Preparation method of anti-fouling self-cleaning goat glove leather

Abstract

The present invention relates to the technical field of leather products, and in particular to a method for preparing anti-fouling, self-cleaning goat glove leather, comprising the following steps: S1, placing the goat leather in a cleaning tank for salt washing; S2, placing the salt-washed goat leather in a softening tank for softening, and then washing with water after softening; S3, performing acid immersion in a pickling tank, and then tanning after the acid immersion is completed; S4, performing an oxidation treatment in an oxidation tank, and then washing with water to obtain the tanned goat glove leather, which is then immersed in an immersion liquid, taken out, and dried. The present invention not only enhances the leather's resistance to dirt by introducing a copolymer of sulfur-modified polymethyl methacrylate and methylbutene, but also makes it easier for dirt to fall off the leather surface. At the same time, the protective film effectively prevents the penetration of moisture and dirt, thereby extending the service life of the leather.

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, boasting excellent texture, distinctive feel, and superior performance, making it a key component in gloves and other leather goods. Goat leather possesses a distinctive grain and delicate feel. Its thick surface layer offers a strong structure, excellent tensile strength, breathability, and abrasion resistance, making it an ideal choice for high-end gloves. Goat glove leather is not only highly valued for its excellent physical properties, but also for its unique appearance and feel. The subtle undulating texture on its surface imparts a natural aesthetic and layered feel. Furthermore, goat leather's softness and comfort contribute significantly to its popularity, allowing it to conform closely to the contours of the hand, providing an exceptional fit. Goat glove leather is widely used in a variety of glove products, including driving gloves, sports gloves, and etiquette gloves. Driving gloves require excellent grip and abrasion resistance, and goat glove leather meets these requirements, providing a safe and comfortable driving experience. Sports gloves prioritize breathability and flexibility, making goat leather's breathability and softness an ideal material. 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 existing goat glove leather, the cortex is relatively thin, making it susceptible to scratches and abrasions during use. This can compromise the integrity of the gloves after prolonged use. Furthermore, goat leather gloves are typically not washable, limiting cleaning options. To maintain the gloves' aesthetics and extend their lifespan, specialized cleaning and maintenance methods are required, increasing complexity and cost. Due to their limited durability and difficulty cleaning and maintenance, goat leather gloves have a relatively short lifespan, potentially requiring more frequent replacement than more durable leather materials. 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:

[0006] A method for preparing anti-fouling self-cleaning goat glove leather comprises the following steps:

[0007] 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 10-20min, drain, and obtain the goat leather after salt washing;

[0008] S2, put the goat leather after salt washing in the softening tank, add water to adjust the liquid ratio to 1.2-1.3, heat to 36-37 ° C, add ammonium sulfate and pancreatin to soften, rotate for 45-60 min, after softening, transfer to the 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 min to obtain pre-treated leather;

[0009] S3, pre-treated leather is placed in a pickling tank, the water-adjusting liquid ratio is 80%, industrial salt is added, and the rotation is 20-30min, and formic acid with a mass concentration of ≥85% is added 2-3 times for pickling, each addition amount is 8-12‰ of the leather mass, and the rotation is 20-30min after each addition. The pH value is controlled to be 3.4-3.6, and the rotation is continued for 40-60min after the addition. After the pickling is completed, an organophosphine tanning agent is added, and the rotation is 120-160min. The drum is stopped overnight, and the next day, the rotation is continued for 30-40min, and sodium hydroxide is added 2-3 times, and the rotation is 30-40min after each addition. The pH value is adjusted to 5.5-5.7, and then rotated for 60-70min. Synthetic tannin is added and rotated for 60-70min to obtain tanned leather;

[0010] 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 no residue is left, and obtain tanned goat glove leather. Immerse the tanned goat glove leather in the impregnation liquid for 1-2 hours, take out and dry to obtain an anti-fouling and self-cleaning goat glove leather.

[0011] Furthermore, in step S1, the temperature of the salt washing is 29-31° C., the concentration of the sodium chloride solution is 200-220%, and the Baume degree is 6.

[0012] Furthermore, in step S2, the mass of ammonium sulfate added is 0.4-0.45% of the total mass of the leather, and the mass of pancreatic enzyme added is 0.06-0.08% of the total mass of the leather.

[0013] Furthermore, in step S3, the mass of industrial salt added is 6-8% 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 the organic phosphine tanning agent added is 1.5-2.5% of the total mass of the leather, and the mass of the synthetic tannin added is 1.5-2.5% of the total mass of the leather.

[0014] Furthermore, in step S3, the organic phosphine tanning agent is tetrakishydroxymethyl phosphonium chloride or tetrakishydroxymethyl phosphonium sulfate.

[0015] Furthermore, in step S4, the oxidant is hydrogen peroxide or sodium perborate, and the mass of the added oxidant is 0.5-1% of the total mass of the leather.

[0016] Furthermore, the impregnation liquid in step S4 is prepared by the following steps:

[0017] A1. Add polymethyl methacrylate and 3,3'-dithiodipropionic acid to a reactor filled with toluene and stir until completely dissolved. Under the protection of inert gas, add azobisisobutyronitrile and cuprous bromide. Heat to 75-80°C in an oil bath or water bath and stir for 4-6 hours. After the reaction is completed, perform vacuum distillation and collect the distillation residue. Pour the distillation residue into ethanol for precipitation, filter, and dry to constant weight to obtain sulfur-modified polymethyl methacrylate.

[0018] A2. Methylbutene and sulfur-modified polymethyl methacrylate are added to a reactor containing N-methylpyrrolidone and stirred until completely dissolved to form a uniform solution. Under the protection of inert gas, azobisisobutyronitrile is added, and the mixture is heated to 60-65° C. in an oil bath or a water bath. The mixture is stirred and reacted for 10-12 hours. After the reaction is completed, the mixture is distilled under reduced pressure, the distillation residue is collected, poured into ethanol for precipitation, filtered, and the filter cake is washed with ethanol for 3-5 times and dried at 40-50° C. to constant weight to obtain a modified polymer solution precursor. The modified polymer precursor is added to dimethylformamide and sodium dodecylsulfonate to prepare an impregnation solution.

[0019] 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).

[0020] 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).

[0021] Furthermore, in step A2, the mass ratio of the modified polymer precursor, dimethylformamide and sodium dodecylsulfonate is (9-10): (22-25): (0.5-2).

[0022] Beneficial effects of the present invention:

[0023] 1. In the technical solution of this invention, 3,3'-dithiodipropionic acid is grafted onto polymethyl methacrylate (PMMA) molecular chains via a free radical addition reaction, introducing sulfur into the PMMA chains 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 chains, resulting in a more stable structure. Under free radical polymerization, methylbutene undergoes polymerization and may be grafted onto the sulfur-modified PMMA molecular chains to form a copolymer. During the copolymerization process, the methylbutene and sulfur-modified PMMA molecular chains crosslink or entangle, forming a three-dimensional network structure, which imparts enhanced strength and toughness to the modified polymer solution precursor. In the impregnation solution, the modified polymer molecules exist as a dispersed phase. Sodium dodecyl sulfate acts as a surfactant, reducing the surface tension between the modified polymer molecules and the solvent, making them more easily dispersed in the solvent, forming a stable suspension or solution. The sulfur in the sulfur-modified PMMA molecular chain forms hydrogen bonds with hydrogen atoms in hydroxyl or carboxyl groups on the leather surface, forming a stable adsorption layer on the leather surface. When free amino groups are present on the leather surface, the sulfur may form covalent bonds with the nitrogen atoms in the amino groups, further strengthening the bond between the sulfur-modified PMMA and the leather surface, thereby improving the leather's resistance to dirt. Once the modified polymer molecules adhere to the leather surface, they alter its surface energy and polarity, making the surface smoother and more resistant to dirt.

[0024] 2. In this technical solution, the modified polymer molecules form a dense protective film on the leather surface, which has a certain electrostatic repulsion effect, loosening the contact between dirt molecules and the leather surface, making it easier to fall off the leather. In addition, the protective film prevents moisture and dirt from penetrating into the leather, thereby extending the leather's service life. DETAILED DESCRIPTION

[0025] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0026] Unless otherwise specified, the raw materials used in the present invention are all conventional products purchased from the market.

[0027] Preparation Example 1

[0028] The impregnation solution comprises the following steps:

[0029] A1. Add 1 kg of polymethyl methacrylate and 0.2 kg of 3,3'-dithiodipropionic acid to a reactor containing 10 kg of toluene and stir until completely dissolved. Under nitrogen protection, add 0.01 kg of azobisisobutyronitrile and 0.005 kg of cuprous bromide. Heat in an oil bath to 75°C and stir for 4 hours. After the reaction is completed, perform vacuum distillation and 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.

[0030] A2. 0.6 kg of methylbutene and 0.5 kg of sulfur-modified polymethyl methacrylate were added to a reactor containing 5 kg of N-methylpyrrolidone and stirred until completely dissolved to form a uniform solution. Under nitrogen protection, 0.005 kg of azobisisobutyronitrile was added and the oil bath was heated to 60 ° C. The reaction was stirred for 10 hours. After completion of the reaction, the mixture was distilled under reduced pressure, the distillation residue was collected, poured into 5 kg of ethanol for precipitation, filtered, and the filter cake was washed 3 times with ethanol and dried at 40 ° C to constant weight to obtain a modified polymer solution precursor. 0.9 kg of the modified polymer precursor was added to 2.2 kg of dimethylformamide and 0.05 kg of sodium laurylsulfonate to prepare an impregnation solution.

[0031] Preparation Example 2

[0032] The impregnation solution comprises the following steps:

[0033] A1. Add 1.1 kg of polymethyl methacrylate and 0.25 kg of 3,3'-dithiodipropionic acid to a reactor containing 10 kg of toluene and stir until completely dissolved. Under nitrogen protection, add 0.015 kg of azobisisobutyronitrile and 0.0065 kg of cuprous bromide. Heat in a water bath to 78°C and stir for 5 hours. After the reaction is completed, perform vacuum distillation and 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.

[0034] A2. 0.65 kg of methylbutene and 0.53 kg of sulfur-modified polymethyl methacrylate were added to a reactor containing 5 kg of N-methylpyrrolidone and stirred until completely dissolved to form a uniform solution. Under nitrogen protection, 0.008 kg of azobisisobutyronitrile was added and heated in a water bath to 63 ° C. The reaction was stirred for 11 hours. After completion of the reaction, the product was distilled under reduced pressure, the distillation residue was collected, poured into 5 kg of ethanol and precipitated, filtered, and the filter cake was washed 4 times with ethanol and dried to constant weight at 45 ° C to obtain a modified polymer solution precursor. 0.95 kg of the modified polymer precursor was added to 2.35 kg of dimethylformamide and 0.1 kg of sodium laurylsulfonate to prepare an impregnation solution.

[0035] Preparation Example 3

[0036] The impregnation solution comprises the following steps:

[0037] A1. Add 1.2 kg of polymethyl methacrylate and 0.3 kg of 3,3'-dithiodipropionic acid to a reactor containing 10 kg of toluene and stir until completely dissolved. Under nitrogen protection, add 0.02 kg of azobisisobutyronitrile and 0.008 kg of cuprous bromide. Heat in an oil bath to 80°C and stir for 6 hours. After the reaction is completed, perform vacuum distillation and 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.

[0038] A2. 0.7 kg methylbutene and 0.55 kg sulfur-modified polymethyl methacrylate were added to a reactor containing 5 kg N-methylpyrrolidone and stirred until completely dissolved to form a uniform solution. Under nitrogen protection, 0.01 kg azobisisobutyronitrile was added and the oil bath was heated to 65 ° C. The reaction was stirred for 12 h. After completion of the reaction, the mixture was distilled under reduced pressure, the distillation residue was collected, poured into 5 kg ethanol for precipitation, filtered, and the filter cake was washed 5 times with ethanol and dried to constant weight at 50 ° C to obtain a modified polymer solution precursor. 1 kg of the modified polymer precursor was added to 2.5 kg of dimethylformamide and 0.2 kg of sodium laurylsulfonate to prepare an impregnation solution.

[0039] Example 1

[0040] A method for preparing anti-fouling self-cleaning goat glove leather comprises the following steps:

[0041] S1. Put 1 kg of goat leather into a cleaning tank, wash it with clean water, transfer it to a salt washing tank, add 6 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 salt-washed goat leather;

[0042] S2, in the softening tank, put the goat leather after salt washing, add water regulating liquid ratio is 1.2, heat to 36 ℃, add 0.4% ammonium sulfate of leather quality and 0.06% pancreatic enzyme of leather quality to soften, rotate 45min, after softening, transfer to the washing tank, regulating liquid ratio is 2.5, control water temperature at 20 ℃, suffocate washing 2 times, each 10min, obtain pre-treated leather;

[0043] S3, in pickling tank, put into pre-treatment leather, adding water regulating liquid ratio is 80%, add 6% industrial salt of leather quality, rotate 20min, controlling degree Baume is 6.0, dividing 2 times and adding mass concentration is that 85% formic acid carries out pickling, each addition is 8‰ of leather quality, rotate 20min after each addition, control pH value is 3.4, continue to rotate 40min after adding, after pickling finishes, add the tetrakis (hydroxymethyl) phosphonium chloride of leather quality 1.5%, rotate 120min, stop drum and spend the night, continue to rotate 30min next day, divide and add sodium hydroxide 2 times, rotate 30min after each addition, regulating pH value is 5.5, rotate 60min again, add synthetic tannin 1.5%, rotate 60min, obtain tanned leather;

[0044] S4. Add tanned leather to the oxidation tank, add water to adjust the liquid ratio to 150%, add 0.5% hydrogen peroxide by weight of the leather for oxidation treatment, rotate for 60 minutes to obtain oxidized leather, transfer the oxidized leather to a washing tank, wash it twice with water until there is no residue, and obtain tanned goat glove leather. Immerse the tanned goat glove leather in the impregnation solution prepared in Preparation Example 1 for 1 hour, take it out and dry it to obtain a kind of anti-fouling self-cleaning goat glove leather.

[0045] Example 2

[0046] A method for preparing anti-fouling self-cleaning goat glove leather comprises the following steps:

[0047] S1. Put 1 kg of goat leather into a cleaning tank, wash it with clean water, transfer it to a salt washing tank, add 6 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 salt-washed goat leather;

[0048] S2, put the goat leather after salt washing in the softening tank, add water to adjust the liquid ratio to 1.25, heat to 36.5 ° C, add 0.43% of ammonium sulfate and 0.07% of pancreatic enzyme to soften the leather, rotate for 50 minutes, and after softening, transfer to the washing tank, adjust the liquid ratio to 2.7, control the water temperature at 23 ° C, and wash twice for 10 minutes each time to obtain pre-treated leather;

[0049] S3, in pickling tank, put into pre-treatment leather, adding water regulating liquid ratio is 80%, add 7% industrial salt of leather quality, rotate 25min, controlling degree Baume is 6.2, dividing 2 times and adding mass concentration is that 88% formic acid carries out pickling, each addition is 10‰ of leather quality, rotate 25min after each addition, control pH value is 3.5, add the back and continue to rotate 50min, after pickling finishes, add the tetrakis (hydroxymethyl) phosphonium chloride of leather quality 2%, rotate 140min, stop drum and spend the night, continue to rotate 35min next day, divide and add sodium hydroxide 2 times, rotate 35min after each addition, regulating pH value is 5.6, rotate 65min again, add synthetic tannin 2%, rotate 65min, obtain tanned leather;

[0050] 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 oxidized leather, transfer the oxidized leather to a washing tank, wash twice with water until no residue is left, and obtain tanned goat glove leather. Immerse the tanned goat glove leather in the impregnation solution prepared in Preparation Example 2 for 1.5 hours, take out and dry to obtain a kind of anti-fouling self-cleaning goat glove leather.

[0051] Example 3

[0052] A method for preparing anti-fouling self-cleaning goat glove leather comprises the following steps:

[0053] S1. Place 1 kg of goat leather in a cleaning tank, wash with clean water, transfer to a salt washing tank, add 6 Baume sodium chloride solution with a temperature of 31 ° C and a concentration of 200%, rotate for 20 minutes, drain, and obtain salt-washed goat leather;

[0054] S2, in the softening tank, put the goat leather after salt washing, adding water regulating liquid ratio is 1.3, heated to 37 ℃, add 0.45% ammonium sulfate of leather quality and 0.08% pancreatic enzyme of leather quality to soften, rotate 60min, after softening, transfer to the washing tank, regulating liquid ratio is 3.0, control water temperature at 25 ℃, suffocate washing 3 times, each 15min, obtain pre-treated leather;

[0055] S3, in pickling tank, put into pre-treatment leather, adding water regulating liquid ratio is 80%, add 8% industrial salt of leather quality, rotate 30min, controlling degree Baume is 6.5, dividing and adding mass concentration is that 90% formic acid carries out pickling for 3 times, each addition is 12‰ of leather quality, rotate 30min after each addition, control pH value is 3.6, continue to rotate 60min after adding, after pickling finishes, add the tetrakis (hydroxymethyl) phosphine sulfate of leather quality 2.5%, rotate 160min, stop drum and spend the night, continue to rotate 40min next day, divide and add sodium hydroxide for 3 times, rotate 40min after each addition, regulating pH value is 5.7, rotate 70min again, add synthetic tannin 2.5%, rotate 70min, obtain tanned leather;

[0056] 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 oxidized leather, transfer the oxidized leather to a washing tank, wash it with water 3 times until there is no residue, and obtain tanned goat glove leather. Immerse the tanned goat glove leather in the impregnation solution prepared in Preparation Example 3 for 2 hours, take it out and dry it to obtain a kind of anti-fouling self-cleaning goat glove leather.

[0057] Comparative Example 1

[0058] 0.9 kg of polymethyl methacrylate was added to 2.2 kg of dimethylformamide and 0.05 kg of sodium dodecylsulfonate to prepare an impregnation solution.

[0059] Comparative Example 2

[0060] 0.95 kg of methylbutene was added to 2.35 kg of dimethylformamide and 0.1 kg of sodium laurylsulfonate to prepare an impregnation solution.

[0061] Comparative Example 3

[0062] 1 kg of 3,3'-dithiodipropionic acid was added to 2.5 kg of dimethylformamide and 0.2 kg of sodium dodecylsulfonate to prepare an impregnation solution.

[0063] Comparative Example 4

[0064] 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.

[0065] Comparative Example 5

[0066] 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.

[0067] Comparative Example 6

[0068] 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.

[0069] 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 abrasion tester were set, and the CS-10 grinding wheel was selected with a load of 1000g and a rotation speed of 72rpm, and 2000 wear cycles were performed. After the test, the samples were removed from the tester, and the final thickness and final mass of each sample were measured. The thickness loss and mass loss were calculated as follows: thickness loss = initial thickness - final thickness, and mass loss = initial mass - final mass. The results are shown in Table 1:

[0070] Table 1. Wear resistance test results of Examples 1-3 and Comparative Examples 4-6

[0071]

[0072] With reference to GB / T 41424.1-2022, "Determination of the Soiling Properties of Leather - Part 1: Tumble Method," leather samples from Examples 1-3 and Comparative Examples 4-6 were pretreated. The initial mass of each sample was recorded, and a stain solution was prepared (145 g of synthetic grease was weighed into a 1 L beaker and slowly heated in a water bath until the grease melted. 220 mL of acetone, 220 mL of butanone, and 25.0 mL of petroleum ether were added to the beaker to dilute the grease. 0.90 mL of graphite emulsion was added to the diluted grease solution). The pretreated samples were placed in a drum staining apparatus and tested at 20°C and 65% humidity at a tumbling speed of 30 rpm for 60 minutes. After the test, the final mass of each sample was measured, and the stain gain was calculated as: stain gain = final mass - initial mass. The results are shown in Table 2.

[0073] Table 2. Staining performance test results of Examples 1-3 and Comparative Examples 4-6

[0074]

[0075] As shown in Table 1, the thickness loss and mass loss in Examples 1-3 were significantly lower than those in Comparative Examples 4-6, indicating that the impregnation solutions used in Examples 1-3 significantly improved the wear resistance of the leather. The sulfur-modified copolymer of polymethyl methacrylate and methylbutene in the impregnation solutions of Examples 1-3 likely formed a stronger bond with the leather surface, thereby enhancing the leather's wear resistance. The impregnation solutions in Comparative Examples 4-6 were unmodified and therefore did not provide the same improvement in wear resistance.

[0076] As shown in Table 2, the weight gain after staining in Examples 1-3 was significantly lower than that in Comparative Examples 4-6, indicating that the impregnation solutions in Examples 1-3 effectively improved the leather's anti-staining properties. The modified polymer in the impregnation solution likely formed a thin film on the leather surface that was impermeable to grease, thereby preventing the penetration and adhesion of the staining liquid. The introduction of 3,3'-dithiodipropionic acid and methylbutene likely altered the surface properties of the polymer, making it more stain-resistant. The impregnation solutions in Comparative Examples 4-6 were unmodified and therefore did not provide the same anti-staining properties.

[0077] In the impregnation solutions prepared in Preparation Examples 1-3, the introduction of sulfur into the sulfur-modified polymethyl methacrylate likely altered the polymer's chain structure and surface properties, strengthening its bond to the leather while also providing improved abrasion resistance and stain resistance. Methylbutene may copolymerize with polymethyl methacrylate to form a polymer with specific surface properties, contributing to improved abrasion resistance and stain resistance of the leather.

[0078] In summary, the use of the impregnation solutions prepared in Preparation Examples 1-3 in Examples 1-3 significantly improved the wear resistance and anti-fouling properties of the leather.

[0079] Throughout the specification, references to terms such as "embodiment" or "various embodiments" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or preparation example are included in at least one embodiment or preparation example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or preparation example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or preparation examples.

[0080] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing antifouling self-cleaning goat glove leather, characterized in that: The following steps are involved: S1, goat leather is placed in a cleaning tank, washed with clean water, transferred to a salt washing tank, sodium chloride solution is added for salt washing, rotated for 10-20min, drained, and the goat leather after salt washing is obtained; S2, put the goat leather after salt washing in the softening tank, add water to adjust the liquid ratio to 1.2-1.3, heat to 36-37 ° C, add ammonium sulfate and pancreatin to soften, rotate for 45-60 min, after softening, transfer to the 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 min to obtain pre-treated leather; S3, in pickling tank, put pre-treatment leather, add water adjustment liquid ratio is 80%, add industrial salt, rotate 20-30min, add formic acid 2-3 times for pickling, rotate 20-30min after each addition, control pH value is 3.4-3.6, continue to rotate 40-60min after adding, after pickling finishes, add organophosphine tanning agent, rotate 120-160min, stop drum overnight, continue to rotate 30-40min the next day, add sodium hydroxide 2-3 times, rotate 30-40min after each addition, adjust pH value to 5.5-5.7, then rotate 60-70min, add synthetic tannin, rotate 60-70min, obtain tanned leather; S4, adding tanned leather to an oxidation tank, adding water to adjust the liquid ratio to 150%, adding an oxidant for oxidation treatment, rotating for 60-70 minutes to obtain oxidized leather, transferring the oxidized leather to a washing tank, washing 2-3 times until no residue is left, obtaining tanned goat glove leather, immersing the tanned goat glove leather in an immersion solution, immersing for 1-2 hours, taking out and drying, to obtain a kind of anti-fouling self-cleaning goat glove leather; The impregnation liquid in step S4 is prepared by the following steps: A1. Add polymethyl methacrylate and 3,3'-dithiodipropionic acid to a reactor filled with toluene and stir until completely dissolved. Under the protection of inert gas, add azobisisobutyronitrile and cuprous bromide. Heat to 75-80°C in an oil bath or water bath and stir for 4-6 hours. After the reaction is completed, perform vacuum distillation and 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. Methylbutene and sulfur-modified polymethyl methacrylate are added to a reactor containing N-methylpyrrolidone and stirred until completely dissolved to form a uniform solution. Under the protection of inert gas, azobisisobutyronitrile is added, and the mixture is heated to 60-65° C. in an oil bath or a water bath, stirred and reacted for 2-4 hours, and then the temperature is continuously raised to 70-75° C. and stirred and reacted for 8-10 hours. After the reaction is completed, the mixture is distilled under reduced pressure, the distillation residue is collected, poured into ethanol for precipitation, filtered, washed with ethanol, and dried to constant weight to obtain a modified polymer precursor. The modified polymer precursor is added to dimethylformamide and sodium dodecylsulfonate to prepare an impregnation solution.

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

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

4. The method for preparing antifouling self-cleaning goat glove leather according to claim 1, characterized in that: In step S3, the mass of industrial salt added is 6-8% 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 the organic phosphine tanning agent added is 1.5-2.5% of the total mass of the leather, and the mass of the synthetic tannin added is 1.5-2.5% 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 tetrakis(hydroxymethyl)phosphine chloride or tetrakis(hydroxymethyl)phosphine sulfate.

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 0.5-1% 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 mass ratio of polymethyl methacrylate, 3,3'-dithiodipropionic acid, azobisisobutyronitrile and cuprous bromide in step A1 is (10-12): (2-3): (0.1-0.2): (0.05-0.08).

8. The method for preparing antifouling self-cleaning goat glove leather according to claim 1, characterized in that: The mass ratio of methylbutene, sulfur-modified polymethyl methacrylate and azobisisobutyronitrile in step A2 is (6-7): (5-5.5): (0.05-0.1).

9. The method for preparing antifouling self-cleaning goat glove leather according to claim 1, characterized in that: In step A2, the mass ratio of the modified polymer precursor, dimethylformamide and sodium dodecylsulfonate is (9-10):(22-25):(0.5-2).

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