Modified cotton fiber for adsorbing acidic peculiar smell gas as well as preparation method and application of modified cotton fiber

Abstract

The invention provides a modified cotton fiber for adsorbing acidic peculiar smell gas as well as a preparation method and application of the modified cotton fiber. The preparation method of the modified cotton fiber comprises the following steps: firstly, activating the cotton fiber by using a NaOH solution to obtain the activated cotton fiber; modifying cotton fibers by using a modification solution containing aminated mesoporous silicon and polyethyleneimine to obtain first modified cotton fibers; 2, 3-epoxypropyl trimethyl ammonium chloride is used for modification, NaBH4 is used for reduction, and finally the modified cotton fiber is prepared. The prepared modified cotton fiber has a large specific surface area, high surface energy and more adsorption active sites, the acetic acid adsorption performance is remarkably improved, and when adsorption is conducted for 120 min, the acetic acid adsorption capacity of the modified cotton is improved by 66% compared with that of raw cotton and is improved by 62% compared with that of commercial deodorization cotton; the modified cotton fiber has excellent desorption and cyclic adsorption performance, and the effect is not obviously reduced after five times of cyclic adsorption.

Description

Technical Field

[0001] This invention belongs to the field of acidic gas adsorption material preparation technology, and particularly relates to a modified cotton fiber for adsorbing acidic odor gases, its preparation method and application. Background Technology

[0002] Acetic acid, also known as acetic acid, is a transparent, colorless, flammable, and volatile liquid with a pungent odor. It is widely used in plastics, pharmaceuticals, food, medicine, cosmetics, and textiles. Human sweat, through bacterial metabolism, produces odors on textiles, and acetic acid is a common acidic model gas among these odorous gas molecules. Acetic acid gas can enter the body through the nasal cavity and skin, irritating the mucous membranes of the eyes, nasal cavity, and throat, as well as the skin, causing discomfort such as eyelid edema, conjunctival congestion, and skin erythema. Long-term exposure to high-purity acetic acid may also lead to chronic damage, such as conjunctivitis, chronic pharyngitis, bronchitis, chronic rhinitis, and dermatitis. Furthermore, acetic acid released from harmful chemicals is also a form of air pollution. Therefore, finding rapid absorption methods for acetic acid gas is extremely necessary in both the field of human health and air quality monitoring.

[0003] Adsorption is an effective method for odor removal, primarily through physical and chemical adsorption. In physical adsorption, odor compounds come into contact with the adsorbent through the physical movement of the exhaust stream. Subsequently, odor molecules diffuse into the porous structure of the adsorbent via van der Waals forces. In chemical adsorption, odor molecules are adsorbed onto the adsorbent surface through chemical bonds, Lewis acid-base interactions, etc. Various methods have been explored to obtain advanced textile products with deodorizing properties, including adsorption onto odor adsorbents, fragrance masking, antibacterial treatment, and catalytic decomposition. Zeolites, cyclodextrins, activated carbon fibers, and metal-organic frameworks are commonly used adsorbents for odor control. Zeolites can be coated onto the surface of cellulose fibers using inorganic and organic binders to adsorb odors; however, zeolites have limited adsorption capacity, adsorbing only a certain amount of harmful gases and potentially releasing harmful substances that may pose a risk to human health. Cyclodextrins, natural cyclic oligosaccharides derived from starch molecules, offer the potential to capture odor molecules. However, cyclodextrins are water-soluble, limiting their application in textiles. Activated carbon fibers are among the most effective adsorbents for removing odors. However, the high cost and dark color of activated carbon fiber limit its widespread application in clothing. Masking odors by adding fragrances through microencapsulation is also a common method, but the fragrance only lasts for a few days because the acidity of sweat inhibits fragrance release. The growth of microorganisms in human sweat leads to odor production; therefore, treating fabrics with antibacterial materials can minimize bacterial growth and control odors during use and storage. However, this may threaten the growth of beneficial bacteria. Textiles coated with catalysts such as titanium dioxide can decompose odor compounds into carbon dioxide and water through the generated free radicals under light, but the wash fastness of catalyst-coated textiles decreases significantly. Therefore, it is necessary to investigate alternative adsorbent materials to improve the adsorption performance of acetic acid. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a method for preparing modified cotton fibers for adsorbing acidic odor gases and their application. The modified cotton fibers prepared by this invention have a large specific surface area, high surface energy, and more adsorption active sites, resulting in a significant improvement in the adsorption performance of acetic acid by the modified fibers.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a method for preparing modified cotton fibers for adsorbing acidic odor gases, comprising the following steps:

[0007] Cotton fibers are added to a NaOH solution and soaked to obtain activated cotton fibers;

[0008] Mesoporous silica was dispersed in an ethanol solution of APTES, refluxed, and filtered to obtain aminated mesoporous silica.

[0009] Aminated mesoporous silica and polyethyleneimine were added to water to obtain a modified solution;

[0010] Activated cotton fibers were added to the modification solution, stirred and reacted, and then glutaraldehyde was added, stirred, and filtered to obtain the first modified cotton fiber.

[0011] The first modified cotton fiber was added to a 2,3-epoxypropyltrimethylammonium chloride solution and reacted to obtain the second modified cotton fiber.

[0012] The second modified cotton fiber was added to a NaBH4 solution for reduction to obtain the modified cotton fiber.

[0013] Preferably, cotton fibers are added to a NaOH solution and soaked at 50–60°C for 0.5–1 h, then washed with deionized water until the pH is 8–9; wherein the mass-to-volume ratio of cotton fibers to NaOH solution is 1 g:(30–50) mL, and the mass concentration of the NaOH solution is 1–5%.

[0014] Preferably, mesoporous silica is dispersed in an ethanol solution of APTES, and in the reflux step, the reflux temperature is 60-80°C and the reflux time is 6-12 hours.

[0015] The volume concentration of APTES in the ethanol solution is 5-6%;

[0016] The mass-to-volume ratio of mesoporous silica to APTES in ethanol solution is 1 g:(50-60) mL;

[0017] The mesoporous silica is mesoporous silica MCM-41.

[0018] Preferably, the modified solution contains 3-5% aminated mesoporous silica and 1-2% polyethyleneimine by mass.

[0019] Preferably, activated cotton fibers are added to the modification solution, stirred and reacted at 60-80°C for 4-6 hours, cooled to 20-25°C, glutaraldehyde is added, stirred, and filtered to obtain the first modified cotton fiber.

[0020] The mass-to-volume ratio of cotton fiber to modified solution is 1g:(30-50)mL;

[0021] The mass-to-volume ratio of cotton fiber to glutaraldehyde is 1 g:(0.5-1) mL.

[0022] Preferably, the first modified cotton fiber is added to a 2,3-epoxypropyltrimethylammonium chloride solution and reacted at 50-60°C for 2-4 hours, then filtered to obtain the second modified cotton fiber;

[0023] The mass-to-volume ratio of cotton fiber to 2,3-epoxypropyltrimethylammonium chloride solution is 1g:(30-50)mL;

[0024] The mass concentration of the 2,3-epoxypropyltrimethylammonium chloride solution is 5-10%.

[0025] Preferably, the second modified cotton fiber is added to a NaBH4 solution for a reduction reaction for 30-40 minutes, washed, and dried to obtain the modified cotton fiber;

[0026] The NaBH4 solution concentration is 0.1–0.2 M;

[0027] The mass-to-volume ratio of cotton fiber to NaBH4 solution is 1 g:(30-50) mL.

[0028] Secondly, the present invention also provides a modified cotton fiber, which is prepared by the aforementioned preparation method.

[0029] Thirdly, the present invention also provides a modified cotton fiber prepared by the preparation method described above, or the application of the modified cotton fiber described above in adsorbing acidic gases, inhibiting bacterial growth, and preparing dyed fibers.

[0030] Preferably, the application of modified cotton fiber in the preparation of dyed fiber specifically includes: dyeing the modified cotton fiber to obtain dyed fiber.

[0031] The preparation method and application of modified cotton fibers for adsorbing acidic odor gases of the present invention have the following advantages compared with the prior art:

[0032] 1. The method for preparing modified cotton fibers for adsorbing acidic odor gases according to the present invention involves first activating cotton fibers with NaOH solution to obtain activated cotton fibers; then preparing a modification solution containing aminated mesoporous silica and polyethyleneimine; modifying the cotton fibers with the modification solution containing aminated mesoporous silica and polyethyleneimine to obtain first modified cotton fibers; further modifying the first modified cotton fibers with 2,3-epoxypropyltrimethylammonium chloride to obtain second modified cotton fibers; and finally reducing them with NaBH4 to obtain the final modified cotton fibers. The modified cotton fibers prepared by the present invention have a large specific surface area, high surface energy, and more adsorption active sites. Therefore, the adsorption performance of the modified fibers for acetic acid is significantly improved. After 120 min of adsorption, the adsorption capacity of the modified cotton for acetic acid is 66% higher than that of the original cotton and 62% higher than that of commercial deodorizing cotton. The modified cotton fibers prepared by the present invention have excellent desorption and cyclic adsorption performance, and the effect does not decrease significantly after 5 cycles of adsorption.

[0033] 2. The modified cotton fiber prepared in this invention exhibits an inhibition rate of 96.63% against Staphylococcus aureus and 91.26% against Escherichia coli, while the inhibition rate of unmodified cotton fiber against both Staphylococcus aureus and Escherichia coli is less than 70%. This invention utilizes the quaternary ammonium salt 2,3-epoxypropyltrimethylammonium chloride to improve the cotton fiber. Quaternary ammonium salt possesses certain surface activity and adsorption properties, and can adsorb odor molecules onto its surface through intermolecular van der Waals forces and electrostatic attraction, achieving a deodorizing effect. Simultaneously, the cations of the quaternary ammonium salt can chemically react with some negatively charged odor substances. For example, some acidic odor substances, such as acetic acid, hydrogen sulfide, and sulfur dioxide, can be neutralized by the quaternary ammonium salt, transforming them into odorless or low-odor substances. Mesoporous silica (mesoporous silicon dioxide) has wide applications in the field of gas adsorption due to its high specific surface area, regularly tunable pore size, and rich surface chemical properties. It can adsorb gases through physical processes (surface adsorption, pore size effect, capillary aggregation) and also chemically adsorb acidic gases through acid-base reactions via surface amination modification. Compared with raw cotton fibers, amination-modified fibers have higher dye uptake and fixation rates, more uniform dye distribution, and greater wear value. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1Scanning electron microscope images of the cotton fibers used in Example 1 and the modified cotton fibers prepared in Example 1;

[0036] Figure 2 The infrared absorption spectra of the cotton fibers used in Example 1 and the modified cotton fibers prepared in Example 1 are shown.

[0037] Figure 3 Diagram of a gas adsorption device;

[0038] Figure 4 The adsorption effect of cotton fibers used in Example 1, modified cotton fibers prepared in Example 1, and commercial deodorizing cotton on acetic acid.

[0039] Figure 5 The total surface energy distribution and specific surface area distribution of the cotton fiber used in Example 1 and the modified cotton fiber prepared in Example 1 are shown in Figure 1.

[0040] Figure 6 The inhibition rate of the cotton fiber used in Example 1 and the modified cotton fiber prepared in Example 1 against Staphylococcus aureus;

[0041] Figure 7 The inhibition rate of Escherichia coli against the cotton fiber used in Example 1 and the modified cotton fiber prepared in Example 1;

[0042] Figure 8 The images show a comparison of the cotton fibers used in Example 1 and the modified cotton fibers prepared in Example 1 before and after dyeing, including the dyeing rate and fixation rate. Detailed Implementation

[0043] To facilitate understanding of the present invention, a more comprehensive description of the invention will be provided below in conjunction with specific embodiments. Preferred embodiments of the invention are given in the specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0044] The order in which the embodiments are described below is not intended to limit the preferred order of the embodiments. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". Various embodiments of the invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0045] This invention provides a method for preparing modified cotton fibers for adsorbing acidic odor gases, comprising the following steps:

[0046] S1. Add cotton fibers to NaOH solution and soak them to obtain activated cotton fibers;

[0047] S2. Disperse mesoporous silica in an ethanol solution of APTES (i.e., 3-aminopropyltriethoxysilane, silane coupling agent KH-550), reflux, and filter to obtain aminated mesoporous silica.

[0048] S3. Add aminated mesoporous silica and polyethyleneimine to water to obtain a modified solution;

[0049] S4. Add the activated cotton fiber to the modification solution, stir and react, then add glutaraldehyde, stir, filter, and obtain the first modified cotton fiber.

[0050] S5. The first modified cotton fiber is added to 2,3-epoxypropyltrimethylammonium chloride (i.e., GPTAC, 2,3-epoxypropyltrimethylammonium chloride, CAS No.: 3033-77-0, chemical formula C6H). 14 The reaction was carried out in a ClNO) solution to obtain the second modified cotton fiber.

[0051] S6. The second modified cotton fiber is added to NaBH4 solution for reduction to obtain modified cotton fiber.

[0052] In some embodiments, cotton fibers are added to a NaOH solution and soaked at 50–60°C for 0.5–1 h, and then washed with deionized water until the pH is 8–9; wherein the mass-to-volume ratio of cotton fibers to NaOH solution is 1 g:(30–50) mL, and the mass concentration of the NaOH solution is 1–5%.

[0053] In some embodiments, mesoporous silica is dispersed in an ethanol solution of APTES, and in the reflux step, the reflux temperature is 60-80°C and the reflux time is 6-12 h.

[0054] The volume concentration of APTES in the ethanol solution is 5-6%;

[0055] The mass-to-volume ratio of mesoporous silica to APTES in ethanol solution is 1 g:(50-60) mL;

[0056] The mesoporous silica is mesoporous silica MCM-41.

[0057] In some embodiments, the modified solution contains 3-5% by mass of aminated mesoporous silica and 1-2% by mass of polyethyleneimine.

[0058] In some embodiments, activated cotton fibers are added to a modified solution, stirred and reacted at 60-80°C for 4-6 hours, cooled to 20-25°C, glutaraldehyde is added, stirred, and filtered to obtain the first modified cotton fiber.

[0059] The mass-to-volume ratio of cotton fiber to modified solution is 1g:(30-50)mL;

[0060] The mass-to-volume ratio of cotton fiber to glutaraldehyde is 1 g:(0.5-1) mL.

[0061] In some embodiments, the first modified cotton fiber is added to a 2,3-epoxypropyltrimethylammonium chloride solution and reacted at 50-60°C for 2-4 hours, then filtered to obtain the second modified cotton fiber;

[0062] The mass-to-volume ratio of cotton fiber to 2,3-epoxypropyltrimethylammonium chloride solution is 1g:(30-50)mL;

[0063] The mass concentration of the 2,3-epoxypropyltrimethylammonium chloride solution is 5-10%.

[0064] In some embodiments, the second modified cotton fiber is added to a NaBH4 solution for a reduction reaction for 30-40 minutes, washed, and dried to obtain the modified cotton fiber.

[0065] The NaBH4 solution concentration is 0.1–0.2 M;

[0066] The mass-to-volume ratio of cotton fiber to NaBH4 solution is 1 g:(30-50) mL.

[0067] The present invention discloses a method for preparing modified cotton fibers for adsorbing acidic odor gases. First, cotton fibers are activated using NaOH solution to obtain activated cotton fibers. Then, a modification solution containing aminated mesoporous silica and polyethyleneimine is prepared. The cotton fibers are modified using the modification solution containing aminated mesoporous silica and polyethyleneimine to obtain first modified cotton fibers. The first modified cotton fibers are further modified using 2,3-epoxypropyltrimethylammonium chloride to obtain second modified cotton fibers. Finally, reduction is performed using NaBH4 to obtain the final modified cotton fibers.

[0068] The cotton fiber used in this invention has a wide planting range, huge output, wide availability, low cost, good mechanical properties, is environmentally friendly, contains abundant hydroxyl groups, and is easy to chemically modify.

[0069] The modified cotton fiber prepared by this invention has a large specific surface area, as well as high surface energy and more adsorption active sites. Therefore, the adsorption performance of the modified fiber for acetic acid is significantly improved. After 120 min of adsorption, the adsorption capacity of the modified cotton for acetic acid is 66% higher than that of the original cotton and 62% higher than that of commercial deodorizing cotton. The modified cotton fiber prepared by this invention has excellent desorption and cyclic adsorption performance, and the effect does not decrease significantly after 5 cycles of adsorption.

[0070] The cationic portion of quaternary ammonium salts attracts the negative charge on the bacterial cell membrane surface, then adsorbs onto the cell membrane through electrostatic interactions, disrupting the bacterial cell membrane and inhibiting bacterial growth and reproduction. Cotton fibers modified with quaternary ammonium salt 2,3-epoxypropyltrimethylammonium chloride showed an inhibition rate of 96.63% against Staphylococcus aureus and 91.26% against Escherichia coli, while unmodified cotton fibers showed inhibition rates of less than 70% against both Staphylococcus aureus and Escherichia coli, indicating no antibacterial effect. Furthermore, quaternary ammonium salts possess certain surface activity and adsorption properties, adsorbing odor molecules onto their surfaces through intermolecular van der Waals forces and electrostatic attraction, achieving deodorization. Simultaneously, the cations of quaternary ammonium salts can chemically react with some negatively charged odor substances. For example, some acidic odor substances, such as acetic acid, hydrogen sulfide, and sulfur dioxide, can be neutralized by quaternary ammonium salts, transforming them into odorless or low-odor substances. Mesoporous silica (mesoporous silicon dioxide) has wide applications in gas adsorption due to its high specific surface area, regularly tunable pore size, and rich surface chemical properties. It can adsorb gases through physical processes (surface adsorption, pore size effect, capillary aggregation) and also chemically adsorb acidic gases through acid-base interactions via surface amination. Compared to raw cotton fibers, amination-modified fibers exhibit higher dye uptake and fixation rates, more uniform dye distribution, and greater wearability.

[0071] Based on the same inventive concept, the present invention also provides a modified cotton fiber, which is prepared by the above-described preparation method.

[0072] Based on the same inventive concept, the present invention also provides the application of the modified cotton fiber prepared by the above-mentioned preparation method or the above-mentioned modified cotton fiber in adsorbing acidic gases (such as acetic acid), inhibiting bacterial growth, and preparing dyed fibers.

[0073] In some embodiments, the application of modified cotton fibers in the preparation of dyed fibers specifically includes: dyeing the modified cotton fibers to obtain dyed fibers.

[0074] Specifically, the method for preparing dyed fibers includes the following steps:

[0075] S1. Add the dye to water to obtain a dye bath; the dye is Reactive Red 120 and / or Reactive Brilliant Blue KN-R, and the dye mass concentration is 2%;

[0076] S2. Immerse the modified cotton fiber prepared in this invention in a dye bath at 60-70°C and dye it at 150-160 rpm for 30-40 min; the mass-to-volume ratio of the modified cotton fiber to the dye bath is 1 g:(30-40) mL.

[0077] S3. Add 5-6 mL of sodium sulfate solution with a concentration of 40-45 g / L to the dye bath in S2, and continue dyeing at 60-70℃ for 30-40 min. Then, add 5-6 mL of sodium carbonate solution with a concentration of 20-25 g / L to the dye bath, and continue dyeing at 60-70℃ for 30-40 min. After fixing the color, wash the dyed fabric with water, and then soap it for 10 minutes at 90-95℃ in a solution containing 2 g / L soap powder and 2 g / L Na2CO3 to remove unfixed dye. After soaping, wash the cotton fibers with water again and dry them in an oven to obtain dyed fibers.

[0078] The modified cotton fiber for adsorbing acidic odor gases, its preparation method, and its application are further illustrated below with specific embodiments. This section further illustrates the content of the present invention in conjunction with specific embodiments, but should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the art.

[0079] In the following examples, the cotton fibers used were provided by Winner Medical (Wuhan) Co., Ltd.

[0080] In the following examples, mesoporous silica MCM-41, brand Sigma-Aldrich, CAS 7631-86-9, item number 643645, is used.

[0081] Example 1

[0082] This embodiment provides a method for preparing modified cotton fibers for adsorbing acidic odor gases, including the following steps:

[0083] S1. Add 1g of cotton fiber to 50mL of 1% NaOH aqueous solution, soak at 50℃ for 0.5h, and wash with deionized water until pH is 9 to obtain activated cotton fiber;

[0084] S2. Disperse 10g of mesoporous silica MCM-41 in 500mL of ethanol solution of APTES with a volume concentration of 5%, reflux at 70℃ for 10h, and filter to obtain aminated mesoporous silica.

[0085] S3. Add 1.5g of aminated mesoporous silica and 0.5g of polyethyleneimine to 50mL of deionized water to obtain a modified solution.

[0086] S4. Add the activated cotton fiber from S1 to the modified solution in S3, stir and react at 60°C for 4 hours, cool to 25°C, add 1 mL of glutaraldehyde, stir for 2 hours, filter and wash with deionized water to obtain the first modified cotton fiber.

[0087] The first modified cotton fiber in S5 and S4 was added to 30 mL of 5% (w / w) 2,3-epoxypropyltrimethylammonium chloride aqueous solution and reacted at 50 °C for 24 h. After filtration, the second modified cotton fiber was obtained.

[0088] S6. Add the second modified cotton fiber from S5 to 30 mL of 0.1 M (mol / L) NaBH4 solution, and reduce it at room temperature (25 °C) for 30 min. Wash and dry (dry at 60 °C for 12 h) to obtain the modified cotton fiber (denoted as CE / GA / PEI).

[0089] Performance testing

[0090] The microstructure of the cotton fiber (CE, i.e., the original cotton fiber) used in Example 1 and the modified cotton fiber (CE / GA / PEI) prepared in Example 1 were observed using a scanning electron microscope (JEOL-7800F, Nippon Electronics Co., Ltd.). The test results are shown in [Figure number missing]. Figure 1 .

[0091] Figure 1 (a) is a SEM image of the original cotton fiber, and (b) is a SEM image of the modified cotton fiber (CE / GA / PEI) prepared in Example 1.

[0092] from Figure 1As can be seen, the original cotton fiber surface is smooth and the fiber is flat and curled, but the modified cotton fiber surface is significantly rougher and the curl is reduced. This may be because the cellulose swelling causes it to become thicker, and the introduced groups on the surface make the surface rougher, and it is loaded with a certain amount of silica balls.

[0093] The infrared absorption spectra of the cotton fiber (CE, i.e., the original cotton fiber) used in Example 1 and the modified cotton fiber (CE / GA / PEI) prepared in Example 1 were tested using Fourier transform infrared spectroscopy (Nicolet is50, Thermo Fisher Scientific, USA). The results are shown in the figure. Figure 2 .

[0094] Figure 2 In this context, CE represents the original cotton fiber, while CE / GA / PEI represents the modified cotton fiber prepared in Example 1.

[0095] according to Figure 2 FTIR spectral analysis showed that, compared with the original cotton fiber CE, the modified cotton fiber CE / GA / PEI had a higher spectral density at 1554.8 cm⁻¹. -1 and 1467.6cm -1 New characteristic peaks appeared at [values ​​missing], attributed to the stretching vibrations of C=N and CN, respectively, confirming that the aldehyde group of glutaraldehyde (GA) and the amino group of polyethyleneimine (PEI) were successfully cross-linked via a Schiff base reaction. Furthermore, [values ​​missing] at 1000-1100 cm⁻¹ -1 The broad and strong absorption peaks appearing within the range correspond to the antisymmetric stretching vibrations of the Si-O-Si bonds, indicating that mesoporous silicon has been successfully loaded into the composite material.

[0096] Acetic acid adsorption properties and adsorption mechanism of modified cotton fibers

[0097] Using a gas detection system built in the laboratory (see...) Figure 3 The adsorption performance of acetic acid by the cotton fiber (CE, i.e., the original cotton fiber) used in Example 1, the modified cotton fiber (CE / GA / PEI) prepared in Example 1, and commercial deodorizing cotton was tested. The odor detection system consists of a gas circulation pump ( Figure 3 Gas pump), sample chamber ( Figure 3 (Sample chamber) and infrared spectrometer ( Figure 3 FTIR gas analyzer and data acquisition unit ( Figure 3The experiment consisted of a data collector. The specific experimental procedure was as follows: all test samples (CE, CE / GA / PEI, and deodorizing cotton) were left to stand for 48 hours at (20±2℃, relative humidity 65±2%) before testing. Adsorption experiments were conducted at room temperature in a fume hood. Two grams of each test sample were placed in the sample chamber of the gas detection system. The sample chamber was completely sealed, and 10 μL of acetic acid was injected into the gas pump using a microsyringe. The acetic acid was rapidly vaporized and circulated in the odor detection system. The real-time concentration change of acetic acid was detected using time-resolved infrared spectroscopy. The desorption experiment was performed as follows: 2 g of the test sample and 80 μL of acetic acid were placed together in a sealed container (5L). The container was first placed in a 50℃ oven for 30 minutes, and then at 20℃ for 8 hours to allow gas adsorption saturation. The sample was then quickly placed into the sample chamber and sealed. The gas release process was monitored using an infrared spectrometer. The cyclic testing process is as follows: After each gas adsorption test, CE and CE / GA / PEI fibers are placed in a laboratory environment at a temperature of 20±2℃ for at least 12 hours to allow their adsorption capacity to recover before the next round of cyclic testing. The cyclic test is repeated 5 times.

[0098] The adsorption, desorption, and cyclic adsorption effects of raw cotton fiber (CE) and modified cotton fiber (CE / GA / PEI) are shown in [the table]. Figure 4 .

[0099] Specifically, Figure 4 The adsorption effects of CE, CE / GA / PEI, and commercial deodorizing cotton (CE-Commercial) on acetic acid are shown in (a); the changes in acetic acid concentration in the odor detection system during the desorption experiment are shown in (b); and the adsorption rates of CE and CE / GA / PEI on acetic acid during the cyclic adsorption experiment are shown in (c). t Ct represents the real-time concentration of acetic acid in the system at time t, and C0 represents the initial concentration of acetic acid.

[0100] Depend on Figure 4 As shown in Figure (a), after 120 min of adsorption, the original cotton fiber (CE) adsorbed 57.83% of the acetic acid in the system, while the modified cotton fiber (CE / GA / PEI) adsorbed 96.25% of the acetic acid in the system. This indicates that the adsorption capacity of the modified cotton fiber (CE / GA / PEI) for acetic acid is significantly improved. The adsorption capacity of the modified cotton fiber (CE / GA / PEI) for acetic acid is 66% higher than that of the original cotton and 62% higher than that of the commercial deodorizing cotton (CE-Commercial).

[0101] Depend on Figure 4As shown in Figure (b), the modified cotton fiber (CE / GA / PEI) basically does not release acetic acid within 60 min, while the original cotton fiber (CE) releases 40.5 ppm of acetic acid. The results indicate that the modified cotton fiber (CE / GA / PEI) has a high adsorption capacity for acetic acid and does not desorb acetic acid into the environment.

[0102] Depend on Figure 4 As shown in (c), during the five cycles of adsorption, the adsorption rate of acetic acid by the modified cotton fiber (CE / GA / PEI) remained basically unchanged at around 96%, which verifies that the modified cotton fiber (CE / GA / PEI) has a good ability to repeatedly adsorb acetic acid.

[0103] The surface properties and specific surface area of ​​the cotton fibers (CE, i.e., the original cotton fibers) used in Example 1 and the modified cotton fibers (CE / GA / PEI) prepared in Example 1 were tested using a reverse gas chromatography analyzer (IGC-SEA, Surface Measurement Systems, Alperton, Middlesex, UK). The results are shown in [Figure number missing]. Figure 5 .

[0104] Specifically, Figure 5 The total surface energy distribution (a) and specific surface area (b) of CE and CE / GA / PEI are shown.

[0105] Depend on Figure 5 As shown in (a), at a surface coverage of 0.1, the nonpolar surface energy of the original cotton fiber (CE) is greater than that of the modified cotton fiber (CE / GA / PEI), indicating that the modified cotton fiber (CE / GA / PEI) has a greater effect on odor adsorption through physical interactions. The polar surface energy of the modified cotton fiber (CE / GA / PEI) is greater than that of the original cotton fiber (CE), indicating that the modified cotton fiber (CE / GA / PEI) exhibits the best adsorption potential through chemical interactions. Total surface energy is the combination of nonpolar and polar surface energies, representing the number of active sites per unit surface area. The higher total surface energy of the modified cotton fiber (CE / GA / PEI) indicates that it has a greater number of active sites per unit surface area; simultaneously, from... Figure 5 As can be seen in (b), the specific surface area of ​​the original cotton fiber (CE) is 1.25 m². 2 / g, the specific surface area of ​​modified cotton fiber (CE / GA / PEI) is 1.91m². 2 / g, the specific surface area of ​​the modified cotton fiber (CE / GA / PEI) is greater than that of the original cotton fiber (CE); given that the modified cotton fiber (CE / GA / PEI) has both high surface energy and large specific surface area, providing more adsorption active sites, it exhibits better adsorption performance for acetic acid.

[0106] Antibacterial and dyeing properties of modified cotton fibers

[0107] According to GB / T 20944.3-2008 "Evaluation of Antimicrobial Properties of Textiles - Part 3: Shaking Method", Staphylococcus aureus and Escherichia coli were selected as test bacteria to conduct antimicrobial tests on modified cotton fiber (CE / GA / PEI) and original cotton fiber (CE). Specific experimental method: 0.75g each of the original cotton fiber (CE) used in Example 1 and the modified cotton fiber (CE / GA / PEI) sample prepared in Example 1 were placed in 250mL Erlenmeyer flasks, and 70mL of PBS buffer (pH 7.4) was added. A blank control (no sample) was set up. 5mL of bacterial suspension (Staphylococcus aureus and Escherichia coli) was added to both the sample and control flasks. Samples were immediately taken ("0-contact time" group), diluted 10-fold, and poured onto agar plates for incubation. The initial colony count (CFU) was determined. The remaining sample flasks were shaken at 24℃±1℃ and 150r / min for 18h, then sampled again, diluted, and incubated to count the final colony count. The antibacterial rate is calculated by comparing the difference in colony counts before and after shaking. The difference between parallel test data should be ≤15%, and the effective dilution plate should have a colony count of 30–300 CFU. The antibacterial effect of modified cotton fibers is judged by an inhibition rate ≥70%, calculated using the following formula:

[0108]

[0109] In the formula: Y is the antibacterial rate (%); W t Q represents the average viable bacterial concentration (CFU / mL) in the flask after 18 hours of shaking contact with the blank control sample; t This represents the average viable bacterial concentration (CFU / mL) in the flasks after 18 hours of shaking contact with the sample group. Antibacterial test results are shown below. Figures 6-7 .

[0110] from Figure 6 As can be seen, the inhibition rates of modified cotton fiber (CE / GA / PEI) and original cotton fiber (CE) against Staphylococcus aureus were 96.63% and 28.47%, respectively; from Figure 7 As can be seen, the inhibition rates of modified cotton fiber (CE / GA / PEI) and original cotton fiber (CE) against Escherichia coli were 91.26% and 21.53%, respectively. The inhibition rate of original cotton fiber (CE) against both Staphylococcus aureus and Escherichia coli was less than 70%, indicating no antibacterial effect. In contrast, modified cotton fiber (CE / GA / PEI) showed good inhibition rates against both Staphylococcus aureus and Escherichia coli, with CE / GA / PEI achieving an inhibition rate of 96.63% against Staphylococcus aureus and 91.26% against Escherichia coli.

[0111] The fibers were dyed using two dyes, Reactive Red 120 and Reactive Brilliant Blue KN-R, to obtain dyed fibers.

[0112] Specifically, the dyeing treatment of fibers using Reactive Red 120 includes the following steps:

[0113] S1. Add Reactive Red 120 to water to obtain a dye bath; the mass concentration of Reactive Red 120 is 2%;

[0114] S2. Immerse the modified cotton fiber prepared in Example 1 in a dye bath at 60°C and dye it at 150 rpm for 30 min; the mass-to-volume ratio of the modified cotton fiber to the dye bath is 1 g: 30 mL.

[0115] S3. Add 5 mL of sodium sulfate solution with a concentration of 40 g / L to the dye bath in S2, and continue dyeing at 60℃ for 30 min. Then, add 5 mL of sodium carbonate solution with a concentration of 20 g / L to the dye bath, and continue dyeing at 60℃ for 30 min. After fixing the color, wash the dyed fabric with water, and then soap it in a solution containing 2 g / L soap powder and 2 g / L Na2CO3 at 90℃ for 10 minutes to remove unfixed dye. After soaping, wash the cotton fibers with water again, and dry them in an oven to obtain dyed fibers.

[0116] Following the same method described above, Reactive Red 120 was replaced with Reactive Brilliant Blue KN-R, while all other process parameters remained unchanged. The modified cotton fibers prepared in Example 1 were then dyed using Reactive Brilliant Blue KN-R.

[0117] Following the same method described above, the modified cotton fiber prepared in Example 1 was replaced with the original cotton fiber (CE), with all other process parameters remaining unchanged, and the original cotton fiber (CE) was dyed using Reactive Red 120.

[0118] Following the same method described above, the modified cotton fiber prepared in Example 1 was replaced with the original cotton fiber (CE), and Reactive Red 120 was replaced with Reactive Brilliant Blue KN-R. All other process parameters remained unchanged, and the original cotton fiber (CE) was dyed using Reactive Brilliant Blue KN-R.

[0119] Comparison of raw cotton fiber (CE) and modified cotton fiber (CE / GA / PEI) before and after dyeing, as well as dyeing rate and fixation rate, are shown in the figure. Figure 8 .

[0120] Figure 8 The images show a comparison of the cotton fiber (CE, i.e., the original cotton fiber) used in Example 1 and the modified cotton fiber (CE / GA / PEI) prepared in Example 1 before and after dyeing (a), dyeing rate (b), and fixation rate (c).

[0121] Dye uptake rate: After dyeing with reactive dyes, the percentage of dye adsorbed by the fiber from the dye bath relative to the total amount of dye in the initial dye bath reflects the efficiency of dye transfer from the dye bath to the fiber.

[0122] Fixation rate: refers to the percentage of dye fixed on the fiber after dyeing out of the total amount of dye adsorbed on the fiber (i.e., the proportion of dye firmly bonded to the fiber through chemical bonds (covalent bonds, ionic bonds) or physical interactions (van der Waals forces, hydrogen bonds), i.e., the percentage of dye finally fixed on the fiber after soaping to remove floating dye out of the total amount of dye), reflecting the degree of fixation of dye on the fiber (i.e., the proportion of dye that has not been hydrolyzed or detached).

[0123] from Figure 8 As can be seen from (b) to (c), when dyeing with Reactive Red 120, the original cotton fiber (CE) had a fixation rate of 9.33% and a dye uptake of 21%, while the modified cotton fiber (CE / GA / PEI) had a fixation rate of 78.5% and a dye uptake of 90.6%.

[0124] When dyeing with reactive brilliant blue KN-R (KN-R), the fixation rate of the original cotton fiber (CE) is 33.1% and the dye uptake is 46.1%, while the fixation rate of the modified cotton fiber (CE / GA / PEI) is 88.5% and the dye uptake is 95.7%.

[0125] After dyeing with different reactive dyes, the modified cotton fibers showed significantly improved dye uptake and fixation rates compared to the original cotton fibers. The fixation rate of the modified cotton fibers (CE / GA / PEI) was significantly higher than that of the original cotton fibers (CE). Combined with the dye uptake data, this indicates that modification not only allows more dye to be adsorbed onto the fiber (higher dye uptake) but also enables these dyes to bind more firmly to the fiber (higher fixation). This may be because the chemical environment on the fiber surface changes after modification, promoting fixation reactions such as covalent bonding between the reactive dyes and the fiber. This could explain... Figure 8 The modified cotton fibers in (a) have brighter colors and better color fastness (such as wash fastness) after dyeing.

[0126] It is understood that the technical features of the above embodiments can be combined arbitrarily. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0127] The above are merely preferred embodiments of this application, and only specifically describe the technical principles of this application. These descriptions are only for explaining the principles of this application and should not be construed as limiting the scope of protection of this application in any way. Based on this explanation, any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application, as well as other specific embodiments of this application that can be conceived by those skilled in the art without creative effort, should be included within the scope of protection of this application.

Claims

1. A method for preparing modified cotton fibers for adsorbing acidic odor gases, characterized in that, Includes the following steps: Cotton fibers are added to a NaOH solution and soaked to obtain activated cotton fibers; Mesoporous silica was dispersed in an ethanol solution of APTES, refluxed, and filtered to obtain aminated mesoporous silica. Aminated mesoporous silica and polyethyleneimine were added to water to obtain a modified solution; Activated cotton fibers were added to the modification solution, stirred and reacted, and then glutaraldehyde was added, stirred, and filtered to obtain the first modified cotton fiber. The first modified cotton fiber was added to a 2,3-epoxypropyltrimethylammonium chloride solution and reacted to obtain the second modified cotton fiber. The second modified cotton fiber was added to a NaBH4 solution for reduction to obtain the modified cotton fiber.

2. The method for preparing modified cotton fiber for adsorbing acidic odor gases as described in claim 1, characterized in that, Cotton fibers are added to NaOH solution and soaked at 50-60℃ for 0.5-1h, then washed with deionized water until the pH is 8-9; wherein the mass-volume ratio of cotton fibers to NaOH solution is 1g:(30-50)mL, and the mass concentration of NaOH solution is 1-5%.

3. The method for preparing modified cotton fiber as described in claim 1, characterized in that, Mesoporous silica is dispersed in an ethanol solution of APTES. In the reflux step, the reflux temperature is 60-80℃ and the reflux time is 6-12h. The volume concentration of APTES in the ethanol solution is 5-6%; The mass-to-volume ratio of mesoporous silica to APTES in ethanol solution is 1 g:(50-60) mL; The mesoporous silica is mesoporous silica MCM-41.

4. The method for preparing modified cotton fiber for adsorbing acidic odor gases as described in claim 1, characterized in that, The modified solution contains 3-5% aminated mesoporous silica and 1-2% polyethyleneimine by mass.

5. The method for preparing modified cotton fiber for adsorbing acidic odor gases as described in claim 1, characterized in that, The activated cotton fibers were added to the modified solution and stirred at 60-80°C for 4-6 hours. After cooling to 20-25°C, glutaraldehyde was added, stirred, and filtered to obtain the first modified cotton fiber. The mass-to-volume ratio of cotton fiber to modified solution is 1g:(30-50)mL; The mass-to-volume ratio of cotton fiber to glutaraldehyde is 1 g:(0.5-1) mL.

6. The method for preparing modified cotton fiber for adsorbing acidic odor gases as described in claim 1, characterized in that, The first modified cotton fiber was added to a 2,3-epoxypropyltrimethylammonium chloride solution and reacted at 50-60°C for 2-4 hours. After filtration, the second modified cotton fiber was obtained. The mass-to-volume ratio of cotton fiber to 2,3-epoxypropyltrimethylammonium chloride solution is 1g:(30-50)mL; The mass concentration of the 2,3-epoxypropyltrimethylammonium chloride solution is 5-10%.

7. The method for preparing modified cotton fiber for adsorbing acidic odor gases as described in claim 1, characterized in that, The second modified cotton fiber was added to NaBH4 solution for reduction reaction for 30-40 min, washed, and dried to obtain the modified cotton fiber. The NaBH4 solution concentration is 0.1–0.2 M; The mass-to-volume ratio of cotton fiber to NaBH4 solution is 1 g:(30-50) mL.

8. A modified cotton fiber, characterized in that, It is prepared by any one of the preparation methods described in claims 1 to 7.

9. The application of a modified cotton fiber prepared by any one of the preparation methods described in claims 1 to 7, or the modified cotton fiber described in claim 8, in adsorbing acidic gases, inhibiting bacterial growth, and preparing dyed fibers.

10. The application as described in claim 9, specifically including: The modified cotton fibers were dyed to obtain dyed fibers.

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