Anti-mite, antibacterial and moisture-permeable composite fiber material and its preparation process

Abstract

The present invention discloses an anti-mite, bacteriostatic and moisture-permeable composite fiber material and its preparation process, belonging to the technical field of composite fiber preparation. The present invention is used to solve the technical problems that the anti-mite and bacteriostatic effects of composite fiber materials in the prior art need to be improved, and the retention of the anti-mite and bacteriostatic effects of composite fibers is poor after multiple water washes. The anti-mite, bacteriostatic and moisture-permeable composite fiber material is prepared by electrospinning a spinning solution composed of the following components in parts by weight: 1-3 parts of antibacterial and anti-mite agent, 1-3 parts of polyurethane, 4-12 parts of polyacrylonitrile, and 30-90 parts of N,N-dimethylformamide. The present invention not only effectively improves the anti-mite and bacteriostatic effects of composite fiber materials, but also can organically blend the anti-mite and bacteriostatic agents with the composite fiber materials, so that the composite fiber materials still have good anti-mite and bacteriostatic effects after multiple water washes, and improve the moisture-permeability of the fabrics prepared from the composite fiber materials.

Description

Technical Field

[0001] The present invention relates to the technical field of composite fiber preparation, and specifically relates to a mite-proof, bacteriostatic and moisture-permeable composite fiber material and its preparation process. Background Art

[0002] Composite fiber is a kind of multi-component man-made fiber. By using composite fiber manufacturing technology, a two-component fiber with the characteristics of two polymers can be obtained. There are side-by-side type, core-shell type, sea-island type and other composite fibers, and the fiber cross-section is circular and irregular. The fiber has three-dimensional crimp, high bulkiness and covering property, good conductivity, antistatic property and flame retardancy.

[0003] Composite fiber materials are usually used as raw materials for textiles. During the use of the finished products prepared from composite fiber materials, the temperature and humidity of the environment where they are located are very suitable for the growth of mites. During the storage process between seasons, a large number of mites and germs are easily bred on them, which can easily cause great damage to the human body.

[0004] In the prior art, the mite-proof and bacteriostatic effects of the fabrics prepared from composite fiber materials need to be improved. To avoid the breeding of a large number of mites or germs on them, the fabrics prepared from composite fiber materials need to be frequently replaced and washed. In the prior art, the mite-proof and bacteriostatic effects of composite fiber materials are usually achieved by padding the composite fiber materials with a mite-proof and antibacterial liquid, so that the composite fiber materials have mite-proof and bacteriostatic effects. However, after multiple water washes of the composite fiber materials, the mite-proof and bacteriostatic agents on the composite fibers are easily separated from the composite fibers, reducing their mite-proof and bacteriostatic effects, resulting in a low retention rate of the mite-proof and antibacterial effects of the composite fiber materials after water washing, and it is inconvenient to use.

[0005] In view of this technical defect, a solution is now proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a mite-proof, bacteriostatic and moisture-permeable composite fiber material and its preparation process, which are used to solve the technical problems that the mite-proof and bacteriostatic effects of composite fiber materials in the prior art need to be improved, and the mite-proof and bacteriostatic effects of the composite fibers in the prior art are usually achieved by padding the finished composite fiber products with a mite-proof and bacteriostatic liquid, so that the composite fibers have mite-proof and bacteriostatic effects. After multiple water washes of the composite fiber materials, the mite-proof and bacteriostatic effects of the composite fibers are significantly reduced, and the retention rate of the mite-proof and bacteriostatic effects of the composite fibers after multiple water washes is poor.

[0007] The purpose of the present invention can be achieved by the following technical solutions:

[0008] The mite-proof, bacteriostatic and moisture-permeable composite fiber material is prepared by electrospinning a spinning solution composed of the following components in parts by weight: 1-3 parts of antibacterial and anti-mite agent, 1-3 parts of polyurethane, 4-12 parts of polyacrylonitrile, and 30-90 parts of N,N-dimethylformamide;

[0009] The anti-mite and antibacterial agent is prepared by reacting trifluoroethylene, acrylic acid, 4-aminostyrene, tetrahydrofuran and an initiator through a chemical reaction to obtain intermediate I with a long straight-chain structure, and then grafting methyl 5-allyl-3-methoxysalicylate and methyltriphenylphosphonium bromide onto intermediate I.

[0010] Furthermore, the voltage of the electrospinning machine is 50 kV, the receiving distance is 18 cm, and the roller rotation speed is 70 r / min.

[0011] The preparation process of the anti-mite, antibacterial and moisture-permeable composite fiber material includes the following operating steps:

[0012] S1. Weigh 16 - 32 parts by weight of trifluoroethylene, 9 - 18 parts by weight of acrylic acid, 12 - 24 parts by weight of 4-aminostyrene, 50 - 100 parts by weight of tetrahydrofuran and 1 - 3 parts by weight of an initiator, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 50 - 60 °C and react for 6 - 8 h. After the reaction, carry out post-treatment to obtain intermediate I;

[0013] The synthesis principle of intermediate I is as follows:

[0014]

[0015] S2. Weigh 10 - 20 parts by weight of methyl 5-allyl-3-methoxysalicylate, 30 - 60 parts by weight of 20 wt% sodium hydroxide solution and 30 - 60 parts by weight of toluene, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 80 - 90 °C and carry out post-treatment after the reaction to obtain intermediate II;

[0016] The synthesis reaction of intermediate II is as follows:

[0017]

[0018] S3. Weigh 40 - 80 parts by weight of intermediate I, 20 - 40 parts by weight of intermediate II, 60 - 120 parts by weight of ethyl acetate and 2 - 4 parts by weight of a catalyst, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 60 - 70 °C and react for 10 - 14 h. After the reaction, carry out post-treatment to obtain intermediate III;

[0019] The synthesis reaction of intermediate III is as follows:

[0020]

[0021] S4. Weigh 60 - 120 parts by weight of intermediate III and 90 - 180 parts by weight of acetone, add them to a three-necked flask and stir. Weigh 60 - 120 parts by weight of 50 wt% aqueous solution of methyltriphenylphosphonium bromide and slowly add it to the three-necked flask, stir for 1 - 2 h, and carry out post-treatment after the reaction to obtain the anti-mite and antibacterial agent;

[0022] S5. Weigh 1 - 3 parts by weight of the anti - mite and antibacterial agent, 1 - 3 parts of polyurethane, 4 - 12 parts of polyacrylonitrile, and 30 - 90 parts of N,N - dimethylformamide, add them to a beaker and stir. Raise the temperature to 40 - 60 °C and stir until the system becomes clear to obtain a spinning solution.

[0023] S6. The spinning solution is pumped into an electrospinning machine through a metering pump for spinning to obtain a composite fiber material.

[0024] Furthermore, in step S1, the initiator is azobisisobutyronitrile, diacyl peroxide, or persulfate, and in step S3, the catalyst is 2 - iodo - 5 - methoxybenzeneboronic acid.

[0025] Furthermore, the post - treatment operation steps after the reaction in step S1 are: After the reaction is completed, perform vacuum distillation until no liquid flows out to obtain intermediate I.

[0026] Furthermore, the post - treatment operation steps after the reaction in step S2 are: After the reaction is completed, cool the three - necked flask to room temperature, let it stand for 30 - 50 min, separate the liquid. Wash the organic phase three times with 60 - 120 parts by weight of saturated sodium carbonate solution. Add the organic phase to the three - necked flask, raise the temperature of the three - necked flask to 80 - 90 °C, and perform vacuum distillation until no liquid flows out to obtain intermediate II.

[0027] Furthermore, the post - treatment operation steps in step S3 are: After the reaction is completed, lower the temperature of the three - necked flask to 10 - 20 °C, add 20wt% sodium hydroxide solution dropwise to the three - necked flask until the pH of the system is 7 - 8, stir for 2 - 3 h, let it stand and separate the liquid. Wash the organic phase three times with 60 - 120 parts of purified water, and perform vacuum distillation until no liquid flows out to obtain intermediate III.

[0028] Furthermore, the post - treatment operation steps in step S4 are: Raise the temperature of the three - necked flask to 70 - 80 °C, perform vacuum distillation until no liquid flows out. Then add 90 - 180 parts of toluene and 30 - 60 parts of purified water to the three - necked flask, stir for 30 - 50 min, let it stand and separate the liquid. Raise the temperature of the three - necked flask to 70 - 80 °C and perform vacuum distillation until no liquid flows out to obtain the anti - mite and antibacterial agent.

[0029] The present invention has the following beneficial effects:

[0030] 1. In the anti-mite and antibacterial agent of the present invention, methyl 5-allyl-3-methoxysalicylate and methyltriphenylphosphonium bromide are grafted together. 2-methoxy-4-(2-propenyl)phenol on methyl 5-allyl-3-methoxysalicylate has a strong clove and spicy aroma and has good repellent and killing effects on mites. Methyltriphenylphosphonium bromide has good bactericidal effects, so that the anti-mite and antibacterial agent has good mite inhibition rate and bacteria inhibition rate. The anti-mite and antibacterial agent, polyurethane, and polyacrylonitrile all have long straight-chain structures. The anti-mite and antibacterial agent, polyurethane, and polyacrylonitrile are intertwined, cross-linked, mixed, and melted together to form a whole, improving the anti-mite and antibacterial effects of the composite fiber material and reducing the separation amount of the anti-mite and antibacterial agent and the composite fiber during the washing process. The composite fiber material still has good mite inhibition rate and bacteria inhibition rate after washing.

[0031] 2. The anti-mite and antibacterial agent of the present invention has a carbon skeleton with a long straight-chain structure. After hydrolysis pretreatment of methyl 5-allyl-3-methoxysalicylate, the 2-methoxy-4-(2-propenyl)phenol group on methyl 5-allyl-3-methoxysalicylate is bonded to the carbon skeleton through an ester bond to form a stable chemical bond with the carbon skeleton. Methyltriphenylphosphonium bromide is connected to the carbon skeleton through an ionic bond, avoiding the separation of the 2-methoxy-4-(2-propenyl)phenol group or methyltriphenylphosphonium bromide from the composite fiber during the washing process, thereby preventing the rapid decrease of the mite inhibition rate and bacteria inhibition rate of the composite fiber after washing, and enabling the composite fiber to have a good retention of the mite inhibition rate and bacteria inhibition rate after multiple washes.

[0032] 3. The carbon skeleton of the long straight-chain structure of the anti-mite and antibacterial agent of the present invention contains a large number of C-F bonds, making the anti-mite and antibacterial agent have good hydrophobic properties, enabling the composite fiber material to have good hydrophobic properties, and further avoiding the swelling of the composite fiber material after absorbing water, thus ensuring the stability of the pores formed between the radial fibers and transverse fibers on the fabric prepared from the composite material. In addition, the 2-methoxy-4-(2-propenyl)phenol group and methyltriphenylphosphorus on the anti-mite and antibacterial agent are stably connected to the carbon skeleton through chemical bonds, preventing the disordered distribution of 2-methoxy-4-(2-propenyl)phenol and methyltriphenylphosphonium bromide from causing the external surface of the composite fiber material to be uneven, and further improving the moisture permeability of the composite fiber material. Detailed Embodiments

[0033] Next, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0034] Example 1

[0035] The mite-proof, bacteriostatic and moisture-permeable composite fiber material of this example is prepared by electrospinning a spinning solution composed of the following components in parts by weight: 2 g of antibacterial and acaricidal agent, 2 g of polyurethane, 8 g of polyacrylonitrile, and 60 g of N,N-dimethylformamide;

[0036] The acaricidal and antibacterial agent is prepared by a chemical reaction of trifluoroethylene, acrylic acid, 4-aminostyrene, tetrahydrofuran and an initiator to obtain an intermediate I with a long straight-chain structure, and then grafting methyl 5-allyl-3-methoxysalicylate and methyltriphenylphosphonium bromide on the intermediate I.

[0037] The voltage of the electrospinning machine is 50 kV, the receiving distance is 18 cm, and the roller speed is 70 r / min.

[0038] Example 2

[0039] The preparation process of the mite-proof, bacteriostatic and moisture-permeable composite fiber material of this example includes the following operating steps:

[0040] S1. Weigh 32 g of trifluoroethylene, 19 g of acrylic acid, 24 g of 4-aminostyrene, 100 g of tetrahydrofuran and 2 g of azobisisobutyronitrile in parts by weight, add them to a three-necked flask and stir. The temperature of the three-necked flask is raised to 50 °C and reacted for 6 h. After the reaction is completed, distill under reduced pressure until no liquid flows out to obtain intermediate I;

[0041] S2. Weigh 30 g of methyl 5-allyl-3-methoxysalicylate, 90 g of 20 wt% sodium hydroxide solution and 90 g of toluene in parts by weight, add them to a three-necked flask and stir. The temperature of the three-necked flask is raised to 80 °C. After the reaction is completed, the temperature of the three-necked flask is cooled to room temperature, allowed to stand for 30 min, separated by liquid, and the organic phase is washed three times with 180 g of saturated sodium carbonate solution. The organic phase is added to the three-necked flask, and the temperature of the three-necked flask is raised to 80 °C, and distilled under reduced pressure until no liquid flows out to obtain intermediate II;

[0042] S3. Weigh 40 g of intermediate I, 20 g of intermediate II, 60 g of ethyl acetate and 2 g of 2-iodo-5-methoxyphenylboronic acid in parts by weight, add them to a three-necked flask and stir. The temperature of the three-necked flask is raised to 60 °C and reacted for 10 h. After the reaction is completed, the temperature of the three-necked flask is lowered to 10 °C, and 20 wt% sodium hydroxide solution is added dropwise to the three-necked flask until the system pH = 7, stirred for 2 h, allowed to stand and separated by liquid. The organic phase is washed three times with 60 g of purified water, and distilled under reduced pressure until no liquid flows out to obtain intermediate III;

[0043] S4. Weigh 60 g of intermediate III and 90 g of acetone by weight parts, add them to a three-necked flask and stir. Weigh 60 g of a 50 wt% aqueous solution of methyltriphenylphosphonium bromide, slowly add it to the three-necked flask, stir for 1 h. After the reaction is completed, raise the temperature of the three-necked flask to 70 °C, and distill under reduced pressure until no liquid flows out. Then add 90 g of toluene and 30 g of purified water to the three-necked flask, stir for 30 min, let it stand for liquid separation, raise the temperature of the three-necked flask to 70 °C and distill under reduced pressure until no liquid flows out to obtain an anti-mite and antibacterial agent;

[0044] S5. Weigh 2 g of the anti-mite and antibacterial agent, 2 g of polyurethane, 8 g of polyacrylonitrile and 60 g of N,N-dimethylformamide by weight parts, add them to a beaker and stir. Raise the temperature to 40 °C and stir until the system becomes clear to obtain a spinning solution;

[0045] S6. The spinning solution is pumped into an electrospinning machine through a metering pump for electrospinning to obtain a composite fiber material.

[0046] Example 3

[0047] The preparation process of the anti-mite, antibacterial and moisture-permeable composite fiber material in this example includes the following operating steps:

[0048] S1. Weigh 48 g of trifluoroethylene, 25 g of acrylic acid, 36 g of 4-aminostyrene, 150 g of tetrahydrofuran and 4 g of diacyl peroxide by weight parts, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 55 °C and react for 7 h. After the reaction is completed, distill under reduced pressure until no liquid flows out to obtain intermediate I;

[0049] S2. Weigh 45 g of methyl 5-allyl-3-methoxysalicylate, 135 g of a 20 wt% sodium hydroxide solution and 135 g of toluene by weight parts, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 85 °C. After the reaction is completed, cool the three-necked flask to room temperature, let it stand for 40 min, separate the liquid. Wash the organic phase three times with 270 g of saturated sodium carbonate solution. Add the organic phase to the three-necked flask, raise the temperature of the three-necked flask to 85 °C, and distill under reduced pressure until no liquid flows out to obtain intermediate II;

[0050] S3. Weigh 60 g of intermediate I, 30 g of intermediate II, 80 g of ethyl acetate and 3 g of 2-iodo-5-methoxyphenylboronic acid by weight parts, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 65 °C and react for 12 h. After the reaction is completed, lower the temperature of the three-necked flask to 15 °C, add a 20 wt% sodium hydroxide solution dropwise to the three-necked flask until the pH of the system is 7, stir for 2.5 h, let it stand for liquid separation. Wash the organic phase three times with 80 g of purified water, and distill under reduced pressure until no liquid flows out to obtain intermediate III;

[0051] S4. Weigh 80 g of intermediate III and 135 g of acetone, add them to a three-necked flask and stir. Weigh 80 g of a 50 wt% aqueous solution of methyltriphenylphosphonium bromide, slowly add it to the three-necked flask, stir for 1.5 h. After the reaction is completed, raise the temperature of the three-necked flask to 75 °C and distill under reduced pressure until no liquid flows out. Then add 135 g of toluene and 45 g of purified water to the three-necked flask, stir for 40 min, let it stand for liquid separation, raise the temperature of the three-necked flask to 75 °C and distill under reduced pressure until no liquid flows out to obtain the mite-proof and bacteriostatic agent;

[0052] S5. Weigh 4 g of the mite-proof and bacteriostatic agent, 4 g of polyurethane, 16 g of polyacrylonitrile and 120 g of N,N-dimethylformamide by weight, add them to a beaker and stir. Raise the temperature to 50 °C and stir until the system becomes clear to obtain the spinning solution;

[0053] S6. The spinning solution is pumped into an electrospinning machine through a metering pump for electrospinning to obtain the composite fiber material.

[0054] Example 4

[0055] The preparation process of the mite-proof, bacteriostatic and moisture-permeable composite fiber material in this example includes the following operating steps:

[0056] S1. Weigh 64 g of trifluoroethylene, 36 g of acrylic acid, 48 g of 4-aminostyrene, 200 g of tetrahydrofuran and 6 g of persulfate by weight, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 60 °C and react for 8 h. After the reaction is completed, distill under reduced pressure until no liquid flows out to obtain intermediate I;

[0057] S2. Weigh 60 g of methyl 5-allyl-3-methoxysalicylate, 180 g of a 20 wt% sodium hydroxide solution and 180 g of toluene by weight, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 90 °C. After the reaction is completed, cool the three-necked flask to room temperature, let it stand for 50 min, separate the liquid. Wash the organic phase three times with 360 g of saturated sodium carbonate solution. Add the organic phase to the three-necked flask, raise the temperature of the three-necked flask to 90 °C and distill under reduced pressure until no liquid flows out to obtain intermediate II;

[0058] S3. Weigh 80 g of intermediate I, 40 g of intermediate II, 120 g of ethyl acetate and 4 g of 2-iodo-5-methoxyphenylboronic acid by weight, add them to a three-necked flask and stir. Raise the temperature of the three-necked flask to 70 °C and react for 14 h. After the reaction is completed, lower the temperature of the three-necked flask to 20 °C. Add a 20 wt% sodium hydroxide solution dropwise to the three-necked flask until the pH of the system is 7, stir for 3 h, let it stand for liquid separation. Wash the organic phase three times with 120 g of purified water and distill under reduced pressure until no liquid flows out to obtain intermediate III;

[0059] S4. Weigh 120 g of intermediate III and 180 g of acetone by weight parts, add them to a three-necked flask and stir. Weigh 120 g of a 50 wt% aqueous solution of methyltriphenylphosphonium bromide, slowly add it to the three-necked flask, stir for 2 h. After the reaction is completed, raise the temperature of the three-necked flask to 80 °C, and distill under reduced pressure until no liquid flows out. Then add 180 g of toluene and 60 g of purified water to the three-necked flask, stir for 50 min, let it stand for liquid separation, raise the temperature of the three-necked flask to 80 °C and distill under reduced pressure until no liquid flows out to obtain an anti-mite and antibacterial agent;

[0060] S5. Weigh 6 g of the anti-mite and antibacterial agent, 6 g of polyurethane, 24 g of polyacrylonitrile and 180 g of N,N-dimethylformamide by weight parts, add them to a beaker and stir. Raise the temperature to 60 °C and stir until the system becomes clear to obtain a spinning solution;

[0061] S6. The spinning solution is pumped into an electrospinning machine through a metering pump for spinning to obtain a composite fiber material.

[0062] Comparative Example 1

[0063] The difference between this comparative example and Example 4 is that the anti-mite and antibacterial agent in Step S5 is a mixture of 2-methoxy-4-(2-propenyl)phenol and methyltriphenylphosphonium bromide.

[0064] Comparative Example 2

[0065] The difference between this comparative example and Example 4 is that the operation step S2 is cancelled.

[0066] Comparative Example 3

[0067] The difference between this comparative example and Example 4 is that the pH of the reaction system is not adjusted with sodium hydroxide solution in the post-treatment operation of S3.

[0068] Performance test:

[0069] The anti-mite effect and antibacterial effect of the composite fibers prepared in Examples 2-4 and Comparative Examples 1-3 before washing and after washing 60 times are detected, and the composite fibers are made into fabrics to detect their moisture permeability. Among them, the anti-mite effect is detected for the composite fibers with reference to the standard GB / T 24353-2009 "Evaluation of anti-mite performance of textiles", and the antibacterial consumption is detected for the composite fibers with reference to the third part of the standard GB / T 20944.3-2008 "Evaluation of antibacterial performance of textiles": Oscillation method. The specific detection results are shown in the following table:

[0070]

[0071] Analysis based on the data in the above table:

[0072] 1) Analyze the data of Comparative Example 1 and Example 4. Before water washing, the bacteriostatic rate and acarid inhibitory rate of Comparative Example 1 were similar to those of Example 4, indicating that 2-methoxy-4-(2-propenyl)phenol grafted on Intermediate I and methyltriphenylphosphonium bromide had acarid and antibacterial effects. However, after 60 times of water washing, the bacteriostatic rate and acarid inhibitory rate of the composite fiber in Comparative Example 1 decreased rapidly. This was because the acarid and bacteriostatic agent in Comparative Example 1 was an auxiliary additive. The acarid and bacteriostatic agent was melted and mixed with the spinning solution, and other components in the spinning solution were wrapped together with the acarid and bacteriostatic agent, with part of the acarid and bacteriostatic agent exposed on the outside of the composite fiber. During the water washing process, 2-methoxy-4-(2-propenyl)phenol and methyltriphenylphosphonium bromide on the composite fiber were separated from the composite fiber, resulting in a decrease in the content of 2-methoxy-4-(2-propenyl)phenol and methyltriphenylphosphonium bromide on the composite fiber, and thus a rapid decrease in the bacteriostatic rate and acarid inhibitory rate of the composite fiber in Comparative Example 1 after water washing. The acarid and bacteriostatic agents in Examples 2-4 were used to prepare Intermediate I through chemical reactions. Intermediate I was a high molecular polymer with a long straight-chain structure. Intermediate I was similar to polyurethane and polyacrylonitrile in structure, all having long straight-chain structures. Intermediate I, polyurethane, and polyacrylonitrile were intertwined, crosslinked, mixed, and melted together to form an organic whole. 2-methoxy-4-(2-propenyl)phenol was bonded to Intermediate I through an ester group, and methyltriphenylphosphonium bromide was connected to Intermediate I through an ionic bond, so that 2-methoxy-4-(2-propenyl)phenol and methyltriphenylphosphonium bromide were stably connected to Intermediate I. During the water washing process, since Intermediate I, polyurethane, and polyacrylonitrile were all insoluble in water, Intermediate I could not detach from the synthetic fiber. Therefore, during the water washing process of the composite fiber prepared in Examples 2-4, 2-methoxy-4-(2-propenyl)phenol and methyltriphenylphosphonium bromide on the composite fiber would not be separated from the composite fiber or the amount of separation was small, maintaining a relatively high content of 2-methoxy-4-(2-propenyl)phenol and methyltriphenylphosphonium bromide on the composite fiber. As a result, the composite fiber prepared in Examples 2-4 still had good bacteriostatic rate and acarid inhibitory rate after 60 times of water washing.

[0073] 2) By analyzing the data of Comparative Examples 2-3 and Example 4, before water washing, the bacteriostatic rate and acarid inhibitory rate of Comparative Examples 2-3 were similar to those of Example 4. However, after 60 times of water washing in Comparative Example 2, the acarid inhibitory rate decreased significantly. After 60 times of water washing in Comparative Example 3, the bacteriostatic rate decreased significantly. This is because in Comparative Example 2, operation step S2 was cancelled, and methyl 5-allyl-3-methoxysalicylate could not be hydrolyzed to form intermediate II, which led to that methyl 5-allyl-3-methoxysalicylate could not be grafted onto intermediate I, and 2-methoxy-4-(2-propenyl) phenol could not establish a stable chemical connection with intermediate I. During the water washing process, methyl 5-allyl-3-methoxysalicylate was separated from the composite fiber, resulting in a decrease in the acarid inhibitory rate. This also shows that 2-methoxy-4-(2-propenyl) phenol on methyl 5-allyl-3-methoxysalicylate has good acarid inhibitory effect. In Comparative Example 3, sodium hydroxide solution was not used to adjust the pH of the reaction system in the post-treatment operation, and the carboxyl group on intermediate III could not form sodium salt. In step S4, a large amount of -COO could not be decomposed from intermediate III. - , resulting in that the positively charged methyl triphenylphosphonium separated from the aqueous solution of methyl triphenylphosphonium bromide could not form an ionic covalent bond with intermediate III. During the water washing process, methyl triphenylphosphonium bromide was dissolved and separated from the composite fiber, leading to a significant decrease in the bacteriostatic effect;

[0074] 3) By analyzing the detected data of moisture permeability in the table, it can be seen that the moisture permeability of Comparative Examples 1-3 was much lower than that of Examples 2-4. This is because 2-methoxy-4-(2-propenyl) phenol and methyl triphenylphosphonium bromide on the composite fibers prepared in Comparative Examples 1-3 could not establish a stable connection with the composite fibers. 2-methoxy-4-(2-propenyl) phenol or methyl triphenylphosphonium bromide adhered to the outside of the composite fibers prepared in Comparative Examples 1-3, and there were a large number of protrusions on the outside of the composite fibers, resulting in uneven pore sizes between the radial fibers and the transverse fibers of the fabrics prepared from the composite fibers in Comparative Examples 1-3 by the same textile method as in Examples 2-4. The moisture permeability of the fabrics prepared from Comparative Examples 1-3 was relatively low. Since C-F bonds were introduced into the acarid and bacteriostatic agents in Examples 2-4, the composite fibers had good hydrophobic properties. The acarid and bacteriostatic agent in Comparative Example 1 did not contain C-F bonds, resulting in poor hydrophobic properties of the composite fibers prepared in Comparative Example 1. During the moisture permeability experiment, the water vapor wet the composite fibers, causing the pores on the fabric to further shrink and reducing its moisture permeability.

[0075] The above content is only an example and illustration of the structure of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar ways to replace them. As long as it does not deviate from the structure of the invention or exceed the scope defined by this claim book, it shall fall within the protection scope of the present invention.

[0076] In the description of this specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0077] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the present invention to only the specific implementation manners. Obviously, according to the content of this specification, many modifications and changes can be made. This specification selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the art of this technology can understand and utilize the present invention well. The present invention is only limited by the claim book and its full scope and equivalents.

Claims

1. Preparation process of a composite fiber material with mite-proof, bacteriostatic and moisture-permeable properties, characterized in that, It includes the following operation steps: S1. Weigh 16 - 32 parts by weight of trifluoroethylene, 9 - 18 parts of acrylic acid, 12 - 24 parts of 4 - aminostyrene, 50 - 100 parts of tetrahydrofuran and 1 - 3 parts of initiator, add them into a three - necked flask and stir. Heat the temperature of the three - necked flask to 50 - 60 °C, react for 6 - 8 h, and perform post - treatment after the reaction to obtain intermediate I; S2. Weigh 10 - 20 parts by weight of methyl 5 - allyl - 3 - methoxysalicylate, 30 - 60 parts of 20 wt% sodium hydroxide solution and 30 - 60 parts of toluene, add them into a three - necked flask and stir. Heat the temperature of the three - necked flask to 80 - 90 °C, and perform post - treatment after the reaction to obtain intermediate II; S3. Weigh 40 - 80 parts by weight of intermediate I, 20 - 40 parts of intermediate II, 60 - 120 parts of ethyl acetate and 2 - 4 parts of catalyst, add them into a three - necked flask and stir. Heat the temperature of the three - necked flask to 60 - 70 °C, react for 10 - 14 h, and perform post - treatment after the reaction to obtain intermediate III. Among them, the post - treatment operation steps are: after the reaction is completed, lower the temperature of the three - necked flask to 10 - 20 °C, dropwise add 20 wt% sodium hydroxide solution to the three - necked flask until the pH of the system is 7 - 8, stir for 2 - 3 h, let it stand for liquid separation, wash the organic phase three times with 60 - 120 parts of purified water, and perform reduced - pressure distillation until no liquid flows out to obtain intermediate III; S4. Weigh 60 - 120 parts by weight of intermediate III and 90 - 180 parts of acetone, add them into a three - necked flask and stir. Weigh 60 - 120 parts of 50 wt% aqueous solution of methyltriphenylphosphonium bromide, slowly add it into the three - necked flask, stir for 1 - 2 h, and perform post - treatment after the reaction to obtain the mite - proof and antibacterial agent; S5. Weigh 1 - 3 parts by weight of the mite - proof and antibacterial agent, 1 - 3 parts of polyurethane, 4 - 12 parts of polyacrylonitrile and 30 - 90 parts of N,N - dimethylformamide, add them into a beaker and stir. Heat the temperature to 40 - 60 °C, stir until the system becomes clear to obtain the spinning solution; S6. The spinning solution is pumped into an electrospinning machine through a metering pump for spinning to obtain the composite fiber material.

2. The preparation process of the mite-proof, bacteriostatic and moisture-permeable composite fiber material according to claim 1, characterized in that, In step S1, the initiator is azobisisobutyronitrile, diacyl peroxide or persulfate, and in step S3, the catalyst is 2 - iodo - 5 - methoxyphenylboronic acid.

3. The preparation process of the mite-proof, bacteriostatic and moisture-permeable composite fiber material according to claim 1, characterized in that, The post - treatment operation steps after the reaction in step S1 are: after the reaction is completed, perform reduced - pressure distillation until no liquid flows out to obtain intermediate I.

4. The preparation process of the mite-proof, bacteriostatic and moisture-permeable composite fiber material according to claim 1, characterized in that, The post - treatment operation steps in step S2 are: after the reaction is completed, cool the three - necked flask to room temperature, let it stand for 30 - 50 min, perform liquid separation, wash the organic phase three times with 60 - 120 parts by weight of saturated sodium carbonate solution, add the organic phase into the three - necked flask, heat the temperature of the three - necked flask to 80 - 90 °C, and perform reduced - pressure distillation until no liquid flows out to obtain intermediate II.

5. The preparation process of the mite-proof, bacteriostatic and moisture-permeable composite fiber material according to claim 1, characterized in that, The post - treatment operation steps in step S4 are: raise the temperature of the three - necked flask to 70 - 80 °C, perform reduced - pressure distillation until no liquid flows out, then add 90 - 180 parts of toluene and 30 - 60 parts of purified water into the three - necked flask, stir for 30 - 50 min, let it stand for liquid separation, raise the temperature of the three - necked flask to 70 - 80 °C and perform reduced - pressure distillation until no liquid flows out to obtain the mite - proof and antibacterial agent.

6. The preparation process of the mite-proof, bacteriostatic and moisture-permeable composite fiber material according to claim 1, characterized in that, In step S5, the voltage of the electrospinning machine is 50 kV, the receiving distance is 18 cm, and the roller rotation speed is 70 r / min.

7. A composite fiber material with mite-proof, bacteriostatic and moisture-permeable properties, characterized in that, The mite-proof, bacteriostatic and moisture-permeable composite fiber material is processed by using the preparation process of the mite-proof, bacteriostatic and moisture-permeable composite fiber material according to any one of claims 1-6.

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