Preparation method of antifouling self-cleaning goat glove leather

Abstract

The invention relates to the technical field of leather products, in particular to a preparation method of antifouling self-cleaning goat glove leather, which comprises the following steps: S1, putting goat leather into a cleaning tank for salt washing; s2, putting the goat leather subjected to salt washing into a softening tank for softening, and washing with water after softening; s3, acid leaching is conducted in an acid leaching tank, and tanning is conducted after acid leaching is completed; and S4, oxidation treatment is conducted in an oxidation tank, washing is conducted after oxidation treatment, tanned goat glove leather is obtained, the tanned goat glove leather is soaked in the steeping liquor, and the goat glove leather is taken out and dried. By introducing the copolymer of sulfur-modified polymethyl methacrylate and methyl butene, not only is the resistance of the leather to dirt enhanced, but also the dirt is easier to fall off from the surface of the leather. Meanwhile, the protective film effectively prevents water and dirt from permeating, so that the service life of the leather is prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of leather products, in particular to a method for preparing anti-fouling self-cleaning goat glove leather. Background Art

[0002] Goat glove leather is a unique leather material with excellent texture, unique feel and excellent performance. It occupies an important position in gloves and other leather products. Goat leather itself has a unique texture and delicate texture. Its surface layer is thick, the structure is strong, the tensile strength is good, and it has good breathability and wear resistance, making goat leather an ideal choice for making high-end gloves. Goat glove leather not only has excellent physical properties, but is also favored for its unique appearance and feel. The subtle concave and convex texture on its surface gives the gloves a natural beauty and layering. In addition, the softness and comfort of goat leather are also one of the important reasons for its popularity. It can fit the contour of the hand closely and provide an excellent wearing experience. Goat glove leather is widely used in various glove products, such as driving gloves, sports gloves, etiquette gloves, etc. Driving gloves need to have good grip and wear resistance. Goat glove leather just meets these requirements, providing drivers with a safe and comfortable driving experience. Sports gloves pay more attention to breathability and flexibility. The breathability and softness of goat leather make it an ideal material for making sports gloves. Ceremonial gloves pay more attention to appearance and texture. The delicate texture and unique luster of goat glove leather make it an excellent product for ceremonial occasions.

[0003] In the prior art, the cortex of goat glove leather is relatively thin, which makes it easy to be scratched or worn during use. After long-term use, the integrity of the gloves will be affected. At the same time, goat glove leather cannot usually be washed and cleaned, which limits its cleaning methods. In order to maintain the beauty of the gloves and extend their service life, professional cleaning and maintenance methods are required, which increases the complexity and cost of use. Due to the general durability of goat glove leather and the difficulty in cleaning and maintenance, its service life is relatively short. Compared with some more durable leather materials, goat glove leather may need to be replaced more frequently. Summary of the invention

[0004] In order to solve the problems mentioned in the above background technology, the present invention provides a method for preparing anti-fouling self-cleaning goat glove leather.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: A method for preparing anti-fouling self-cleaning goat glove leather comprises the following steps: S1. Put the goat leather into a cleaning tank, wash it with clean water to remove surface oil and impurities, transfer it to a salt washing tank, add sodium chloride solution, rotate for 10-20 minutes, drain the liquid, and obtain the salt-washed goat leather; S2, put the salt-washed goat leather in a softening tank, add water to adjust the liquid ratio to 1.2-1.3, heat to 36-37 ° C, add ammonium sulfate and pancreatic enzyme to soften, rotate for 45-60 minutes, and after softening, transfer to a washing tank, adjust the liquid ratio to 2.5-3.0, control the water temperature at 20-25 ° C, and wash 2-3 times, each time for 10-15 minutes to obtain pre-treated leather; S3, put the pre-treated leather in the pickling tank, add water to adjust the liquid ratio to 80%, add industrial salt, rotate for 20-30min, add formic acid with a mass concentration of ≥85% for pickling in 2-3 times, each addition amount is 8-12‰ of the leather mass, rotate for 20-30min after each addition, control the pH value to 3.4-3.6, continue to rotate for 40-60min after adding, after the pickling is completed, add organic phosphine tanning agent, rotate for 120-160min, stop the drum overnight, continue to rotate for 30-40min the next day, add sodium hydroxide in 2-3 times, rotate for 30-40min after each addition, adjust the pH value to 5.5-5.7, rotate for 60-70min, add synthetic tannin, rotate for 60-70min, and obtain tanned leather; S4. Add tanned leather to an oxidation tank, add water to adjust the liquid ratio to 150%, add an oxidant for oxidation treatment, rotate for 60-70 minutes to obtain oxidized leather, transfer the oxidized leather to a washing tank, wash with water 2-3 times until there is no residue, obtain tanned goat glove leather, immerse the tanned goat glove leather in the impregnation solution, immerse for 1-2 hours, take out and dry, and obtain a stain-resistant and self-cleaning goat glove leather.

[0006] Furthermore, in step S1, the temperature of salt washing is 29-31° C., the concentration of the sodium chloride solution is 200% to 220%, and the Baume degree is 6.

[0007] Furthermore, in step S2, the mass of ammonium sulfate added is 0.4% to 0.45% of the total mass of the leather, and the mass of pancreatic enzyme added is 0.06% to 0.08% of the total mass of the leather.

[0008] Furthermore, in step S3, the mass of industrial salt added is 6% to 8% of the total mass of the leather, the Baume degree is controlled to be 6.0-6.5, the mass of formic acid added each time is 8-12‰ of the total mass of the leather, the mass of organic phosphine tanning agent added is 1.5% to 2.5% of the total mass of the leather, and the mass of synthetic tannin added is 1.5% to 2.5% of the total mass of the leather.

[0009] Furthermore, in step S3, the organic phosphine tanning agent is tetrakishydroxymethyl phosphonium chloride or tetrakishydroxymethyl phosphonium sulfide.

[0010] Furthermore, in step S4, the oxidant is hydrogen peroxide or sodium perborate, and the mass of the added oxidant is 0.5% to 1% of the total mass of the leather.

[0011] Furthermore, the impregnation liquid in step S4 is prepared by the following steps: A1. Add polymethyl methacrylate and 3,3'-dithiodipropionic acid into a reactor filled with toluene, stir until completely dissolved, add azobisisobutyronitrile and cuprous bromide under the protection of inert gas, heat to 75-80°C in an oil bath or water bath, stir and react for 4-6 hours, and after the reaction is completed, perform vacuum distillation, collect the distillation residue, pour the distillation residue into ethanol for precipitation, filter, and dry to constant weight to obtain sulfur-modified polymethyl methacrylate; A2. Add methylbutene and sulfur-modified polymethyl methacrylate to a reactor containing N-methylpyrrolidone, stir until completely dissolved to form a uniform solution, add azobisisobutyronitrile under the protection of inert gas, heat to 60-65° C. in an oil bath or a water bath, stir and react for 10-12 hours, and after the reaction is completed, distill under reduced pressure, collect the distillation residue, pour it into ethanol for precipitation, filter, wash the filter cake with ethanol for 3-5 times, and dry it at 40-50° C. to constant weight to obtain a modified polymer solution precursor, add the modified polymer precursor to dimethylformamide, add sodium dodecylsulfonate, and prepare an impregnation solution.

[0012] Furthermore, in step A1, the mass ratio of polymethyl methacrylate, 3,3'-dithiodipropionic acid, azobisisobutyronitrile and cuprous bromide is (10-12): (2-3): (0.1-0.2): (0.05-0.08).

[0013] Furthermore, in step A2, the mass ratio of methylbutene, sulfur-modified polymethyl methacrylate and azobisisobutyronitrile is (6-7): (5-5.5): (0.05-0.1).

[0014] Furthermore, in step A2, the mass ratio of the modified polymer precursor, dimethylformamide and sodium dodecyl sulfonate is (9-10): (22-25): (0.5-2).

[0015] Beneficial effects of the present invention: 1. In the technical solution of the present invention, 3,3'-dithiodipropionic acid is grafted onto the molecular chain of polymethyl methacrylate (PMMA) through a free radical addition reaction, and sulfur is introduced into the PMMA molecular chain to form sulfur-modified PMMA. The introduction of sulfur not only changes the surface energy, polarity and compatibility of PMMA with other materials, but also introduces new active sites into the molecular chain to form a more stable structure. Under the initiation of free radical polymerization, methylbutene undergoes polymerization reaction and may be grafted onto the sulfur-modified PMMA molecular chain to form a copolymer. During the copolymerization process, the methylbutene molecular chain and the sulfur-modified PMMA molecular chain are cross-linked or entangled to form a three-dimensional network structure, so that the modified polymer solution precursor has higher strength and toughness. In the impregnation solution, the modified polymer molecules exist in the form of a dispersed phase, and sodium dodecyl sulfate, as a surfactant, can reduce the surface tension between the modified polymer molecules and the solvent, so that the modified polymer molecules are more easily dispersed in the solvent to form a stable suspension or solution. The sulfur element on the sulfur-modified PMMA molecular chain forms hydrogen bonds with the hydrogen atoms in the hydroxyl or carboxyl groups on the leather surface, forming a stable adsorption layer on the leather surface. When there are free amino groups on the leather surface, the sulfur element may form covalent bonds with the nitrogen atoms in the amino groups, thereby further enhancing the binding force between the sulfur-modified PMMA and the leather surface, thereby improving the leather's resistance to dirt. After the modified polymer molecules attach to the leather surface, they will change the surface energy, polarity, etc. of the leather surface, making the leather surface smoother and flatter, and less likely to absorb dirt.

[0016] 2. In the technical solution of the present invention, the modified polymer molecules form a dense protective film on the leather surface, which has a certain electrostatic repulsion effect, making the contact between the dirt molecules and the leather surface loose, so that it is easier to fall off the leather surface. In addition, the protective film can prevent moisture and dirt from penetrating into the leather, thereby extending the service life of the leather. DETAILED DESCRIPTION

[0017] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] Unless otherwise specified, the raw materials used in the present invention are all conventional products purchased from the market.

[0019] Preparation Example 1 The impregnation solution comprises the following steps: A1. Add 1 kg of polymethyl methacrylate and 0.2 kg of 3,3'-dithiodipropionic acid into a reactor containing 10 kg of toluene, stir until completely dissolved, add 0.01 kg of azobisisobutyronitrile and 0.005 kg of cuprous bromide under nitrogen protection, heat the oil bath to 75°C, stir and react for 4 hours, and after the reaction is completed, perform vacuum distillation, collect the distillation residue, pour the distillation residue into 10 kg of ethanol for precipitation, filter, and dry at 60°C to constant weight to obtain sulfur-modified polymethyl methacrylate; A2. Add 0.6 kg of methylbutene and 0.5 kg of sulfur-modified polymethyl methacrylate into a reactor containing 5 kg of N-methylpyrrolidone, stir until completely dissolved to form a uniform solution, add 0.005 kg of azobisisobutyronitrile under nitrogen protection, heat the oil bath to 60 ° C, stir and react for 10 hours, and after the reaction is completed, distill under reduced pressure, collect the distillation residue, pour it into 5 kg of ethanol for precipitation, filter, wash the filter cake 3 times with ethanol, and dry it at 40 ° C to constant weight to obtain a modified polymer solution precursor, add 0.9 kg of the modified polymer precursor into 2.2 kg of dimethylformamide, add 0.05 kg of sodium dodecylsulfonate, and prepare an impregnation solution.

[0020] Preparation Example 2 The impregnation solution comprises the following steps: A1. Add 1.1 kg of polymethyl methacrylate and 0.25 kg of 3,3'-dithiodipropionic acid into a reactor containing 10 kg of toluene, stir until completely dissolved, add 0.015 kg of azobisisobutyronitrile and 0.0065 kg of cuprous bromide under nitrogen protection, heat to 78° C. in a water bath, stir and react for 5 hours, and after the reaction is completed, perform vacuum distillation, collect the distillation residue, pour the distillation residue into 10 kg of ethanol for precipitation, filter, and dry at 60° C. to constant weight to obtain sulfur-modified polymethyl methacrylate; A2. Add 0.65 kg of methylbutene and 0.53 kg of sulfur-modified polymethyl methacrylate into a reactor containing 5 kg of N-methylpyrrolidone, stir until completely dissolved to form a uniform solution, add 0.008 kg of azobisisobutyronitrile under nitrogen protection, heat to 63 ° C in a water bath, stir and react for 11 hours, and after the reaction is completed, distill under reduced pressure, collect the distillation residue, pour it into 5 kg of ethanol for precipitation, filter, wash the filter cake 4 times with ethanol, and dry it at 45 ° C to constant weight to obtain a modified polymer solution precursor, add 0.95 kg of the modified polymer precursor into 2.35 kg of dimethylformamide, add 0.1 kg of sodium dodecylsulfonate, and prepare an impregnation solution.

[0021] Preparation Example 3 The impregnation solution comprises the following steps: A1. Add 1.2 kg of polymethyl methacrylate and 0.3 kg of 3,3'-dithiodipropionic acid into a reactor containing 10 kg of toluene, stir until completely dissolved, add 0.02 kg of azobisisobutyronitrile and 0.008 kg of cuprous bromide under nitrogen protection, heat the oil bath to 80°C, stir and react for 6 hours, and after the reaction is completed, perform vacuum distillation, collect the distillation residue, pour the distillation residue into 10 kg of ethanol for precipitation, filter, and dry at 60°C to constant weight to obtain sulfur-modified polymethyl methacrylate; A2. Add 0.7 kg of methylbutene and 0.55 kg of sulfur-modified polymethyl methacrylate into a reactor containing 5 kg of N-methylpyrrolidone, stir until completely dissolved to form a uniform solution, add 0.01 kg of azobisisobutyronitrile under nitrogen protection, heat the oil bath to 65 ° C, stir and react for 12 hours, and after the reaction is completed, distill under reduced pressure, collect the distillation residue, pour it into 5 kg of ethanol for precipitation, filter, wash the filter cake with ethanol 5 times, and dry it at 50 ° C to constant weight to obtain a modified polymer solution precursor, add 1 kg of the modified polymer precursor into 2.5 kg of dimethylformamide, add 0.2 kg of sodium dodecylsulfonate, and prepare an impregnation solution.

[0022] Example 1

[0023] A method for preparing anti-fouling self-cleaning goat glove leather comprises the following steps: S1. Put 1 kg of goat leather into a cleaning tank, wash it with clean water, transfer it to a salt washing tank, add a 6-degree Baume sodium chloride solution with a temperature of 29°C and a concentration of 200%, rotate for 10 minutes, drain the liquid, and obtain the goat leather after salt washing; S2, put the goat leather washed with salt in a softening tank, add water to adjust the liquid ratio to 1.2, heat to 36 ° C, add 0.4% of ammonium sulfate by weight of the leather and 0.06% of pancreatic enzyme by weight of the leather to soften, rotate for 45 minutes, and after softening, transfer to a washing tank, adjust the liquid ratio to 2.5, control the water temperature at 20 ° C, and wash twice, each time for 10 minutes to obtain pre-treated leather; S3, put the pre-treated leather in the pickling tank, add water to adjust the liquid ratio to 80%, add 6% of the leather mass of industrial salt, rotate for 20min, control the Baume degree to 6.0, add 85% formic acid by mass concentration for pickling twice, each addition amount is 8‰ of the leather mass, rotate for 20min after each addition, control the pH value to be 3.4, continue to rotate for 40min after adding, after pickling, add 1.5% of the leather mass of tetrakis hydroxymethyl phosphonium chloride, rotate for 120min, stop the drum overnight, continue to rotate for 30min the next day, add sodium hydroxide twice, rotate for 30min after each addition, adjust the pH value to 5.5, rotate for 60min, add 1.5% synthetic tannin, rotate for 60min, and obtain tanned leather; S4. Add tanned leather to the oxidation tank, add water to adjust the liquid ratio to 150%, add hydrogen peroxide at 0.5% of the leather mass for oxidation treatment, rotate for 60 minutes to obtain the oxidized leather, transfer the oxidized leather to the washing tank, wash it with water twice until there is no residue, and obtain the tanned goat glove leather. Immerse the tanned goat glove leather in the impregnation solution prepared in Preparation Example 1, immerse for 1 hour, take out and dry, and obtain a kind of anti-fouling self-cleaning goat glove leather.

[0024] Example 2

[0025] A method for preparing anti-fouling self-cleaning goat glove leather comprises the following steps: S1. Put 1 kg of goat leather into a cleaning tank, wash it with clean water, transfer it to a salt washing tank, add a 6-degree Baume sodium chloride solution with a temperature of 30°C and a concentration of 200%, rotate for 15 minutes, drain the liquid, and obtain the goat leather after salt washing; S2, put the goat leather washed with salt in a softening tank, add water to adjust the liquid ratio to 1.25, heat to 36.5 ° C, add 0.43% of ammonium sulfate by weight of the leather and 0.07% of pancreatic enzyme by weight of the leather to soften, rotate for 50 minutes, and after softening, transfer to a washing tank, adjust the liquid ratio to 2.7, control the water temperature at 23 ° C, and wash twice, each time for 10 minutes to obtain pre-treated leather; S3, put pre-treated leather in the pickling tank, add water to adjust the liquid ratio to 80%, add 7% of the leather mass of industrial salt, rotate for 25min, control the Baume degree to 6.2, add 88% formic acid by mass concentration for pickling in 2 times, each addition amount is 10‰ of the leather mass, rotate for 25min after each addition, control the pH value to be 3.5, continue to rotate for 50min after adding, after pickling, add 2% of the leather mass of tetrakis hydroxymethyl phosphonium chloride, rotate for 140min, stop the drum overnight, continue to rotate for 35min the next day, add sodium hydroxide in 2 times, rotate for 35min after each addition, adjust the pH value to 5.6, rotate for 65min, add synthetic tannin 2%, rotate for 65min, and obtain tanned leather; S4. Add tanned leather to the oxidation tank, add water to adjust the liquid ratio to 150%, add 0.8% hydrogen peroxide by weight of the leather for oxidation treatment, rotate for 65 minutes to obtain the oxidized leather, transfer the oxidized leather to the washing tank, wash twice with water until there is no residue, and obtain the tanned goat glove leather. Immerse the tanned goat glove leather in the impregnation solution prepared in Preparation Example 2, immerse for 1.5 hours, take out and dry, and obtain a kind of anti-fouling self-cleaning goat glove leather.

[0026] Example 3

[0027] A method for preparing anti-fouling self-cleaning goat glove leather comprises the following steps: S1. Put 1 kg of goat leather into a cleaning tank, wash it with clean water, transfer it to a salt washing tank, add a 6-degree Baume sodium chloride solution with a temperature of 31°C and a concentration of 200%, rotate for 20 minutes, drain the liquid, and obtain the goat leather after salt washing; S2, put the goat leather washed with salt in a softening tank, add water to adjust the liquid ratio to 1.3, heat to 37 ° C, add 0.45% of ammonium sulfate by weight of the leather and 0.08% of pancreatic enzyme by weight of the leather to soften, rotate for 60 minutes, and after softening, transfer to a washing tank, adjust the liquid ratio to 3.0, control the water temperature at 25 ° C, and wash 3 times, each time for 15 minutes to obtain pre-treated leather; S3, put the pre-treated leather in the pickling tank, add water to adjust the liquid ratio to 80%, add 8% of the leather mass of industrial salt, rotate for 30min, control the Baume degree to 6.5, add 90% formic acid by mass concentration for pickling 3 times, each addition amount is 12‰ of the leather mass, rotate for 30min after each addition, control the pH value to be 3.6, continue to rotate for 60min after adding, after pickling, add 2.5% of the leather mass of tetrakis hydroxymethyl phosphide, rotate for 160min, stop the drum overnight, continue to rotate for 40min the next day, add sodium hydroxide 3 times, rotate for 40min after each addition, adjust the pH value to 5.7, rotate for 70min, add synthetic tannin 2.5%, rotate for 70min, and obtain tanned leather; S4. Add tanned leather to the oxidation tank, add water to adjust the liquid ratio to 150%, add 1% of the leather mass of sodium perborate for oxidation treatment, rotate for 70 minutes to obtain the oxidized leather, transfer the oxidized leather to the washing tank, wash it with water 3 times until there is no residue, and obtain the tanned goat glove leather. Immerse the tanned goat glove leather in the impregnation solution prepared in Preparation Example 3, immerse for 2 hours, take out and dry, and obtain a kind of anti-fouling self-cleaning goat glove leather.

[0028] Comparative Example 1 0.9 kg of polymethyl methacrylate was added to 2.2 kg of dimethylformamide, and 0.05 kg of sodium dodecyl sulfate was added to prepare an impregnation solution.

[0029] Comparative Example 2 0.95 kg of methylbutene was added to 2.35 kg of dimethylformamide and 0.1 kg of sodium dodecylsulfonate to prepare an impregnation solution.

[0030] Comparative Example 3 1 kg of 3,3'-dithiodipropionic acid was added to 2.5 kg of dimethylformamide and 0.2 kg of sodium dodecyl sulfate to prepare an impregnation solution.

[0031] Comparative Example 4 The difference between this comparative example and Example 1 is that the impregnation solution prepared in Comparative Example 1 is used, and the remaining steps are the same as those in Example 1.

[0032] Comparative Example 5 The difference between this comparative example and Example 2 is that the impregnation solution prepared in Comparative Example 2 is used, and the remaining steps are the same as those in Example 2.

[0033] Comparative Example 6 The difference between this comparative example and Example 3 is that the impregnation solution prepared in Comparative Example 3 is used, and the remaining steps are the same as those in Example 3.

[0034] With reference to GB / T 43818.1-2024 "Determination of the wear resistance of leather Part 1: Taber method", leather samples were selected from Examples 1-3 and Comparative Examples 4-6, and the initial thickness and initial mass of each sample were measured. The parameters of the Taber wear tester were set, and the CS-10 grinding wheel was selected, the load was 1000g, the rotation speed was 72rpm, and 2000 wear cycles were performed. After the test, the samples were removed from the tester, the final thickness and final mass of each sample were measured, and the thickness loss and mass loss were calculated. Thickness loss = initial thickness - final thickness, mass loss = initial mass - final mass. The results are shown in Table 1:

[0035] Table 1. Wear resistance test results of Examples 1-3 and Comparative Examples 4-6

[0036] With reference to GB / T 41424.1-2022 "Determination of Leather Staining Properties Part 1: Tumbling Method", leather samples were selected from Examples 1-3 and Comparative Examples 4-6 for pretreatment, the initial mass of each sample was recorded, and the dirty liquid was prepared (145g of synthetic oil was weighed, placed in a 1L beaker, and slowly heated in a water bath until the oil melted. 220mL of acetone, 220mL of butanone and 25.0mL of petroleum ether were added to the beaker in sequence to dilute the oil, and 0.90mL of graphite emulsion was added to the diluted oil solution). At 20°C and 65% humidity, each pretreated sample was loaded into a drum staining device for testing, with a tumbling speed of 30rpm and a tumbling time of 60min. After the test, the final mass of each sample was measured, and the stain weight gain was calculated, stain weight gain = final mass - initial mass. The results are shown in Table 2:

[0037] Table 2. Staining performance test results of Examples 1-3 and Comparative Examples 4-6

[0038] As can be seen from Table 1, the thickness loss and mass loss of Examples 1-3 are significantly less than those of Comparative Examples 4-6, indicating that the impregnation liquid used in Examples 1-3 significantly improves the wear resistance of the leather. The copolymer of sulfur-modified polymethyl methacrylate and methylbutylene in the impregnation liquid of Examples 1-3 may form a stronger bond with the leather surface, thereby enhancing the wear resistance of the leather. The impregnation liquid in Comparative Examples 4-6 has not been modified and therefore cannot provide the same improvement in wear resistance.

[0039] As can be seen from Table 2, the weight gain of stains in Examples 1-3 is significantly less than that in Comparative Examples 4-6, indicating that the impregnation solutions in Examples 1-3 effectively improve the anti-staining properties of the leather. The modified polymer in the impregnation solution may form a thin film on the leather surface that is not easily penetrated by grease, thereby preventing the penetration and adhesion of the dirty liquid. The introduction of 3,3'-dithiodipropionic acid and methylbutene may have changed the surface properties of the polymer, making it more resistant to stains. The impregnation solutions in Comparative Examples 4-6 have not been modified and therefore cannot provide the same anti-staining properties.

[0040] In the impregnation solution prepared in Preparation Examples 1-3, the introduction of sulfur in sulfur-modified polymethyl methacrylate may change the chain structure and surface properties of the polymer, making it more firmly bonded to the leather and providing better wear resistance and anti-fouling properties. Methylbutene may copolymerize with polymethyl methacrylate to form a polymer with specific surface properties, which helps to improve the wear resistance and anti-fouling properties of the leather.

[0041] In summary, the use of the impregnation liquid prepared in Preparation Examples 1-3 in Examples 1-3 significantly improves the wear resistance and anti-fouling properties of the leather.

[0042] In the description of the specification, the description with reference to the terms "embodiment", "various embodiments" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or preparation example are included in at least one embodiment or preparation example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or preparation example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or preparation examples in a suitable manner.

[0043] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing anti-fouling self-cleaning goat glove leather, characterized in that: The following steps are involved: S1. Put the goat leather into a cleaning tank, wash it with clean water, transfer it to a salt washing tank, add sodium chloride solution for salt washing, rotate for 10-20 minutes, drain the liquid, and obtain the salt-washed goat leather; S2, put the salt-washed goat leather in a softening tank, add water to adjust the liquid ratio to 1.2-1.3, heat to 36-37 ° C, add ammonium sulfate and pancreatic enzyme to soften, rotate for 45-60 minutes, and after softening, transfer to a washing tank, adjust the liquid ratio to 2.5-3.0, control the water temperature at 20-25 ° C, and wash 2-3 times, each time for 10-15 minutes to obtain pre-treated leather; S3, put the pre-treated leather in the pickling tank, add water to adjust the liquid ratio to 80%, add industrial salt, rotate for 20-30min, add formic acid 2-3 times for pickling, rotate for 20-30min after each addition, control the pH value to 3.4-3.6, continue to rotate for 40-60min after adding, add organic phosphine tanning agent after pickling, rotate for 120-160min, stop the drum overnight, continue to rotate for 30-40min the next day, add sodium hydroxide 2-3 times, rotate for 30-40min after each addition, adjust the pH value to 5.5-5.7, rotate for 60-70min, add synthetic tannin, rotate for 60-70min, and obtain tanned leather; S4. Add tanned leather to an oxidation tank, add water to adjust the liquid ratio to 150%, add an oxidant for oxidation treatment, rotate for 60-70 minutes to obtain oxidized leather, transfer the oxidized leather to a washing tank, wash with water 2-3 times until there is no residue, obtain tanned goat glove leather, immerse the tanned goat glove leather in the impregnation solution, immerse for 1-2 hours, take out and dry, and obtain a stain-resistant and self-cleaning goat glove leather.

2. The method for preparing antifouling self-cleaning goat glove leather according to claim 1, characterized in that: The temperature of salt washing in step S1 is 29-31° C., the concentration of the sodium chloride solution is 200% to 220%, and the Baume degree is 6.

3. The method for preparing the anti-fouling self-cleaning goat glove leather according to claim 1, characterized in that: The mass of ammonium sulfate added in step S2 is 0.4% to 0.45% of the total mass of the leather, and the mass of pancreatic enzyme added is 0.06% to 0.08% of the total mass of the leather.

4. The method for preparing the antifouling self-cleaning goat glove leather according to claim 1, characterized in that: The mass of industrial salt added in step S3 is 6% to 8% of the total mass of the leather, the Baume degree is controlled to be 6.0-6.5, the mass of formic acid added each time is 8-12‰ of the total mass of the leather, the mass of organic phosphine tanning agent added is 1.5% to 2.5% of the total mass of the leather, and the mass of synthetic tannin added is 1.5% to 2.5% of the total mass of the leather.

5. The method for preparing antifouling self-cleaning goat glove leather according to claim 1, characterized in that: In step S3, the organic phosphine tanning agent is tetrakishydroxymethylphosphonium chloride or tetrakishydroxymethylphosphonium sulfide.

6. The method for preparing antifouling self-cleaning goat glove leather according to claim 1, characterized in that: In step S4, the oxidant is hydrogen peroxide or sodium perborate, and the mass of the added oxidant is 0.5% to 1% of the total mass of the leather.

7. The method for preparing antifouling self-cleaning goat glove leather according to claim 1, characterized in that: The impregnation solution in step S4 is prepared by the following steps: A1. Add polymethyl methacrylate and 3,3'-dithiodipropionic acid into a reactor filled with toluene, stir until completely dissolved, add azobisisobutyronitrile and cuprous bromide under the protection of inert gas, heat to 75-80°C in an oil bath or water bath, stir and react for 4-6 hours, and after the reaction is completed, perform vacuum distillation, collect the distillation residue, pour the distillation residue into ethanol for precipitation, filter, and dry to constant weight to obtain sulfur-modified polymethyl methacrylate; A2. Add methylbutene and sulfur-modified polymethyl methacrylate to a reactor containing N-methylpyrrolidone, stir until completely dissolved to form a uniform solution, add azobisisobutyronitrile under the protection of inert gas, heat to 60-65°C in an oil bath or water bath, stir and react for 2-4 hours, continue to heat to 70-75°C, stir and react for 8-10 hours, after the reaction is completed, distill under reduced pressure, collect the distillation residue, pour into ethanol for precipitation, filter, wash with ethanol, and dry to constant weight to obtain a modified polymer solution precursor, add the modified polymer precursor to dimethylformamide, add sodium dodecyl sulfate, and prepare an impregnation solution.

8. The method for preparing antifouling self-cleaning goat glove leather according to claim 7, characterized in that: In step A1, the mass ratio of polymethyl methacrylate, 3,3'-dithiodipropionic acid, azobisisobutyronitrile and cuprous bromide is (10-12): (2-3): (0.1-0.2): (0.05-0.08).

9. The method for preparing antifouling self-cleaning goat glove leather according to claim 7, characterized in that: In step A2, the mass ratio of methylbutene, sulfur-modified polymethyl methacrylate and azobisisobutyronitrile is (6-7): (5-5.5): (0.05-0.1).

10. The method for preparing antifouling self-cleaning goat glove leather according to claim 7, characterized in that: In step A2, the mass ratio of the modified polymer precursor, dimethylformamide and sodium dodecyl sulfonate is (9-10): (22-25): (0.5-2).

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