A fiber containing plant-based composite mosquito repellent material

Abstract

This invention relates to the field of functional fiber technology, specifically to a fiber containing a plant-based composite mosquito-repellent material. The fiber preparation method includes the preparation of sulfonated polyimide, the preparation of an emulsion, the formation of a coating, and spinning. This invention, by coating the mosquito-repellent active ingredients with an inorganic-organic hybrid shell, not only improves the stability of the active ingredients during fiber preparation and reduces the loss rate, but also provides good dispersibility, making it suitable for various fiber matrices such as viscose, acrylic, lyocell, modal, polyester, nylon, and polypropylene. Adding the prepared plant-based composite mosquito-repellent material to the fiber not only imparts a mosquito-repellent effect but also provides long-lasting antibacterial efficacy. Simultaneously, the plant-based composite mosquito-repellent material exhibits good compatibility with the fiber matrix, avoiding any impact on the fiber's mechanical and dyeing properties.

Description

Technical Field

[0001] This invention relates to the field of functional fiber technology, specifically to a fiber containing plant-based composite mosquito repellent material. Background Technology

[0002] With increasing awareness of health and environmental protection, traditional chemical mosquito repellent products such as mosquito repellent liquids and coils are drawing growing attention due to their irritation, toxicity, and environmental pollution. Natural mosquito repellent active ingredients, with their advantages of good biocompatibility, no residue, gentleness on the human body, and environmental friendliness, have become a research hotspot and development trend in the field of functional fibers. Functional mosquito repellent fibers, as an important component of protective textiles, can be widely used in clothing, mosquito nets, tents, outdoor products, and other fields. They can effectively reduce the risk of disease transmission from mosquito bites, improve user comfort and safety, and market demand continues to grow.

[0003] Currently, the core of functional mosquito-repellent fiber preparation lies in loading mosquito-repellent active ingredients into the fiber matrix to combine mosquito-repellent function with fiber performance. Plant-based mosquito-repellent ingredients are derived from natural extracts and have good mosquito-repellent effects and environmental compatibility. However, these natural ingredients themselves have drawbacks such as poor stability, volatility, and susceptibility to inactivation due to external conditions.

[0004] Currently, the preparation of functional mosquito-repellent fibers in existing technologies uses plant essential oils or plant ingredients as the core mosquito-repellent components. These fibers are prepared through direct addition or simple compounding, combined with specific fiber textile processes, and can be broadly categorized into the following three types: 1. Mosquito-repellent functional components are attached to a single fiber substrate by means of padding, coating, or direct mixing into spinning solution, but the loss is relatively high; 2. After encapsulating the mosquito-repellent active ingredients with microcapsules, melt spinning or wet spinning is performed. However, the microcapsule shell is relatively brittle and is easily ruptured by the pressure of the spinneret, resulting in the loss of the mosquito-repellent active ingredients. 3. By using methods such as core-sheath structure, mosquito repellent ingredients are loaded onto the surface or core of the fiber to optimize the release efficiency of the mosquito repellent effect. However, core-sheath fibers are mostly synthetic fibers, and the spinning temperature is relatively high, so the active ingredients for mosquito repelling are easily destroyed by high temperature.

[0005] Given the wide variety of existing fiber substrates and the significant differences in textile processes for different fibers (such as viscose, modal, lyocell, polyester, nylon, spandex, etc.), how to adapt the same plant-based composite mosquito repellent material to various fiber spinning processes has become a critical issue that urgently needs to be addressed. Summary of the Invention

[0006] The purpose of this invention is to provide a fiber containing plant-based composite mosquito repellent material, thereby improving the stability of the mosquito repellent active ingredients in the fiber and its compatibility with different fibers.

[0007] A fiber containing plant-based composite mosquito repellent material, wherein the fiber is prepared by: Preparation of S1, sulfonated polyimide Under nitrogen atmosphere, 2,2'-bis(sulfonic acid) benzidine and triethylamine were added to m-cresol and stirred until dissolved. Then, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid were added. The mixture was stirred at room temperature for 50–60 min, heated to 70–90 °C and reacted for 5–6 h. The temperature was then raised to 180–200 °C and the reaction was continued for 18–24 h. After the reaction was completed, the reaction system was cooled to 60–70 °C, and deionized water was added to precipitate the precipitate. The precipitate was washed 2–3 times with deionized water and dried to obtain sulfonated polyimide.

[0008] Preferably, the molar ratio of 2,2'-disulfonic acid benzidine, triethylamine, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid is 1-1.2:2.0-2.5:1.2-1.3:2.3-2.6.

[0009] Preferably, the ratio of 2,2'-bissulfonic acid benzidine to m-cresol is 1g:15-20mL.

[0010] Preferably, the amount of deionized water added during the precipitation is 8 to 10 times the volume of the reaction system.

[0011] S2, Emulsion Preparation Sulfonated polyimide was added to deionized water, and dilute ammonia was added to adjust the pH to 8-9. The mixture was stirred until dissolved, and then calcium chloride solution was slowly added and stirred to form a colloidal dispersion. Plant extracts with mosquito-repellent function and surfactants were added to the colloidal dispersion and subjected to high-speed shearing to form an emulsion.

[0012] Preferably, the mass ratio of the sulfonated polyimide to deionized water is 1:20-25.

[0013] Preferably, the calcium chloride solution has a mass fraction of 3-5%.

[0014] Preferably, the molar ratio of the sulfonated polyimide to calcium ions in the calcium chloride solution is 1:1.1 to 1.3.

[0015] Preferably, the amount of the plant extract with mosquito-repellent function added is 30-40% of the mass of the sulfonated polyimide.

[0016] Preferably, the mass fraction of the dilute ammonia solution is 1-2%.

[0017] Preferably, the plant extract with mosquito-repellent function is one or more of the following: eucalyptus extract, rosemary extract, Japanese cypress extract, peppermint extract, cedarwood extract, Masson pine extract, grapefruit extract, camphor extract, thyme extract, chrysanthemum extract, bamboo leaf and Sichuan pepper extract, arborvitae extract, lemongrass extract, cinnamon extract, geranium extract, artemisia extract, lavender extract, and sweet basil extract.

[0018] Furthermore, all the plant extracts with mosquito-repellent properties are commercially available essential oils.

[0019] Preferably, the high-speed shearing rate is 10,000 to 12,000 rpm, and the time is 5 to 7 minutes.

[0020] Preferably, the surfactant is one or more of polyoxyethylene sorbitan fatty acid ester and sorbitan fatty acid ester, and the amount added is 2 to 4% of the mass of the plant extract with mosquito repellent function.

[0021] S3. Formation of the coating While stirring, sodium carbonate solution was added to the emulsion. After the addition was complete, stirring was continued for 3-4 hours. After standing for 10-12 hours, the coated material was collected by centrifugation and filtration. The material was washed 2-3 times with deionized water and then freeze-dried to obtain a plant-based composite mosquito repellent material with D90 < 2 μm.

[0022] Preferably, the sodium carbonate solution has a mass fraction of 3-5% and a dropping rate of 1-3 mL / min.

[0023] Preferably, the amount of sodium carbonate solution added is based on the molar ratio of sodium carbonate in the sodium carbonate solution to calcium ions in the emulsion, which is 1.05 to 1.2:1.

[0024] Preferably, the stirring rate is 300-400 rpm.

[0025] Preferably, the freeze-drying temperature is -50 to -40°C, and the time is 10 to 12 hours.

[0026] In deionized water, the sulfonate groups in sulfonated polyimide complex and crosslink with calcium ions in calcium chloride to form a colloid. Plant extracts and surfactants with mosquito-repellent function are added to the colloidal dispersion. The crosslinked sulfonated polyimide is adsorbed on the surface of the oil droplets. The calcium sulfonate groups are hydrophilic on the outside and the hydrophobic main chain is lipophilic on the inside, forming a preliminary stable interface. After the addition of sodium carbonate, the sodium carbonate reacts with the calcium ions on the interface to generate calcium carbonate in situ, which further solidifies the shell and generates an inorganic-organic hybrid shell, thereby encapsulating the mosquito-repellent essential oil.

[0027] Polyimide exhibits good heat resistance and stability, but its poor hydrophobicity limits its application in the fiber industry. When used in fibers, it can negatively impact dyeing properties, resulting in dyeing uniformity of only 1-2 grades. While sulfonated polyimide prepared using sulfonated diamine monomers can improve the hydrophobicity of polyimide, when used as a coating material, it exhibits water absorption and swelling after complexing and cross-linking with calcium ions. This swelling and breakage during subsequent padding and washing processes can cause a sudden release of the mosquito-repellent active ingredient, potentially affecting the overall durability of the fiber's mosquito-repellent effect. Therefore, adding sodium carbonate solution to the emulsion allows the sodium carbonate to react with calcium ions at the interface to form calcium carbonate precipitate, which is then uniformly deposited within the polymer network, acting as a filler and providing skeletal support. This improves wash resistance and, when added to the fiber, does not affect its dyeing properties.

[0028] S4, spinning The plant-based composite mosquito repellent material can be added to the spinning solution or polymer chips for blending, and then obtained by wet spinning or melt spinning to obtain fibers containing the plant-based composite mosquito repellent material.

[0029] Preferably, the spinning solution is one of viscose spinning solution, acrylic spinning solution, lyocell spinning solution, or modal spinning solution.

[0030] Preferably, the polymer chips are one of polyester chips, nylon chips, and polypropylene chips.

[0031] By adopting the above technical solution, the technical effect achieved by this invention is as follows: 1. This invention utilizes an inorganic-organic hybrid shell to encapsulate the mosquito-repellent active ingredients, which not only improves the stability of the mosquito-repellent active ingredients during fiber preparation and reduces the loss rate, but also provides good dispersibility, making it suitable for various fiber matrices such as viscose fiber, acrylic fiber, lyocell fiber, modal fiber, polyester, nylon, and polypropylene.

[0032] 2. The plant-based composite mosquito repellent material prepared by this invention, when added to fibers, not only gives the fibers a mosquito repellent effect, but also satisfies the function of long-lasting antibacterial properties.

[0033] 3. The plant-based composite mosquito repellent material prepared by this invention has good compatibility with the fiber substrate, thus avoiding any impact on the mechanical and dyeing properties of the fiber. Detailed Implementation

[0034] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0035] Example 1: A fiber containing plant-based composite mosquito repellent material, the fiber being prepared by: Preparation of S1, sulfonated polyimide Under nitrogen atmosphere, 2,2'-bis(sulfonic acid) benzidine and triethylamine were added to m-cresol and stirred until dissolved. Then, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid were added. The mixture was stirred at room temperature for 55 min, heated to 80 °C and reacted for 5.5 h, and then heated to 190 °C and reacted for another 20 h. After the reaction was completed, the reaction system was cooled to 65 °C, and deionized water was added to precipitate the precipitate. The precipitate was washed three times with deionized water and dried to obtain sulfonated polyimide.

[0036] The molar ratio of 2,2'-disulfonic acid benzidine, triethylamine, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid is 1.1:2.2:1.25:2.5.

[0037] The ratio of 2,2'-disulfonic acid benzidine to m-cresol is 1 g: 18 mL.

[0038] The amount of deionized water added during precipitation is 9 times the volume of the reaction system.

[0039] S2, Emulsion Preparation Sulfonated polyimide was added to deionized water, and dilute ammonia was added to adjust the pH to 8.5. The mixture was stirred until dissolved, and then calcium chloride solution was slowly added and stirred to form a colloidal dispersion. Plant extracts with mosquito-repellent function and surfactants were added to the colloidal dispersion and subjected to high-speed shearing to form an emulsion.

[0040] The mass ratio of the sulfonated polyimide to deionized water is 1:22.

[0041] The calcium chloride solution has a mass fraction of 4%.

[0042] The molar ratio of the sulfonated polyimide to calcium ions in the calcium chloride solution is 1:1.2.

[0043] The amount of the plant extract with mosquito-repellent function added is 35% of the mass of the sulfonated polyimide.

[0044] The mass fraction of the dilute ammonia solution is 1.5%.

[0045] The plant extract with mosquito-repellent function is eucalyptus oil and rosemary oil in a mass ratio of 8:2.

[0046] The high-speed shearing rate was 11,000 rpm, and the time was 6 minutes.

[0047] The surfactant is polyoxyethylene sorbitan fatty acid ester, and the amount added is 3% of the mass of the plant extract with mosquito-repellent function.

[0048] S3. Formation of the coating Sodium carbonate solution was added to the emulsion while stirring. After the addition was complete, stirring was continued for 3.5 hours. After standing for 11 hours, the coated material was collected by centrifugation and filtration. The material was washed three times with deionized water and then freeze-dried to obtain a plant-based composite mosquito repellent material with D90 < 2 μm.

[0049] The sodium carbonate solution has a mass fraction of 4% and a dropping rate of 2 mL / min.

[0050] The amount of sodium carbonate solution added is based on the molar ratio of sodium carbonate in the sodium carbonate solution to calcium ions in the emulsion, which is 1.1:1.

[0051] The stirring speed is 350 rpm.

[0052] The freeze-drying temperature was -45℃ and the time was 11 hours.

[0053] S4, spinning PA6 chips were crushed to 200 mesh, then mixed with plant-based composite mosquito repellent material and blended evenly. The mixture was then melt-extruded, granulated, and dried using a twin-screw extruder to produce mosquito repellent functional granules. The mosquito-repellent functional particles were blended with PA6 chips, melt-spun and cooled, and then stretched and heat-set to obtain nylon filaments containing plant-based composite mosquito-repellent materials.

[0054] The PA6 slices need to be dried before use.

[0055] The mass ratio of the PA6 slices to the plant-based composite mosquito repellent material is 95:5.

[0056] The temperatures of zones 1 to 5 of the twin-screw extruder are 245℃, 250℃, 255℃, 245℃, and 235℃, respectively, and the rotation speed is 100 r / min.

[0057] The mass ratio of the mosquito-repellent functional particles to PA6 slices is 8:92.

[0058] The parameters for melt spinning are: spinning box temperature of 260℃ and side blowing temperature of 20℃.

[0059] The stretching ratio is 4 times, and the heat setting temperature is 190℃.

[0060] Example 2: A fiber containing plant-based composite mosquito repellent material, the fiber being prepared by: Preparation of S1, sulfonated polyimide Under nitrogen atmosphere, 2,2'-bis(sulfonic acid) benzidine and triethylamine were added to m-cresol and stirred until dissolved. Then, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid were added. The mixture was stirred at room temperature for 50 min, heated to 70 °C and reacted for 5 h, and then heated to 180 °C and reacted for another 24 h. After the reaction was completed, the reaction system was cooled to 60 °C, and deionized water was added to precipitate the precipitate. The precipitate was washed twice with deionized water and dried to obtain sulfonated polyimide.

[0061] The molar ratio of 2,2'-bissulfonic acid benzidine, triethylamine, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid is 1:2.0:1.2:2.3.

[0062] The ratio of 2,2'-bissulfonic acid benzidine to m-cresol is 1 g: 15 mL.

[0063] The amount of deionized water added during precipitation is 8 times the volume of the reaction system.

[0064] S2, Emulsion Preparation Sulfonated polyimide was added to deionized water, and dilute ammonia was added to adjust the pH to 8. The mixture was stirred until dissolved, and then calcium chloride solution was slowly added and stirred to form a colloidal dispersion. Plant extracts with mosquito-repellent properties and surfactants were added to the colloidal dispersion and subjected to high-speed shearing to form an emulsion.

[0065] The mass ratio of the sulfonated polyimide to deionized water is 1:20.

[0066] The calcium chloride solution has a mass fraction of 3%.

[0067] The molar ratio of the sulfonated polyimide to calcium ions in the calcium chloride solution is 1:1.1.

[0068] The amount of the plant extract with mosquito-repellent function added is 30% of the mass of the sulfonated polyimide.

[0069] The mass fraction of the dilute ammonia solution is 1%.

[0070] The plant extract with mosquito-repellent function is eucalyptus oil and rosemary oil in a mass ratio of 8:2.

[0071] The high-speed shearing rate is 10,000 rpm, and the time is 7 minutes.

[0072] The surfactant is polyoxyethylene sorbitan fatty acid ester, and the amount added is 2% of the mass of the plant extract with mosquito-repellent function.

[0073] S3. Formation of the coating Sodium carbonate solution was added to the emulsion while stirring. After the addition was complete, stirring was continued for 3 hours. After standing for 10 hours, the coated material was collected by centrifugation and filtration. The material was washed twice with deionized water and then freeze-dried to obtain a plant-based composite mosquito repellent material with D90 < 2 μm.

[0074] The sodium carbonate solution has a mass fraction of 3% and a dropping rate of 1 mL / min.

[0075] The amount of sodium carbonate solution added is based on the molar ratio of sodium carbonate in the sodium carbonate solution to calcium ions in the emulsion, which is 1.05:1.

[0076] The stirring speed is 300 rpm.

[0077] The freeze-drying temperature is -50℃ and the time is 10 hours.

[0078] S4, spinning PA6 chips were crushed to 200 mesh, then mixed with plant-based composite mosquito repellent material and blended evenly. The mixture was then melt-extruded, granulated, and dried using a twin-screw extruder to produce mosquito repellent functional granules. The mosquito-repellent functional particles were blended with PA6 chips, melt-spun and cooled, and then stretched and heat-set to obtain nylon filaments containing plant-based composite mosquito-repellent materials.

[0079] The PA6 slices need to be dried before use.

[0080] The mass ratio of the PA6 slices to the plant-based composite mosquito repellent material is 95:5.

[0081] The temperatures of zones 1 to 5 of the twin-screw extruder are 245℃, 250℃, 255℃, 245℃, and 235℃, respectively, and the rotation speed is 100 r / min.

[0082] The mass ratio of the mosquito-repellent functional particles to PA6 slices is 8:92.

[0083] The parameters for melt spinning are: spinning box temperature of 260℃ and side blowing temperature of 20℃.

[0084] The stretching ratio is 4 times, and the heat setting temperature is 190℃.

[0085] Example 3: A fiber containing plant-based composite mosquito repellent material, the fiber being prepared by: Preparation of S1, sulfonated polyimide Under nitrogen atmosphere, 2,2'-bis(sulfonic acid) benzidine and triethylamine were added to m-cresol and stirred until dissolved. Then, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid were added. The mixture was stirred at room temperature for 60 min, heated to 90 °C and reacted for 6 h, and then heated to 200 °C and reacted for another 18 h. After the reaction was completed, the reaction system was cooled to 70 °C, and deionized water was added to precipitate the precipitate. The precipitate was washed three times with deionized water and dried to obtain sulfonated polyimide.

[0086] The molar ratio of 2,2'-bissulfonic acid benzidine, triethylamine, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid is 1.2:2.5:1.3:2.6.

[0087] The ratio of 2,2'-disulfonic acid benzidine to m-cresol is 1 g: 20 mL.

[0088] The amount of deionized water added during precipitation is 10 times the volume of the reaction system.

[0089] S2, Emulsion Preparation Sulfonated polyimide was added to deionized water, and dilute ammonia was added to adjust the pH to 9. The mixture was stirred until dissolved, and then calcium chloride solution was slowly added and stirred to form a colloidal dispersion. Plant extracts with mosquito-repellent function and surfactants were added to the colloidal dispersion and subjected to high-speed shearing to form an emulsion.

[0090] The mass ratio of the sulfonated polyimide to deionized water is 1:25.

[0091] The calcium chloride solution has a mass fraction of 5%.

[0092] The molar ratio of the sulfonated polyimide to calcium ions in the calcium chloride solution is 1:1.3.

[0093] The amount of the plant extract with mosquito-repellent function added is 40% of the mass of the sulfonated polyimide.

[0094] The mass fraction of the dilute ammonia solution is 2%.

[0095] The plant extract with mosquito-repellent function is eucalyptus oil and rosemary oil in a mass ratio of 8:2.

[0096] The high-speed shearing rate is 12,000 rpm, and the time is 5 minutes.

[0097] The surfactant is polyoxyethylene sorbitan fatty acid ester, and the amount added is 4% of the mass of the plant extract with mosquito-repellent function.

[0098] S3. Formation of the coating Sodium carbonate solution was added to the emulsion while stirring. After the addition was complete, stirring was continued for 4 hours. After standing for 12 hours, the coated material was collected by centrifugation and filtration. The material was washed three times with deionized water and then freeze-dried to obtain a plant-based composite mosquito repellent material with D90 < 2 μm.

[0099] The sodium carbonate solution has a mass fraction of 5% and a dropping rate of 3 mL / min.

[0100] The amount of sodium carbonate solution added is based on the molar ratio of sodium carbonate in the sodium carbonate solution to calcium ions in the emulsion, which is 1.2:1.

[0101] The stirring speed is 400 rpm.

[0102] The freeze-drying temperature is -40℃ and the time is 12 hours.

[0103] S4, spinning PA6 chips were crushed to 200 mesh, then mixed with plant-based composite mosquito repellent material and blended evenly. The mixture was then melt-extruded, granulated, and dried using a twin-screw extruder to produce mosquito repellent functional granules. The mosquito-repellent functional particles were blended with PA6 chips, melt-spun and cooled, and then stretched and heat-set to obtain nylon filaments containing plant-based composite mosquito-repellent materials.

[0104] The PA6 slices need to be dried before use.

[0105] The mass ratio of the PA6 slices to the plant-based composite mosquito repellent material is 95:5.

[0106] The temperatures of zones 1 to 5 of the twin-screw extruder are 245℃, 250℃, 255℃, 245℃, and 235℃, respectively, and the rotation speed is 100 r / min.

[0107] The mass ratio of the mosquito-repellent functional particles to PA6 slices is 8:92.

[0108] The parameters for melt spinning are: spinning box temperature of 260℃ and side blowing temperature of 20℃.

[0109] The stretching ratio is 4 times, and the heat setting temperature is 190℃.

[0110] Comparative Example 1: Select the representative Example 1, remove step S3, and spray dry the emulsion obtained in S2 to obtain a plant-based composite mosquito repellent material with D90 < 2 μm. The inlet air temperature of the spray drying is 140°C, the outlet air temperature is 80°C, and the pressure is 0.5 MPa. All other conditions are the same as in Example 1.

[0111] Comparative Example 2: Select a representative Example 1, remove step S3 and remove the calcium chloride solution in S2, and spray dry the emulsion obtained in S2 to obtain a plant-based composite mosquito repellent material with D90 < 2 μm. The inlet air temperature of the spray drying is 140°C, the outlet air temperature is 80°C, and the pressure is 0.5 MPa. All other conditions are the same as in Example 1.

[0112] The nylon filaments obtained in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests, as detailed in Table 1.

[0113] Table 1 The nylon filaments obtained in Examples 1-3 and Comparative Examples 1-2 were used to make fabrics, wherein the fabric composition was 54% polyester + 42% nylon filament + 4% spandex. The mosquito repellent effect and antibacterial effect of the fabrics were tested, as shown in Table 2.

[0114] Table 2 Testing standards: Dyeing uniformity: Determined by gray scale level according to "Test and Evaluation of Dyeing Uniformity of Viscose Filament (FZ / T 50015-2009)".

[0115] Color fastness to washing: GB-T / 3921-2008 Textiles - Tests for color fastness to soap washing.

[0116] Antibacterial rate: GB / T 20944.3-2008 Shaking method.

[0117] Mosquito repellency rate: GB / T 30126-2013 Test and evaluation of mosquito repellency performance of textiles.

[0118] In summary, the nylon filaments prepared using Examples 1-3, when combined with the plant-based composite mosquito-repellent material, exhibit better mosquito-repellent and antibacterial effects, stronger persistence of the mosquito-repellent active ingredients, and better dyeing performance. Furthermore, they possess a good cooling effect, with the fabric prepared using Example 1 exhibiting a cooling sensation of 0.21 J / cm². 2 ·s.

[0119] The poor mechanical properties of Comparative Examples 1 and 2 are due to the poor mechanical strength of the plant-based composite mosquito repellent materials prepared in Comparative Examples 1 and 2. As a result, there are more breakages during spinning, leading to greater losses. In addition, the materials also swell and break during washing, resulting in poor water washing stability. Furthermore, during the spinning process, some of the plant-based composite mosquito repellent materials in Comparative Examples 1 and 2 ruptured, causing essential oil leakage and increasing fiber defects. As a result, the mechanical properties of Comparative Examples 1 and 2 decreased slightly.

[0120] Unless otherwise specified, all proportions and percentages mentioned in this invention are mass proportions and mass percentages; all raw materials are commercially available.

[0121] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely preferred examples and are not intended to limit the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A fiber containing plant-based composite mosquito repellent material, characterized in that, The fiber preparation method includes the preparation of sulfonated polyimide, the preparation of emulsion, the formation of coating and spinning; The emulsion is prepared as follows: sulfonated polyimide is added to deionized water, dilute ammonia is added to adjust the pH to 8-9 and stirred until dissolved, then calcium chloride solution is slowly added and stirred to form a colloidal dispersion; plant extracts with mosquito-repellent function and surfactants are added to the colloidal dispersion and subjected to high-speed shearing to form an emulsion. The coating is formed as follows: sodium carbonate solution is added to the emulsion while stirring. After the addition is complete, stirring is continued for 3-4 hours. After standing for 10-12 hours, the coating is collected by centrifugation and filtration. The coating is washed 2-3 times with deionized water and then freeze-dried to obtain a plant-based composite mosquito repellent material with D90 < 2 μm.

2. The fiber containing plant-based composite mosquito repellent material according to claim 1, characterized in that, The sulfonated polyimide was prepared by adding 2,2'-bis(sulfonated) benzidine and triethylamine to m-cresol under nitrogen atmosphere and stirring until dissolved. Then, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid were added, and the mixture was stirred at room temperature for 50-60 minutes. The temperature was then raised to 70-90°C and reacted for 5-6 hours. The temperature was then raised to 180-200°C and the reaction was continued for 18-24 hours. After the reaction was completed, the reaction system was cooled to 60-70°C, and deionized water was added to precipitate the precipitate. The precipitate was washed 2-3 times with deionized water and dried to obtain sulfonated polyimide.

3. The fiber containing plant-based composite mosquito repellent material according to claim 2, characterized in that, The molar ratio of 2,2'-disulfonic acid benzidine, triethylamine, 1,4,5,8-naphthalenetetracarboxylic anhydride and benzoic acid is 1-1.2:2.0-2.5:1.2-1.3:2.3-2.

6.

4. The fiber containing plant-based composite mosquito repellent material according to claim 2, characterized in that, The ratio of 2,2'-disulfonic acid benzidine to m-cresol is 1g:15-20mL; The amount of deionized water added during precipitation is 8 to 10 times the volume of the reaction system.

5. The fiber containing plant-based composite mosquito repellent material according to claim 1, characterized in that, The mass ratio of the sulfonated polyimide to deionized water is 1:20-25; The calcium chloride solution has a mass fraction of 3-5%; The molar ratio of the sulfonated polyimide to calcium ions in the calcium chloride solution is 1:1.1 to 1.

3.

6. The fiber containing plant-based composite mosquito repellent material according to claim 1, characterized in that, The amount of the plant extract with mosquito-repellent function added is 30-40% of the mass of sulfonated polyimide; The plant extracts with mosquito-repellent function are one or more of the following: eucalyptus extract, rosemary extract, Japanese cypress extract, peppermint extract, cedarwood extract, Masson pine extract, grapefruit extract, camphor extract, thyme extract, chrysanthemum extract, bamboo leaf and Sichuan pepper extract, arborvitae extract, lemongrass extract, cinnamon extract, geranium extract, artemisia extract, lavender extract, and sweet basil extract.

7. The fiber containing plant-based composite mosquito repellent material according to claim 1, characterized in that, The high-speed shearing rate is 10,000 to 12,000 rpm, and the time is 5 to 7 minutes; The surfactant is one or more of polyoxyethylene sorbitan fatty acid ester and sorbitan fatty acid ester, and the amount added is 2 to 4% of the mass of the plant extract with mosquito repellent function.

8. The fiber containing plant-based composite mosquito repellent material according to claim 1, characterized in that, The sodium carbonate solution has a mass fraction of 3-5% and a dropping rate of 1-3 mL / min. The amount of sodium carbonate solution added is based on the molar ratio of sodium carbonate in the sodium carbonate solution to calcium ions in the emulsion, which is 1.05 to 1.2:

1. The stirring speed is 300-400 rpm; The freeze-drying temperature is -50 to -40°C, and the time is 10 to 12 hours.

9. The fiber containing plant-based composite mosquito repellent material according to claim 1, characterized in that, The spinning process involves adding the plant-based composite mosquito repellent material to a spinning solution or polymer chips, blending them together, and then performing wet spinning or melt spinning to obtain fibers containing the plant-based composite mosquito repellent material.

10. The fiber containing plant-based composite mosquito repellent material according to claim 1, characterized in that, The spinning solution is one of viscose spinning solution, acrylic spinning solution, lyocell spinning solution, or modal spinning solution; The polymer chips are one of polyester chips, nylon chips, or polypropylene chips.

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