fiber provided in this embodiment has fluorescent characteristics that are not possessed by the common viscose fiber.
The carbon quantum dot-loaded fluorescent viscose fiber provided in example 1 has a fluorescent effect, shows blue color under an ultraviolet lamp, shows the same color as the carbon quantum dot solution, and has no obvious change in fluorescence after washing. The higher the fluorescence intensity of the carbon quantum dot solution, the higher the fluorescence effect of the viscose fiber.
Fig. 5 is a graph of the cyclic adsorption effect of fluorescent viscose fibers provided in example 1 of the present application on methyl orange; wherein, the effect of the behavior in dark environment and under the irradiation of ultraviolet lamp is located above, and the effect of the behavior in bright environment is located below. As can be seen from fig. 5, the fluorescence of the fibers did not fade during cyclic adsorption, and after adsorption, no fluorescence was seen, and after desorption of the dried fibers, the fluorescence was restored. The adsorption process of the fluorescent viscose fiber can be tracked and analyzed through fluorescent detection, and the fluorescent viscose fiber has wide application prospect as a circulating renewable adsorption material.
Fig. 6 is a graph showing the effect of fluorescence properties of the amine-rich quantum dots prepared in example 1 under an ultraviolet lamp. As can be seen from fig. 6, the amine-rich quantum dots showed very remarkable fluorescence characteristics under the uv lamp.
The technical features of the above embodiments may be arbitrarily combined, and for brevity, all of the possible combinations of the technical features of the above embodiments are not described; these examples, which are not explicitly written, should also be considered as being within the scope of the present description.
The invention has been described above with particularity and detail in connection with general description and specific embodiments. It should be noted that it is obvious that several variations and modifications can be made to this specific embodiment without departing from the spirit of the present invention, which are all within the scope of protection of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (7)
1. The preparation method of the fluorescent viscose fiber is characterized by comprising the following steps of:
s1, preparing a rich amine quantum dot by using citric acid as a carbon source and branched polyethyleneimine as an amination reagent through a hydrothermal method;
s2, carboxymethyl modification is carried out on the viscose fiber to obtain carboxymethyl modified viscose fiber;
s3, preparing the carbon quantum dot functionalized fluorescent viscose fiber by using the carboxymethyl modified viscose fiber obtained in the S2 as a matrix, and the rich amine quantum dot obtained in the S1 as a functionalizing agent through a hydrothermal method;
the specific operation of S3 comprises the following steps:
after the amine-rich quantum dots prepared in the step S1 are cooled to room temperature, the amine-rich quantum dots and the carboxymethyl modified viscose fibers prepared in the step S2 are mixed according to the mass ratio of 1:10, then adding water until the carboxymethyl modified viscose fiber is completely immersed in water, then sealing a reaction container, and reacting for 6-8 hours at 120-140 ℃; filtering out the obtained fiber material after the reaction is finished, washing the fiber material with hot water at 60 ℃ for several times until the pH value is neutral, and drying the washed fiber material to obtain the fluorescent viscose fiber.
2. The preparation method of the fluorescent viscose fiber according to claim 1, wherein the specific operation of S1 comprises the following steps:
taking branched polyethyleneimine as an amination reagent and citric acid as a carbon source, mixing the branched polyethyleneimine and the citric acid according to a mass ratio of 2:1-3:1 to obtain a mixed material, mixing the mixed material with water according to a mass ratio of 1:5-1:6, and then reacting for 6-8 hours at 160-180 ℃; and cooling, filtering, washing and drying after the reaction is finished to obtain the amine-rich quantum dot.
3. The method for preparing fluorescent viscose fiber according to claim 2, wherein the specific drying mode is vacuum freeze drying.
4. The preparation method of the fluorescent viscose fiber according to claim 1, wherein the specific operation of S2 comprises the following steps:
mixing the viscose fiber fibril dried to constant weight with 0.5mol/L NaOH aqueous solution according to a solid-to-liquid ratio of 0.02g/mL, immersing the viscose fiber fibril in the 0.5mol/L NaOH aqueous solution, and stirring for 0.5h at normal temperature to obtain a solution A; stirring chloroacetic acid and 1mol/L sodium hydroxide aqueous solution uniformly according to a solid-to-liquid ratio of 1-1.1 g/mL to obtain solution B, adding the solution B into the solution A, stirring to uniformly mix the solutions, sealing, and heating in a water bath at 70 ℃ for reaction for 4-5 h; and cooling, filtering, washing and drying after the reaction is finished to obtain the carboxymethyl modified viscose fiber.
5. The method for preparing fluorescent viscose fiber according to claim 1, wherein the drying mode of the washed fiber material is specifically as follows: drying at 60deg.C under vacuum overnight.
6. A fluorescent viscose fiber characterized by being obtained by the preparation method of claim 1.
7. Use of the fluorescent viscose fiber according to claim 6 for preparing a cyclic renewable adsorption material.
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