Modified high-performance fiber material and preparation method thereof

Abstract

The invention provides a modified high-performance fiber material and a preparation method thereof, and belongs to the technical field of adsorption materials, and the preparation method comprises the following steps: mixing indoleacetic acid, an acetic acid aqueous solution, N-(3-dimethylaminopropyl)-N '-ethylcarbodiimide hydrochloride, 4-dimethylaminopyridine and CNCs for reaction, washing and drying to obtain indole modified CNCs; the preparation method comprises the following steps: adding gamma-CD-MOFs into an ethanol solution for ultrasonic treatment, adding citral and cinnamyl aldehyde, mixing and stirring, centrifuging to take precipitate, washing and drying to obtain an MOF (at) citral / cinnamyl aldehyde composite material; mixing and stirring the indole modified CNCs and the MOF citral / cinnamyl aldehyde composite material, standing, centrifuging, taking precipitate, washing and drying to obtain the modified high-performance fiber material. The composite material can be used as an adsorption material for adsorbing and removing pollutants and has antibacterial and bacteriostatic characteristics.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adsorption materials, and particularly relates to a modified high-performance fiber material and a preparation method thereof. BACKGROUND

[0002] Textile industry, metal processing, electronics and other industries result in a large number of synthetic dyes, heavy metal ions and bacteria and fungi in water, and their allothogenicity, high chemical stability and reactivity make it difficult for traditional wastewater treatment systems to effectively remove them completely. Therefore, researchers have explored many advanced technologies for treating contaminated wastewater, such as microbial degradation under aerobic and anaerobic conditions, advanced oxidation technology and reverse osmosis method, electrochemical method, biological and enzyme treatment, membrane filtration and adsorption technology based on adsorption materials. Among them, the use of adsorption materials to remove pollutants is a relatively simple and energy-saving way. Unlike some other methods, adsorption can be applied to the removal process of inorganic and organic pollutants in almost the minimum space and time; the properties of the adsorption material are also very important for the adsorption of specific pollutants from aqueous solution; in addition, due to the change of charge, a single adsorption material cannot effectively remove different types of pollutants.

[0003] Natural biomass fiber materials not only have abundant sources and low prices, but also have the characteristics of being renewable, biodegradable and environmentally friendly, which meet the development direction of green materials. Among them, cellulose is the most abundant macromolecular compound in nature, which often exists in plant resources such as wood, cotton and crop straw. Cellulose nanocrystals (CNCs) can be obtained by mechanical, chemical or enzymatic treatment, which have the potential to be used as adsorption materials due to their characteristics of being renewable, biodegradable, large specific surface area and excellent mechanical properties; however, many cellulose-based adsorption materials have low adsorption capacity for pollutants and poor adsorption capacity for complex component pollutants.

[0004] The patent application file with the publication number CN109529785A discloses a preparation method of cellulose nanocrystal / zinc oxide composite material with the functions of adjusting morphology and super-fast absorbing cationic dyes. The method uses citric acid / hydrochloric acid mixed acid to treat bamboo or bamboo products to obtain cellulose nanocrystals, which are used as a template regulator and dispersant for nano-zinc oxide to prepare cellulose nanocrystal / zinc oxide composite material. The composite material has antibacterial property and the performance of absorbing cationic dyes, but a large amount of acid is used in the preparation of cellulose nanocrystals; in addition, although zinc oxide has excellent antibacterial property, its biological safety in water environment has been controversial as a metal oxide nanoparticle, and the release of zinc ions may cause secondary pollution.

[0005] Therefore, it is necessary to provide a modified high-performance fiber material and a preparation method thereof to solve the problems existing in the prior art. SUMMARY

[0006] Therefore, the application provides a modified high-performance fiber material and a preparation method thereof, which can be used as an adsorption material for adsorbing and removing pollutants and has antibacterial properties.

[0007] To achieve the above-mentioned purpose, the application provides a preparation method of a modified high-performance fiber material, which comprises the following steps: S1, mixing indole acetic acid, an aqueous acetic acid solution, N-(3-dimethylaminopropyl)-N'-ethyl carbodiimide hydrochloride, 4-dimethylaminopyridine and CNCs for reaction, and washing and drying to obtain indole-modified CNCs; S2, adding γ-CD-MOFs to an ethanol solution for ultrasonic treatment, adding citral and cinnamaldehyde for mixing and stirring, centrifuging to obtain a precipitate, and washing and drying to obtain a MOF@citral / cinnamaldehyde composite material; S3, mixing indole-modified CNCs and the MOF@citral / cinnamaldehyde composite material for stirring and standing, centrifuging to obtain a precipitate, and washing and drying to obtain a modified high-performance fiber material.

[0008] In the application, indole acetic acid is used as a modifier, and through the help of N-(3-dimethylaminopropyl)-N'-ethyl carbodiimide hydrochloride and 4-dimethylaminopyridine, grafting of indole acetic acid and CNCs is performed to obtain indole-modified CNCs. The introduction of an indole ring endows the material with certain antibacterial effect, and the mechanism is that the indole ring is combined with the hydrophobic region of the cell membrane and destroys the integrity of the membrane, the aromatic structure of the indole ring can be inserted into the hydrophobic lipid region of the cell membrane, thereby affecting the stability of the membrane and achieving the antibacterial effect; the indole modification also increases the content of the negative charge (negative Zeta potential) on the surface of the CNCs, which also enhances the complexation of the CNCs with heavy metal ions and promotes the adsorption capacity of the CNCs for metal ions; at the same time, the modification of the indole acetic acid introduces the aromatic π-π stacking effect on the surface of the CNCs, which greatly improves the adsorption capacity of the CNCs for aromatic compounds and azo dyes, and has a significant advantage in dye removal and other applications; in addition, the indole ring as an aromatic structure with strong ultraviolet absorption performance effectively improves the ultraviolet resistance of the modified CNCs, slows down the photodegradation process under ultraviolet radiation, and prolongs the service life and stability of the material.

[0009] The application utilizes the hydrophobic cavity of γ-cyclodextrin (γ-CD) in γ-CD-MOFs to efficiently load natural antibacterial materials (citral, cinnamaldehyde) through molecular inclusion, and significantly reduces the volatilization and degradation thereof; and utilizes the structural stability, large specific surface area and internal porous network of γ-CD-MOFs to provide abundant adsorption sites for small molecule pollutants. The dual action makes the MOF@citral / cinnamaldehyde composite material not only have good physical screening and pore adsorption performance, but also can realize high loading of antibacterial materials and enhance the sustained antibacterial capacity of the material.

[0010] In the application, the indole-modified CNCs and γ-CD-MOFs realize the encapsulation of the MOF@citral / cinnamaldehyde composite material by the indole-modified CNCs through hydrogen bonding and crosslinking agent, form a stable interface network, significantly improve the structural integrity of the overall material and the capacity of pollutant capture, and realize the multiple adsorption of synthetic dyes, heavy metal ions and microorganisms and long-acting antibacterial performance. Among them, the aromatic indole ring is introduced on the surface of the indole-modified CNCs, which can adsorb aromatic organic pollutants through π-π stacking, and the addition of the indole group enhances the hydrophobicity, further improving the ability of the overall material to capture hydrophobic organic pollutants; the residual carboxyl and hydroxyl groups on the surface of the indole-modified CNCs can form complexes or electrostatic adsorption with heavy metal ions, providing the removal capacity for inorganic pollutants. The γ-CD-MOFs rely on its porous structure and large specific surface area to realize the physical screening and pore adsorption of small molecule organic matters and ions, and the inclusion of antibacterial molecules such as citral and cinnamaldehyde in the hydrophobic cavity of γ-cyclodextrin can stabilize the antibacterial molecules and realize the slow release of the antibacterial molecules, so that the composite system can effectively adsorb pollutants and also play a role in inhibiting bacteria. Under the synergistic action of the two, the indole-modified CNCs serve as a rigid skeleton to enhance the adsorption structure stability and provide chemical adsorption sites through π-π interaction and complexation; the γ-CD-MOFs provide large capacity capture capacity through pore physical adsorption and molecular recognition.

[0011] Alternatively, the CNCs are obtained by adding 4-10 parts by mass of pretreated wood pulp material, 8-15 parts by mass of potassium permanganate and 2.5-6 parts by mass of sodium bisulfite into a 5% sulfuric acid solution, stirring and reacting at room temperature for 3-5 h, adding hydrogen peroxide and mixing and stirring for 5 min, centrifuging to take the precipitate, washing with deionized water for 2-5 times, and drying at 40-50°C for 10-15 h.

[0012] In the application, KMnO4 is used as an oxidizing agent for preparing CNCs, wherein MnO 4- can be reduced to Mn 3+ , so that KMnO4 and Mn 3+ can quickly oxidize the amorphous region of cellulose. In order to avoid Mn 3+Reduced to Mn 2+ , resulting in reduced oxidation performance, sodium bisulfite was introduced to quickly reduce MnO 4- to generate highly active Mn 3+ , and it can reduce the MnO2 generated in the reaction system to Mn 3+ , thereby enhancing the oxidation capacity of the system, and further generating CNCs with higher oxidation degree. High oxidation degree CNCs contain more carboxyl and hydroxyl groups on the surface, which provides more reaction sites for subsequent indole acetic acid modification and combination with gamma-CD-MOFs; at the same time, the introduction of carboxyl groups enhances the complexing ability of heavy metal ions and the electrostatic adsorption effect on organic pollutants, thereby significantly improving the adsorption performance of the material; in addition, higher oxidation degree is conducive to forming stronger interfacial forces, improving the stress transfer efficiency of the composite material, and making it perform better in mechanical properties and stability.

[0013] Optionally, the pretreated wood pulp material is obtained by crushing wood pulp, soaking in a 5% NaOH solution for 18-24 hours, washing with deionized water, and drying.

[0014] The present application removes hemicellulose, lignin and other impurities in the wood pulp by soaking it in a NaOH solution to obtain relatively pure cellulose raw materials.

[0015] Optionally, in step S1, indole acetic acid is dissolved in a 1.2%-1.5% volume concentration aqueous acetic acid solution under stirring at room temperature, then N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 4-dimethylaminopyridine and CNCs are added, ultrasonic treatment is carried out at a power of 200-400W for 5min, stirring reaction is carried out for 32-36h, ethanol and deionized water are used for washing in sequence, and drying is carried out at 40-60℃ for 12-16h to obtain indole-modified CNCs.

[0016] After adding CNCs, the present application first carries out ultrasonic treatment to disperse CNC aggregates and increase the reaction surface area, which is more conducive to uniform modification.

[0017] Optionally, the gamma-CD-MOFs are obtained by mixing gamma-cyclodextrin, KOH, deionized water and methanol and stirring for 5-10min, then standing at 50℃ for 10-15min, ultrasonic treatment at a power of 300-540W for 10-15min, then adding methanol and polyethylene glycol 8000, stirring for 5-10min, standing for 30-40min, centrifuging at a speed of 2000-3000rpm for 5-10min, taking the precipitate, washing with ethanol for 2-5 times, and drying at 40-50℃ for 10-12h.

[0018] The application uses γ-cyclodextrin to form a stable three-dimensional porous network with metal ions under alkaline conditions, and the porous structure brings a large specific surface area, providing a large number of active sites, and the internal hydrophobic cavity of γ-cyclodextrin cooperates to realize the subsequent loading of citral and cinnamic aldehyde through adsorption and inclusion.

[0019] Optionally, the γ-CD-MOFs include the following mass parts of raw materials: 1.2-2 parts of γ-cyclodextrin, 0.45-0.7 parts of KOH, 40 parts of deionized water, 67.26-75.17 parts of methanol, and 0.5-1 part of polyethylene glycol 8000.

[0020] Optionally, in the step S2, the ultrasonic treatment time is 5-10 min, the mixing and stirring temperature is 20-30℃, the time is 12-16h, the centrifugal rate is 2000-3000rpm, the time is 5-15min, the washing detergent is ethanol, the washing times is 2-5 times, the drying temperature is 40℃, and the time is 12-18h.

[0021] Optionally, in the step S3, the indole-modified CNCs are added to deionized water, ultrasonic dispersion is performed at a power of 200W for 5-8min, the MOF@citral / cinnamic aldehyde composite material is added, mixing is performed, stirring is performed at room temperature for 8-12h, standing is performed at 40-50℃ for 1-2h, centrifugation is performed at a rate of 500rpm for 5-10min, the precipitate is taken, washing is performed 3-5 times with an ethanol solution, and drying is performed at 40℃ for 12-18h to obtain the modified high-performance fiber material.

[0022] Optionally, in the step S3, 0.2-0.5 parts by mass of a polyhydroxy crosslinking agent is added when the MOF@citral / cinnamic aldehyde composite material is added; the polyhydroxy crosslinking agent is one of glycerol, sorbitol, and citric acid.

[0023] The application further provides a modified high-performance fiber material, which includes the following mass parts of raw materials: 0.2-0.5 parts of indole acetic acid, 1.5-2 parts of CNCs, 0.35-0.5 parts of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 0.02 parts of 4-dimethylaminopyridine, 1-1.2 parts of γ-CD-MOFs, 0.3-1.5 parts of citral, and 0.6-1 part of cinnamic aldehyde.

[0024] The modified high-performance fiber material prepared by using the above components in the application can be used as an adsorbent material to realize adsorption of pollutants and has a certain removal effect on bacteria and fungi.

[0025] The above technical solution of the application at least has the following beneficial effects: 1、The application realizes bacteriostasis, pi-pi stacking adsorption and enhanced complexing ability with heavy metal ions by introducing indole ring to modify CNCs, and improves the anti-ultraviolet performance and material stability, giving the material multifunctional adsorption and long-term application potential.

[0026] 2、The application realizes efficient adsorption of pollutants by using the high specific surface area and porous structure of gamma-CD-MOFs, and at the same time, the hydrophobic cavity of gamma-cyclodextrin stabilizes the load of citral and cinnamaldehyde through molecular inclusion, reduces its volatile degradation, and gives the material high specific surface area and excellent long-term bacteriostatic performance.

[0027] 3、The application builds a stable interface network through the synergistic effect of indole modified CNCs and MOF@citral / cinnamaldehyde composite material, significantly improves the material structure integrity and adsorption capacity of complex pollutants. The surface of indole modified CNCs contains aromatic indole ring which can adsorb aromatic organic pollutants, and the carboxyl and hydroxyl groups can complex or electrostatically adsorb heavy metal ions. The MOF@citral / cinnamaldehyde composite material has high specific surface area and porous structure due to the presence of gamma-CD-MOFs, providing large capacity capture ability and multiple adsorption performance for the overall material, and at the same time, the antibacterial molecules of citral and cinnamaldehyde are included and released slowly, giving the material long-term bacteriostatic performance. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. The described embodiments are part of the embodiments of the present application, and all other embodiments obtained by those skilled in the art based on the described embodiments of the present application are within the scope of protection of the present application.

[0029] Example 1 After 30 g of wood pulp was crushed, it was immersed in 300 mL of a 5% mass concentration NaOH solution for 24 h, washed with deionized water, and dried to obtain a pretreated wood pulp material; 10 g of the pretreated wood pulp material, 10 g of potassium permanganate, and 3.5 g of sodium bisulfite were added to 400 mL of a 5% mass concentration sulfuric acid solution, stirred at room temperature for 5 h, 5 min of hydrogen peroxide was added and stirred, the precipitate was centrifuged, washed with deionized water 5 times, and dried at 50°C for 15 h to obtain CNCs; 0.5 g of indole acetic acid was dissolved in 30 mL of a 1.5% volume concentration aqueous acetic acid solution under stirring at room temperature, then 0.5 g of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 0.02 g of 4-dimethylaminopyridine, and 2 g of CNCs were added, ultrasonic treatment was performed at a power of 400 W for 5 min, stirring reaction was performed for 36 h, ethanol and deionized water were used for washing 5 times in sequence, and drying was performed at 40°C for 14 h to obtain indole-modified CNCs.

[0030] After 2 g of γ-cyclodextrin, 0.7 g of KOH, 40 mL of deionized water, and 25 mL of methanol were mixed and stirred for 10 min, they were left to stand at 50°C for 15 min, ultrasonic treatment was performed at a power of 540 W for 10 min, 70 mL of methanol and 1 g of polyethylene glycol 8000 were mixed and stirred for 10 min, then left to stand for 40 min, centrifuged at a speed of 2000 rpm for 10 min, the precipitate was washed with ethanol 5 times, and dried at 40°C for 12 h to obtain γ-CD-MOFs; 1.2 g of γ-CD-MOFs was added to 100 mL of an ethanol solution, ultrasonic treatment was performed for 10 min, 1.5 g of citral and 1 g of cinnamaldehyde were added, stirring was performed at 30°C for 14 h, centrifugation was performed at a speed of 3000 rpm for 8 min, the precipitate was washed with ethanol 5 times, and drying was performed at 40°C for 18 h to obtain a MOF@citral / cinnamaldehyde composite material.

[0031] The indole-modified CNCs were added to 80 mL of deionized water, ultrasonic dispersion was performed at a power of 200 W for 8 min, the MOF@citral / cinnamaldehyde composite material and 0.5 g of citric acid were mixed, stirring was performed at room temperature for 12 h, then left to stand at 40°C for 2 h, centrifugation was performed at a speed of 500 rpm for 10 min, the precipitate was washed with an ethanol solution 5 times, and drying was performed at 40°C for 18 h to obtain a modified high-performance fiber material.

[0032] Example 2 The 30 g wood pulp was crushed and then immersed in 300 mL of a 5% mass concentration NaOH solution for 18 h, washed with deionized water, and dried to obtain a pretreated wood pulp material; 4 g of the pretreated wood pulp material, 8 g of potassium permanganate, and 2.5 g of sodium bisulfite were added to 300 mL of a 5% mass concentration sulfuric acid solution, stirred at room temperature for 3 h, 5 min of mixing was performed after the addition of hydrogen peroxide, the precipitate was separated by centrifugation, washed twice with deionized water, and dried at 40°C for 10 h to obtain CNCs; 0.2 g of indole acetic acid was dissolved in 30 mL of a 1.2% volume concentration aqueous acetic acid solution under stirring at room temperature, then 0.35 g of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 0.02 g of 4-dimethylaminopyridine, and 1.5 g of the CNCs were added, ultrasonic treatment was performed at a power of 200 W for 5 min, stirring was performed for 32 h, the product was washed twice with ethanol and deionized water in sequence, and dried at 40°C for 12 h to obtain indole-modified CNCs.

[0033] 1.2 g of γ-cyclodextrin, 0.45 g of KOH, 40 mL of deionized water, and 25 mL of methanol were mixed and stirred for 5 min, then left to stand at 50°C for 10 min, ultrasonic treatment was performed at a power of 300 W for 10 min, 60 mL of methanol and 0.5 g of polyethylene glycol 8000 were added and mixed and stirred for 5 min, then left to stand for 30 min, centrifuged at a speed of 2000 rpm for 5 min, the precipitate was washed twice with ethanol, and dried at 40°C for 10 h to obtain γ-CD-MOFs; 1 g of the γ-CD-MOFs was added to 100 mL of an ethanol solution, ultrasonic treatment was performed for 5 min, 0.3 g of citral and 0.6 g of cinnamaldehyde were added, mixed and stirred at 20°C for 12 h, centrifuged at a speed of 2000 rpm for 5 min, the precipitate was washed twice with ethanol, and dried at 40°C for 12 h to obtain a MOF@citral / cinnamaldehyde composite material.

[0034] The indole-modified CNCs were added to 80 mL of deionized water, ultrasonic dispersion was performed at a power of 200 W for 5 min, the MOF@citral / cinnamaldehyde composite material and 0.2 g of glycerol were added, mixed and stirred at room temperature for 8 h, then left to stand at 40°C for 1 h, centrifuged at a speed of 500 rpm for 5 min, the precipitate was washed three times with an ethanol solution, and dried at 40°C for 12 h to obtain a modified high-performance fiber material.

[0035] Example 3 After 30 g of wood pulp was crushed, it was immersed in 300 mL of a 5% mass concentration NaOH solution for 18 h, washed with deionized water, and dried to obtain a pretreated wood pulp material; 8 g of the pretreated wood pulp material, 15 g of potassium permanganate, and 6 g of sodium bisulfite were added to 400 mL of a 5% mass concentration sulfuric acid solution, stirred at room temperature for 5 h, 5 min of hydrogen peroxide was added and mixed, the precipitate was obtained by centrifugation, washed with deionized water 5 times, and dried at 50°C for 15 h to obtain CNCs; 0.5 g of indole acetic acid was dissolved in 30 mL of a 1.3% volume concentration acetic acid aqueous solution under stirring at room temperature, then 0.5 g of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 0.02 g of 4-dimethylaminopyridine, and 1.8 g of CNCs were added, ultrasonic treatment was performed at a power of 400 W for 5 min, stirring reaction was performed for 34 h, ethanol and deionized water were used for washing 4 times in sequence, and drying was performed at 50°C for 16 h to obtain indole-modified CNCs.

[0036] After 1.8 g of γ-cyclodextrin, 0.6 g of KOH, 40 mL of deionized water, and 25 mL of methanol were mixed and stirred for 8 min, they were left to stand at 50°C for 12 min, ultrasonic treatment was performed at a power of 540 W for 12 min, 65 mL of methanol and 0.8 g of polyethylene glycol 8000 were mixed and stirred for 7 min, then left to stand for 35 min, centrifugation was performed at a speed of 3000 rpm for 10 min, the precipitate was obtained, washed with ethanol 3 times, and dried at 45°C for 11 h to obtain γ-CD-MOFs; 1.1 g of γ-CD-MOFs was added to 100 mL of an ethanol solution, ultrasonic treatment was performed for 7 min, 1.3 g of citral and 0.6 g of cinnamaldehyde were added, stirring was performed at 20°C for 16 h, centrifugation was performed at a speed of 3000 rpm for 15 min, the precipitate was obtained, washed with ethanol 3 times, and dried at 40°C for 14 h to obtain a MOF@citral / cinnamaldehyde composite material.

[0037] The indole-modified CNCs were added to 80 mL of deionized water, ultrasonic dispersion was performed at a power of 200 W for 6 min, the MOF@citral / cinnamaldehyde composite material and 0.4 g of sorbitol were mixed, stirring was performed at room temperature for 10 h, then left to stand at 45°C for 1.5 h, centrifugation was performed at a speed of 500 rpm for 8 min, the precipitate was obtained, washed with an ethanol solution 4 times, and dried at 40°C for 16 h to obtain a modified high-performance fiber material.

[0038] Example 4 After 30 g of wood pulp was crushed, it was immersed in 300 mL of a 5% mass concentration NaOH solution for 20 h, washed with deionized water, and dried to obtain pretreated wood pulp material; 8 g of the pretreated wood pulp material, 12 g of potassium permanganate, and 3.5 g of sodium bisulfite were added to 350 mL of a 5% mass concentration sulfuric acid solution, stirred at room temperature for 1 h, 5 min of mixing were added after hydrogen peroxide was added, the precipitate was centrifuged, washed with deionized water 3 times, and dried at 45°C for 11 h to obtain CNCs; 0.4 g of indole acetic acid was dissolved in 30 mL of a 1.4% volume concentration aqueous acetic acid solution under stirring at room temperature, then 0.4 g of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 0.02 g of 4-dimethylaminopyridine, and 1.8 g of CNCs were added, ultrasonic treatment was performed at a power of 400 W for 5 min, stirring was performed for 34 h, ethanol and deionized water were sequentially used for washing 3 times, and drying was performed at 50°C for 14 h to obtain indole-modified CNCs.

[0039] After 1.6 g of γ-cyclodextrin, 0.5 g of KOH, 40 mL of deionized water, and 25 mL of methanol were mixed and stirred for 8 min, standing was performed at 50°C for 12 min, ultrasonic treatment was performed at a power of 400 W for 12 min, 65 mL of methanol and 0.8 g of polyethylene glycol 8000 were mixed and stirred for 7 min, standing was performed for 35 min, centrifugation was performed at a rate of 2200 rpm for 8 min, the precipitate was taken, washed with ethanol 4 times, and dried at 45°C for 11 h to obtain γ-CD-MOFs; 1 g of γ-CD-MOFs was added to 100 mL of an ethanol solution, ultrasonic treatment was performed for 6 min, 0.3 g of citral and 1 g of cinnamaldehyde were added, stirring was performed at 25°C for 14 h, centrifugation was performed at a rate of 2200 rpm for 10 min, the precipitate was taken, washed with ethanol 4 times, and dried at 40°C for 16 h to obtain a MOF@citral / cinnamaldehyde composite material.

[0040] The indole-modified CNCs were added to 80 mL of deionized water, ultrasonic dispersion was performed at a power of 200 W for 6 min, the MOF@citral / cinnamaldehyde composite material and 0.3 g of citric acid were mixed, stirring was performed at room temperature for 8 h, standing was performed at 40°C for 2 h, centrifugation was performed at a rate of 500 rpm for 8 min, the precipitate was taken, washed with an ethanol solution 4 times, and dried at 40°C for 15 h to obtain a modified high-performance fiber material.

[0041] Example 5 After 30 g of wood pulp was crushed, it was immersed in 300 mL of a 5% mass concentration NaOH solution for 20 h, washed with deionized water, and dried to obtain a pretreated wood pulp material; 10 g of the pretreated wood pulp material, 12 g of potassium permanganate, and 4 g of sodium bisulfite were added to 320 mL of a 5% mass concentration sulfuric acid solution, stirred at room temperature for 5 h, 5 min of hydrogen peroxide was added and mixed, the precipitate was obtained by centrifugation, washed with deionized water for 3 times, and dried at 45°C for 13 h to obtain CNCs; 0.2 g of indole acetic acid was dissolved in 30 mL of a 1.4% volume concentration acetic acid aqueous solution under stirring at room temperature, then 0.4 g of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 0.02 g of 4-dimethylaminopyridine, and 1.6 g of CNCs were added, ultrasonic treatment was performed at a power of 260 W for 5 min, then stirring reaction was performed for 33 h, ethanol and deionized water were used for washing 4 times in sequence, and drying was performed at 50°C for 15 h to obtain indole modified CNCs.

[0042] After 1.2 g of γ-cyclodextrin, 0.7 g of KOH, 40 mL of deionized water, and 25 mL of methanol were mixed and stirred for 10 min, standing was performed at 50°C for 10 min, ultrasonic treatment was performed at a power of 540 W for 10 min, 70 mL of methanol and 0.5 g of polyethylene glycol 8000 were mixed and stirred for 10 min, standing was performed for 30 min, centrifugation was performed at a speed of 3000 rpm for 5 min, the precipitate was obtained, washed with ethanol for 5 times, and drying was performed at 40°C for 12 h to obtain γ-CD-MOFs; 1 g of γ-CD-MOFs was added to 100 mL of an ethanol solution, ultrasonic treatment was performed for 10 min, 0.3 g of citral and 1 g of cinnamaldehyde were added, stirring was performed at 20°C for 16 h, centrifugation was performed at a speed of 3000 rpm for 10 min, the precipitate was obtained, washed with ethanol for 2 times, and drying was performed at 40°C for 16 h to obtain a MOF@citral / cinnamaldehyde composite material.

[0043] The indole modified CNCs were added to 80 mL of deionized water, ultrasonic dispersion was performed at a power of 200 W for 5 min, the MOF@citral / cinnamaldehyde composite material and 0.5 g of sorbitol were mixed, stirring was performed at room temperature for 10 h, standing was performed at 50°C for 1 h, centrifugation was performed at a speed of 500 rpm for 8 min, the precipitate was obtained, washed with an ethanol solution for 3 times, and drying was performed at 40°C for 18 h to obtain a modified high-performance fiber material.

[0044] Example 6 The 30 g wood pulp is crushed and then immersed in 300 mL of 5% mass concentration NaOH solution for 22 h, washed with deionized water and dried to obtain a pretreated wood pulp material; 10 g of the pretreated wood pulp material, 15 g of potassium permanganate and 5 g of sodium bisulfite are added to 360 mL of 5% mass concentration sulfuric acid solution, stirred at room temperature for 4 h, mixed with hydrogen peroxide and stirred for 5 min, centrifuged to obtain a precipitate, washed with deionized water for 2 times, and dried at 45 DEG C for 12 h to obtain CNCs; 0.5 g of indole acetic acid is dissolved in 30 mL of 1.2% volume concentration acetic acid aqueous solution under stirring at room temperature, then 0.35 g of N-(3-dimethylaminopropyl)-N'-ethyl carbodiimide hydrochloride, 0.02 g of 4-dimethylaminopyridine and 1.5 g of CNCs are added, ultrasonic treated at a power of 300 W for 5 min, stirred for 35 h, washed with ethanol and deionized water for 4 times in sequence, and dried at 55 DEG C for 15 h to obtain indole modified CNCs.

[0045] 1.7 g of γ-cyclodextrin, 0.5 g of KOH, 40 mL of deionized water and 25 mL of methanol are mixed and stirred for 8 min, then placed at 50 DEG C for 12 min, ultrasonic treated at a power of 400 W for 12 min, then 65 mL of methanol and 0.8 g of polyethylene glycol 8000 are mixed and stirred for 10 min, then placed for 35 min, centrifuged at a speed of 2000 rpm for 8 min, the precipitate is taken out, washed with ethanol for 4 times, and dried at 45 DEG C for 12 h to obtain γ-CD-MOFs; 1.1 g of γ-CD-MOFs is added to 100 mL of ethanol solution, ultrasonic treated for 8 min, then 0.8 g of citral and 0.7 g of cinnamaldehyde are added, mixed and stirred at 25 DEG C for 12 h, centrifuged at a speed of 3000 rpm for 5 min, the precipitate is taken out, washed with ethanol for 3 times, and dried at 40 DEG C for 16 h to obtain MOF@citral / cinnamaldehyde composite material.

[0046] The indole modified CNCs are added to 80 mL of deionized water, ultrasonic dispersed at a power of 200 W for 5 min, then the MOF@citral / cinnamaldehyde composite material and 0.4 g of glycerol are added, mixed and stirred at room temperature for 9 h, then placed at 45 DEG C for 1.5 h, centrifuged at a speed of 500 rpm for 8 min, the precipitate is taken out, washed with ethanol solution for 3 times, and dried at 40 DEG C for 18 h to obtain modified high-performance fiber material.

[0047] The present application also carries out comparative examples and related tests.

[0048] Comparative Example 1 Compared with Example 1, the only difference is that CNCs are directly used instead of indole modified CNCs, and other preparation methods and components are completely consistent, and finally the modified high-performance fiber material is prepared.

[0049] Comparative Example 2 Comparative Example 2 is the same as Example 1 except that the indole modified CNCs were directly used to replace the MOF@citral / cinnamaldehyde composite material, and the other preparation methods and components were completely consistent, and finally the modified high-performance fiber material was prepared.

[0050] Comparative Example 3 Comparative Example 3 is the same as Example 1 except that the γ-CD-MOFs were directly used to replace the MOF@citral / cinnamaldehyde composite material, and the other preparation methods and components were completely consistent, and finally the modified high-performance fiber material was prepared.

[0051] Performance test I. Determination of the adsorption effect on dyes: The adsorption effect of the modified high-performance fiber materials prepared in Examples 1-6 and Comparative Examples 1-3 on dyes was evaluated using methylene blue. The sample was added to a methylene blue solution with a volume of 30 mL, a concentration of 30 mg / L, and a pH of 11 at a dosage ratio of 0.5 g / L, and shaken in a constant-temperature shaker at 25°C for 4 h. The supernatant was separated by centrifugation, and the methylene blue solution concentration after the reaction was determined by UV-visible spectrophotometry at a wavelength of 664 nm. The removal rate of methylene blue (%R) using the modified high-performance fiber material samples prepared in Examples 1-6 and Comparative Examples 1-3 was calculated according to Formula (I) to evaluate the adsorption effect. %R= (I) In Formula (I), %R is the removal rate of methylene blue, C0(mg / L) is the methylene blue solution concentration at the initial time, and Ct(mg / L) is the methylene blue solution concentration after 4 h. The specific results are shown in Table 1.

[0052] II. Determination of the adsorption effect on heavy metal ions: The modified high-performance fiber material samples prepared in Examples 1-6 and Comparative Examples 1-3 were added to a heavy metal ion solution with a volume of 30 mL at a dosage ratio of 0.5 g / L, and shaken in a constant-temperature shaker at 25°C for 4 h. Similarly, the adsorption capacity was calculated by the change in the concentration of heavy metal ions in the solution. The concentration of heavy metal ions was determined using a UV2450 type UV-visible spectrophotometer, and the adsorption capacity (Qeq) was calculated according to Formula (II). (II) Qeq(mg / g) is the adsorption capacity of heavy metal ions; (mg / mL) is the initial concentration of heavy metal ions solution; (mg / mL) is the concentration of heavy metal ions solution at 4h; V(mL) is the volume of heavy metal ions solution; W(g) is the weight of sample; the specific test results are shown in Table 2.

[0053] III. Antimicrobial performance determination: The experimental bacteria are Staphylococcus aureus ATCC6538, Escherichia coli ATCC25922, and Candida albicans ATCC10231; (1) Preparation of bacterial suspension The experimental bacteria were activated in nutrient broth medium at 37℃ for 24h; the activated bacterial solution was streaked on nutrient agar medium and cultured at 37℃ for 24h; the bacterial lawn was repeatedly blown and washed with 5mL of 0.03mol / L phosphate buffer, and then mixed and diluted with 0.03mol / L phosphate buffer to a concentration of 105cfu / mL; (2) Preparation of test sample solution 0.5g of modified high-performance fiber material samples prepared in Examples 1-6 and Comparative Examples 1-3 were respectively weighed into 95mL of 0.03mol / L phosphate buffer containing 0.09g of Tween 80, and 5mL of prepared bacterial suspension was then added and mixed; (3) Oscillating contact culture, the test sample solution and the blank sample (bacterial suspension) were cultured in a 37℃ constant temperature oscillation incubator at 150rpm for 60min, and then 1mL of bacterial solution was taken and plated on nutrient agar medium at 37℃, and cultured for 48h for bacteria (Staphylococcus aureus, Escherichia coli) and 72h for Candida albicans, and then colony counting was performed, and the inhibition rate (%) was calculated according to formula (III); (III) In formula (II), %IR is the antimicrobial rate (%), B0 is the number of colonies of the blank sample, is the number of colonies of the test sample solution; the specific antimicrobial performance test results are shown in Table 3.

[0054] Table 1

[0055] As shown in Table 1, the methylene blue removal rate of the modified high-performance fiber material samples prepared in Examples 1-6 can reach 96%, which is significantly better than that of Comparative Examples 1-3; wherein, Comparative Example 1 does not use indole acetic acid to modify CNCs, so that the adsorption efficiency of methylene blue is obviously decreased; Comparative Example 2 directly uses indole modified CNCs and citral, cinnamaldehyde as the adsorption material, the specific surface area is small, and the adsorption efficiency of methylene blue is also decreased, which further shows that the modified high-performance fiber material prepared by the application has excellent adsorption capacity for organic dyes.

[0056] Table 2

[0057] As shown in Table 2, the adsorption capacity of the modified high-performance fiber material samples prepared in Examples 1-6 for heavy metal ions is significantly higher than that of Comparative Examples 1-3; wherein, Comparative Example 1 does not use indole acetic acid to modify CNCs, so that the adsorption capacity for heavy metal ions is weakened; Comparative Example 2 directly uses indole modified CNCs and citral, cinnamaldehyde as the adsorption material, the specific surface area is small, and the adsorption capacity for heavy metal ions is significantly decreased.

[0058] Table 3

[0059] As shown in Table 3, the antibacterial performance of the modified high-performance fiber material samples prepared in Examples 1-6 is all good, all of which are above 99.9%. Comparative Example 1 does not modify CNCs, so that the antibacterial rate is decreased; Comparative Example 2 uses only MOF@citral / cinnamaldehyde composite material as the adsorption material, the loading effect of citral and cinnamaldehyde is poor, the specific surface area is small, and the antibacterial rate is obviously decreased; Comparative Example 3 does not incorporate antibacterial material in the γ-CD-MOFs, so that the overall antibacterial performance is significantly decreased.

[0060] In summary, the modified high-performance fiber material prepared by the preparation method of the application has strong adsorption capacity and bacteriostatic effect, realizes the adsorption-antibacterial dual function, and can be used as an adsorption material.

[0061] The above is the preferred embodiment of the application, and those skilled in the art can make some improvements and refinements without departing from the principles of the application, and these improvements and refinements should also be regarded as the protection scope of the application.

Claims

1. A method for producing a modified high-performance fiber material, characterized by It comprises the following steps: S1, mixing indole acetic acid, aqueous acetic acid solution, N-(3-dimethylaminopropyl)-N'-ethyl carbodiimide hydrochloride, 4-dimethylamino pyridine and CNCs to react, washing and drying to obtain indole modified CNCs; S2, adding γ-CD-MOFs into ethanol solution and ultrasonic treatment, adding citral and cinnamaldehyde and mixing, centrifuging to obtain the precipitate, washing and drying to obtain MOF@citral / cinnamaldehyde composite material; S3, mixing indole modified CNCs and MOF@citral / cinnamaldehyde composite material, standing, centrifuging to obtain the precipitate, washing and drying to obtain modified high-performance fiber material.

2. The method for preparing a modified high-performance fiber material according to claim 1, characterized in that, The CNCs are obtained by adding 4-10 parts of pretreated wood pulp material, 8-15 parts of potassium permanganate and 2.5-6 parts of sodium bisulfite into a 5% sulfuric acid solution, stirring and reacting at room temperature for 3-5 h, adding hydrogen peroxide and mixing for 5 min, centrifuging to obtain the precipitate, washing with deionized water for 2-5 times, and drying at 40-50℃ for 10-15 h.

3. The method for preparing a modified high-performance fiber material according to claim 2, characterized in that, The pretreated wood pulp material is obtained by crushing the wood pulp, immersing it in a 5% NaOH solution for 18-24 h, washing with deionized water, and drying.

4. The method for preparing a modified high-performance fiber material according to claim 1, characterized in that, In step S1, indole acetic acid is dissolved in a 1.2%-1.5% volume concentration aqueous acetic acid solution under stirring at room temperature, then N-(3-dimethylaminopropyl)-N'-ethyl carbodiimide hydrochloride, 4-dimethylamino pyridine and CNCs are added, ultrasonic treatment is carried out at a power of 200-400 W for 5 min, stirring reaction is carried out for 32-36 h, washing is carried out with ethanol and deionized water in sequence, and drying is carried out at 40-60℃ for 12-16 h to obtain indole modified CNCs.

5. The method for preparing a modified high-performance fiber material according to claim 1, characterized in that, The γ-CD-MOFs are obtained by mixing γ-cyclodextrin, KOH, deionized water and methanol and stirring for 5-10 min, standing at 50℃ for 10-15 min, ultrasonic treatment at a power of 300-540 W for 10-15 min, mixing methanol and polyethylene glycol 8000 and stirring for 5-10 min, standing for 30-40 min, centrifuging at a speed of 2000-3000 rpm for 5-10 min, washing the precipitate with ethanol for 2-5 times, and drying at 40-50℃ for 10-12 h.

6. The method for preparing a modified high-performance fiber material according to claim 5, characterized in that, The γ-CD-MOFs comprise the following raw materials by mass: 1.2-2 parts of γ-cyclodextrin, 0.45-0.7 parts of KOH, 40 parts of deionized water, 67.26-75.17 parts of methanol, and 0.5-1 part of polyethylene glycol 8000.

7. The method for preparing a modified high-performance fiber material according to claim 1, characterized in that, In step S2, the ultrasonic treatment time is 5-10 min, the mixing and stirring temperature is 20-30℃, the time is 12-16 h, the centrifuging speed is 2000-3000 rpm, the time is 5-15 min, the washing detergent is ethanol, the washing times is 2-5 times, the drying temperature is 40℃, and the time is 12-18 h.

8. The method for preparing a modified high-performance fiber material according to claim 1, characterized in that, In the step S3, the indole modified CNCs are added into deionized water, ultrasonic dispersed for 5-8 min at a power of 200 W, mixed with the MOF@citral / cinnamaldehyde composite material, stirred at room temperature for 8-12 h, and then centrifuged at a speed of 500 rpm for 5-10 min after being placed at 40-50℃ for 1-2 h. The precipitate is taken out, washed with an ethanol solution for 3-5 times, and dried at 40℃ for 12-18 h to obtain the modified high-performance fiber material.

9. The method for preparing a modified high-performance fiber material according to claim 1, characterized in that, In the step S3, 0.2-0.5 parts by mass of a multi-hydroxyl crosslinking agent is further added when the MOF@citral / cinnamaldehyde composite material is mixed. The multi-hydroxyl crosslinking agent is one of glycerol, sorbitol, and citric acid.

10. A modified high performance fiber material, characterized in that, The preparation method according to any one of claims 1-9, which is prepared from the following raw materials: 0.2-0.5 parts by mass of indole acetic acid, 1.5-2 parts by mass of CNCs, 0.35-0.5 parts by mass of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 0.02 parts by mass of 4-dimethylaminopyridine, 1-1.2 parts by mass of γ-CD-MOFs, 0.3-1.5 parts by mass of citral, and 0.6-1 parts by mass of cinnamaldehyde.

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