Wear-resistant and stain-resistant baseball leather treatment process

Abstract

The invention discloses a treatment process for wear-resistant and anti-fouling baseball leather. The treatment process comprises the following steps: S1, soaking and fleshing; s2, unhairing expansion and re-liming; s3, decolorizing and bleaching; s4, pickling treatment; s5, carrying out chrome-free tanning, taking out of a drum and squeezing water; s6, slicing and peeling, rinsing and neutralizing; s7, fat liquoring and retanning; and S8, hanging, airing and staking. Two-step shaping is adopted in the steps of chrome-free tanning and drum-out wringing, so that the leather treated according to the scheme is in a half-cooked state instead of being treated to be in a full-cooked state, and the baseball made of the leather can be shrunk when being hit in the hitting process, so that the color of the baseball is increased, and the color of the baseball is increased. However, leather tanned in the prior art can expand and loosen after being used for a period of time. The anti-hitting performance of baseballs in the market is not good all the time, the baseballs start to deform after being hit for less than 2000 times and cannot rebound, and the baseball leather treated through the process has the excellent performance of being good in anti-hitting performance, resistant to abrasion and free of deformation.

Description

Technical Field

[0001] This invention relates to the field of leather treatment technology, and in particular to a treatment process for wear-resistant and stain-resistant baseball leather. Background Technology

[0002] A baseball is mainly composed of a core, a winding layer, and a leather outer layer. The leather outer layer directly affects the baseball's key characteristics such as its feel, durability, flight stability, and appearance.

[0003] Chromium-free leather completely eliminates heavy metal chromium pollution from the leather-making process at its source, promoting green development and achieving environmental protection goals.

[0004] However, because leather contains a large amount of protein and lacks antibacterial properties, leather sports equipment and footwear are easily stained with sweat and dirt. In humid environments, bacteria can easily grow, harming human health and even causing mold, significantly shortening the leather's lifespan. In current cowhide manufacturing processes, the final product has a relatively smooth surface. When this smooth leather is applied to baseballs, the coefficient of friction between the baseball's surface and the bat is low, making it prone to slipping when swinging the bat, which is detrimental to the baseball player's hitting ability.

[0005] In the leather processing process, fatliquoring agents are generally added. The oil components in fatliquoring agents have a certain degree of hydrophobicity, which can form a continuous waterproof layer on the surface of leather fibers, preventing the penetration of water. This allows the leather to maintain a good dry state in humid environments or when it comes into contact with water, preventing problems such as swelling, deformation, and mold caused by water absorption, and ensuring that the performance and appearance of the baseball are not affected. Summary of the Invention

[0006] To address the problems mentioned in the background section, this invention provides a process for treating wear-resistant and stain-resistant baseball leather.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0009] S1 Soak in water and remove meat:

[0010] The raw hide of the yellow cattle is soaked in deionized water and a compound degreasing agent is added for de-meating treatment; the mass ratio of the compound degreasing agent to the deionized water is 7-10:100.

[0011] S2 hair removal with swelling and graying:

[0012] After the raw hide of the yellow cattle is processed by removing the meat, deionized water, sodium sulfide and quicklime are added to remove hair, expand and re-ash it; then the hide is processed by removing the meat and peeling the ash hide.

[0013] S3 decolorization and bleaching:

[0014] Then add deionized water and oxalic acid for deashing and softening, and add formaldehyde and titanium dioxide for decolorization and bleaching;

[0015] S4 pickling treatment:

[0016] After the cowhide is decolorized and bleached, it is soaked in deionized water, sodium chloride and sulfuric acid for acid treatment; the mass ratio of deionized water, sodium chloride and sulfuric acid is 100:8-11:13-15.

[0017] S5 chrome-free tanning, dewatering after drum extrusion:

[0018] After the leather has been pickled, it is added to hexamethylenetetramine and polyaluminum chloride for 1 hour for tanning. Then, a chromium-free zirconium tanning agent is added and the reaction is carried out at 35-42℃ for 4-6 hours. Acetic acid chloride is added for 1 hour for tanning. Finally, it is left to stand for 1 day to complete the tanning process. The ZrO2 content of the chromium-free zirconium tanning agent is 32%-34%.

[0019] S6. Peel the skin evenly, rinse, and neutralize:

[0020] After the tanning process is completed, the hides are sliced ​​and shaved evenly, and then rinsed and neutralized with deionized water and sodium bicarbonate.

[0021] S7, Fat-added retanning:

[0022] After rinsing and neutralizing, the leather is added to a chromium-free retanning agent and a fatliquoring agent for fatliquoring retanning.

[0023] S8. Hang to dry and soften:

[0024] After the leather is retanned with fat, it is hung to dry until it is completely dry. It is then hung to soften, trimmed, graded, and the finished product is put into storage.

[0025] Preferably, the composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of (7-10):1:1.3.

[0026] Preferably, the mass ratio of the composite degreasing agent to deionized water is 7-10:100.

[0027] Preferably, the fatliquoring agent is one or more of sulfonated oil, castor oil, castor oil phosphate, and sulfite-treated cow hoof oil.

[0028] Preferably, the preparation method of the chromium-free retanning agent includes the following steps:

[0029] S1. Weigh out the following components by weight: 50-60 parts of functional monomer, 20-30 parts of carboxymethyl cellulose, 3-5 parts of composite crosslinking agent, and 0.5-1.5 parts of composite initiator.

[0030] S2. Add 75-80% of the total volume of supercritical carbon dioxide (scCO2) as a solvent to the oil phase and disperse it for 30 minutes at 10000 rpm using a high-pressure homogenizer at 35-40℃ and 10MPa to form a homogeneous and transparent oil phase solution.

[0031] S3. Add 20-25 parts by weight of ferric sulfate, 10-15 parts by weight of zirconium sulfate, 10-15 parts by weight of aluminum sulfate and 5-10 parts by weight of Tween-80 to 45 parts by weight of water, and dissolve at a stirring speed of 200 rpm for 60 min to obtain an aqueous solution.

[0032] S4. Under high-speed shearing conditions of 12000-15000 rpm, the aqueous phase is added dropwise to the oil phase at a rate of 5 mL / min to form a primary emulsion. Then, 10% of the total mass of the oil and aqueous phases of the amphiphilic template agent F127 is added, and shearing is continued for 30 min until a stable water-in-oil dispersion is formed.

[0033] S5. Transfer the dispersion to a high-pressure reactor and carry out a suspension polymerization reaction at 60℃ and 10MPa for 20h. During the reaction, stir at a low speed of 50rpm to ensure the uniformity of the system. After the reaction, recover the scCO2 solvent under normal pressure to obtain wet microcapsules. Freeze-dry at -30℃ and 10Pa for 20-24h to obtain a chromium-free retanning agent.

[0034] Preferably, the composite crosslinking agent is prepared by compounding trimethylolpropane trimethacrylate and polyethylene glycol dimethacrylate in a mass ratio of 1:1.

[0035] Preferably, the composite initiator is prepared by compounding 2,2'-azobisisobutyronitrile and potassium persulfate in a mass ratio of 3:1.

[0036] Preferably, the method for preparing the functional monomer in step S1 includes the following steps:

[0037] S1. Dissolve 2-pyridinecarboxaldehyde and 4-aminopyridine in anhydrous ethanol, add lanthanum trifluoromethanesulfonate and reflux the reaction. After cooling the reaction solution, wash and filter to obtain the intermediate.

[0038] S2. The intermediate was dissolved in tetrahydrofuran, and a tetrahydrofuran solution of phenylphosphonic dichloride was added dropwise under ice bath conditions. The reaction was maintained at a low temperature and then heated to continue the reaction. After adjusting the pH of the reaction solution, the product was extracted, dried, filtered, distilled under reduced pressure and washed, and then dried under vacuum to obtain the functional monomer.

[0039] Preferably, the concentration of the tetrahydrofuran solution of phenylphosphonic dichloride is 25-35 wt%; the temperature during the dropping process is maintained at -6 to -4 °C.

[0040] Compared with the prior art, the beneficial effects of the present invention are:

[0041] 1. This invention employs a two-step shaping process in the chromium-free tanning and dewatering steps, leaving the leather treated according to the above scheme in a semi-cooked state, unlike other leathers that are fully cooked. This allows baseballs made from this leather to shrink more with each hit, while leather treated with existing techniques expands and loosens after a period of use. Baseballs on the market have consistently had poor impact resistance, deforming and failing to rebound after less than 2000 hits. The baseball leather treated with this invention exhibits excellent impact resistance, wear resistance, and non-deformation properties.

[0042] 2. The composite degreasing agent in this invention is a combination of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside. Fatty alcohol polyoxyethylene ether, as a nonionic surfactant, possesses excellent emulsifying ability due to the balance of its hydrophilic and hydrophobic groups. By forming water-in-oil droplets, AEO can disperse the oils between leather fibers into micron-sized particles, significantly increasing the contact area between the lipase and the substrate, thereby accelerating the enzymatic hydrolysis rate. The lipase specifically hydrolyzes the ester bonds of triglycerides, converting the oils into water-soluble fatty acids and glycerol. Alkyl glycoside, as a green nonionic surfactant, enhances permeability without destroying enzyme activity, assisting in the removal of impurities within the leather fibers. Through synergistic emulsification-enzymatic hydrolysis-permeation, the three components significantly improve degreasing efficiency compared to traditional methods, while simultaneously avoiding hardening damage to the leather.

[0043] 3. The chromium-free retanning agent prepared by this invention is safe and environmentally friendly. During the synthesis of the functional monomer, the S1 intermediate undergoes a nucleophilic substitution reaction with phenylphosphonic dichloride in step S2. The phosphonic group is incorporated into the molecular backbone through nucleophilic attack of the pyridine ring nitrogen atom, ultimately forming a functional monomer containing a pyridine nitrogen-phosphonic oxygen dual-coordination group. In this molecular structure, the lone pair electrons of the pyridine ring nitrogen atom and the electron-rich properties of the phosphonic oxygen atom can interact with the Fe in leather fibers through a chelation effect. 3+ 、Zr 4+ 、Al 3+ The formation of a five-membered ring coordination structure by multiple nucleated metal ions increases the coordination constant by 3-5 times compared to a single group, significantly enhancing the binding strength between the retanning agent and collagen fibers.

[0044] When leather is subjected to mechanical stress, the rigid cross-linking nodes (TMPTMA trifunctional groups) in the microcapsule wall material bind to collagen fibers through covalent bonds, while the flexible PEGDMA segments absorb elastic deformation energy, increasing the slip resistance between fibers by 35%. Compared to the agglomerated particles of traditional retanning agents, this uniformly dispersed structure significantly improves the flexural strength of leather, reduces abrasion by more than 20%, and significantly enhances abrasion resistance. Attached Figure Description

[0045] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0046] Figure 1 This is a schematic diagram of the process flow of the present invention. Detailed Implementation

[0047] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0048] The chromium-free zirconium tanning agent was selected from Davitan ZR05 zirconium tanning agent. Other raw materials were purchased from Aladdin and Alibaba, respectively.

[0049] Preparation Example 1

[0050] The preparation method of the chromium-free retanning agent includes the following steps:

[0051] S1. Weigh out the following components by weight: 55 parts functional monomer, 25 parts carboxymethyl cellulose, 4 parts composite crosslinking agent, and 1 part composite initiator.

[0052] S2. Add 80% of the total volume of supercritical carbon dioxide (scCO2) as a solvent to the oil phase and disperse it for 30 min at 10000 rpm using a high-pressure homogenizer at 35℃ and 10MPa to form a homogeneous and transparent oil phase solution.

[0053] S3. Add 20 parts by weight of ferric sulfate, 15 parts by weight of zirconium sulfate, 15 parts by weight of aluminum sulfate and 5 parts by weight of Tween-80 to 45 parts by weight of water, and dissolve at a stirring speed of 200 rpm for 60 min to obtain an aqueous solution.

[0054] S4. Under high-speed shearing conditions of 15000rpm, the aqueous phase is added dropwise to the oil phase at a rate of 5mL / min to form a primary emulsion. Then, 10% of the total mass of the oil and aqueous phases of the amphiphilic template agent F127 is added, and shearing is continued for 30min until a stable water-in-oil dispersion is formed.

[0055] S5. Transfer the dispersion to a high-pressure reactor and carry out a suspension polymerization reaction at 60℃ and 10MPa for 20h. During the reaction, stir at a low speed of 50rpm to ensure the uniformity of the system. After the reaction, recover the scCO2 solvent under normal pressure to obtain wet microcapsules. Freeze-dry at -30℃ and 10Pa for 24h to obtain a chromium-free retanning agent.

[0056] The composite crosslinking agent is prepared by compounding trimethylolpropane trimethacrylate and polyethylene glycol dimethacrylate in a mass ratio of 1:1.

[0057] The composite initiator is prepared by compounding 2,2'-azobisisobutyronitrile and potassium persulfate in a mass ratio of 3:1.

[0058] The preparation method of the functional monomer includes the following steps:

[0059] S1. Dissolve 45g of 2-pyridinecarboxaldehyde and 20g of 4-aminopyridine in 100g of anhydrous ethanol, add 1g of lanthanum trifluoromethanesulfonate and reflux the reaction. After cooling the reaction solution, wash and filter to obtain the intermediate.

[0060] S2. Dissolve 7g of intermediate in 35g of tetrahydrofuran, and add 18g of 30wt% tetrahydrofuran solution of phenylphosphonic dichlorophenate dropwise under ice bath conditions, maintaining the temperature at -5℃ during the dropwise addition process. After the dropwise addition is completed, raise the temperature to 25℃ and continue the reaction for 10h. After the reaction is completed, adjust the pH to 7 with saturated sodium bicarbonate solution, then extract, dry the organic phase with anhydrous sodium sulfate, filter, distill under reduced pressure and wash, and finally dry under vacuum to obtain the functional monomer.

[0061] Preparation Example 2

[0062] The preparation method of the chromium-free retanning agent includes the following steps:

[0063] S1. Weigh out the following components by weight: 50 parts functional monomer, 20 parts carboxymethyl cellulose, 3 parts composite crosslinking agent, and 1.5 parts composite initiator.

[0064] S2. Add 75% of the total volume of supercritical carbon dioxide (scCO2) as a solvent to the oil phase and disperse it for 30 min at 10000 rpm using a high-pressure homogenizer at 40℃ and 10MPa to form a homogeneous and transparent oil phase solution.

[0065] S3. Add 22 parts by weight of ferric sulfate, 10 parts by weight of zirconium sulfate, 10 parts by weight of aluminum sulfate and 8 parts by weight of Tween-80 to 45 parts by weight of water, and dissolve at a stirring speed of 200 rpm for 60 min to obtain an aqueous solution.

[0066] S4. Under high-speed shearing conditions of 12000 rpm, the aqueous phase is added dropwise to the oil phase at a rate of 5 mL / min to form a primary emulsion. Then, 10% of the total mass of the oil and aqueous phases of the amphiphilic template agent F127 is added, and shearing is continued for 30 min until a stable water-in-oil dispersion is formed.

[0067] S5. Transfer the dispersion to a high-pressure reactor and carry out a suspension polymerization reaction at 60℃ and 10MPa for 20h. During the reaction, stir at a low speed of 50rpm to ensure the uniformity of the system. After the reaction, recover the scCO2 solvent under normal pressure to obtain wet microcapsules. Freeze-dry at -30℃ and 10Pa for 20h to obtain a chromium-free retanning agent.

[0068] The composite crosslinking agent is prepared by compounding trimethylolpropane trimethacrylate and polyethylene glycol dimethacrylate in a mass ratio of 1:1.

[0069] The composite initiator is prepared by compounding 2,2'-azobisisobutyronitrile and potassium persulfate in a mass ratio of 3:1.

[0070] The preparation method of the functional monomer includes the following steps:

[0071] S1. Dissolve 45g of 2-pyridinecarboxaldehyde and 20g of 4-aminopyridine in 100g of anhydrous ethanol, add 1g of lanthanum trifluoromethanesulfonate and reflux the reaction. After cooling the reaction solution, wash and filter to obtain the intermediate.

[0072] S2. Dissolve 7g of intermediate in 35g of tetrahydrofuran, and add 18g of 25wt% tetrahydrofuran solution of phenylphosphonic dichloride dropwise under ice bath conditions, maintaining the temperature at -4℃ during the dropwise addition process. After the dropwise addition is completed, raise the temperature to 25℃ and continue the reaction for 10h. After the reaction is completed, adjust the pH to 7 with saturated sodium bicarbonate solution, then extract, dry the organic phase with anhydrous sodium sulfate, filter, distill under reduced pressure and wash, and finally dry under vacuum to obtain the functional monomer.

[0073] Preparation Example 3

[0074] The preparation method of the chromium-free retanning agent includes the following steps:

[0075] S1. Weigh out the following components by weight: 60 parts of functional monomer, 20 parts of carboxymethyl cellulose, 4 parts of composite crosslinking agent, and 1 part of composite initiator.

[0076] S2. Add 80% of the total volume of supercritical carbon dioxide (scCO2) as a solvent to the oil phase and disperse it for 30 min at 10000 rpm using a high-pressure homogenizer at 35-40℃ and 10MPa to form a homogeneous and transparent oil phase solution.

[0077] S3. Add 20 parts by weight of ferric sulfate, 15 parts by weight of zirconium sulfate, 15 parts by weight of aluminum sulfate and 5 parts by weight of Tween-80 to 45 parts by weight of water, and dissolve at a stirring speed of 200 rpm for 60 min to obtain an aqueous solution.

[0078] S4. Under high-speed shearing conditions of 12000 rpm, the aqueous phase is added dropwise to the oil phase at a rate of 5 mL / min to form a primary emulsion. Then, 10% of the total mass of the oil and aqueous phases of the amphiphilic template agent F127 is added, and shearing is continued for 30 min until a stable water-in-oil dispersion is formed.

[0079] S5. Transfer the dispersion to a high-pressure reactor and carry out a suspension polymerization reaction at 60℃ and 10MPa for 20h. During the reaction, stir at a low speed of 50rpm to ensure the uniformity of the system. After the reaction, recover the scCO2 solvent under normal pressure to obtain wet microcapsules. Freeze-dry at -30℃ and 10Pa for 24h to obtain a chromium-free retanning agent.

[0080] The composite crosslinking agent is prepared by compounding trimethylolpropane trimethacrylate and polyethylene glycol dimethacrylate in a mass ratio of 1:1.

[0081] The composite initiator is prepared by compounding 2,2'-azobisisobutyronitrile and potassium persulfate in a mass ratio of 3:1.

[0082] The preparation method of the functional monomer includes the following steps:

[0083] S1. Dissolve 45g of 2-pyridinecarboxaldehyde and 20g of 4-aminopyridine in 100g of anhydrous ethanol, add 1g of lanthanum trifluoromethanesulfonate and reflux the reaction. After cooling the reaction solution, wash and filter to obtain the intermediate.

[0084] S2. Dissolve 7g of intermediate in 35g of tetrahydrofuran, and add 18g of 35wt% tetrahydrofuran solution of phenylphosphonic dichlorophenate dropwise under ice bath conditions, maintaining the temperature at -6℃ during the dropwise addition process. After the dropwise addition is completed, raise the temperature to 25℃ and continue the reaction for 10h. After the reaction is completed, adjust the pH to 7 with saturated sodium bicarbonate solution, then extract, dry the organic phase with anhydrous sodium sulfate, filter, distill under reduced pressure and wash, and finally dry under vacuum to obtain the functional monomer.

[0085] Preparation Example 4

[0086] The preparation method of the chromium-free retanning agent includes the following steps:

[0087] S1. Weigh out the following components by weight: 55 parts functional monomer, 25 parts carboxymethyl cellulose, 4 parts composite crosslinking agent, and 1 part composite initiator.

[0088] S2. Add 75% of the total volume of supercritical carbon dioxide (scCO2) as a solvent to the oil phase and disperse it for 30 min at 10000 rpm using a high-pressure homogenizer at 38℃ and 10MPa to form a homogeneous and transparent oil phase solution.

[0089] S3. Add 22 parts by weight of ferric sulfate, 12 parts by weight of zirconium sulfate, 12 parts by weight of aluminum sulfate and 8 parts by weight of Tween-80 to 45 parts by weight of water, and dissolve at a stirring speed of 200 rpm for 60 min to obtain an aqueous solution.

[0090] S4. Under high-speed shearing conditions of 15000rpm, the aqueous phase is added dropwise to the oil phase at a rate of 5mL / min to form a primary emulsion. Then, 10% of the total mass of the oil and aqueous phases of the amphiphilic template agent F127 is added, and shearing is continued for 30min until a stable water-in-oil dispersion is formed.

[0091] S5. Transfer the dispersion to a high-pressure reactor and carry out a suspension polymerization reaction at 60℃ and 10MPa for 20h. During the reaction, stir at a low speed of 50rpm to ensure the uniformity of the system. After the reaction, recover the scCO2 solvent under normal pressure to obtain wet microcapsules. Freeze-dry at -30℃ and 10Pa for 24h to obtain a chromium-free retanning agent.

[0092] The composite crosslinking agent is prepared by compounding trimethylolpropane trimethacrylate and polyethylene glycol dimethacrylate in a mass ratio of 1:1.

[0093] The composite initiator is prepared by compounding 2,2'-azobisisobutyronitrile and potassium persulfate in a mass ratio of 3:1.

[0094] The preparation method of the functional monomer includes the following steps:

[0095] S1. Dissolve 45g of 2-pyridinecarboxaldehyde and 20g of 4-aminopyridine in 100g of anhydrous ethanol, add 1g of lanthanum trifluoromethanesulfonate and reflux the reaction. After cooling the reaction solution, wash and filter to obtain the intermediate.

[0096] S2. Dissolve 7g of intermediate in 35g of tetrahydrofuran, and add 18g of 32wt% tetrahydrofuran solution of phenylphosphonic dichlorophenate dropwise under ice bath conditions, maintaining the temperature at -5℃ during the dropwise addition process. After the dropwise addition is completed, raise the temperature to 25℃ and continue the reaction for 10h. After the reaction is completed, adjust the pH to 7 with saturated sodium bicarbonate solution, then extract, dry the organic phase with anhydrous sodium sulfate, filter, distill under reduced pressure and wash, and finally dry under vacuum to obtain the functional monomer.

[0097] Preparation Example 5

[0098] The preparation method of the chromium-free retanning agent includes the following steps:

[0099] S1. Weigh out the following components by weight: 52 parts of functional monomer, 24 parts of carboxymethyl cellulose, 5 parts of composite crosslinking agent, and 1 part of composite initiator.

[0100] S2. Add 78% of the total volume of supercritical carbon dioxide (scCO2) as a solvent to the oil phase and disperse it for 30 min at 10000 rpm using a high-pressure homogenizer at 38℃ and 10MPa to form a homogeneous and transparent oil phase solution.

[0101] S3. Add 22 parts by weight of ferric sulfate, 13 parts by weight of zirconium sulfate, 13 parts by weight of aluminum sulfate and 9 parts by weight of Tween-80 to 45 parts by weight of water, and dissolve at a stirring speed of 200 rpm for 60 min to obtain an aqueous solution.

[0102] S4. Under high-speed shearing conditions of 12000 rpm, the aqueous phase is added dropwise to the oil phase at a rate of 5 mL / min to form a primary emulsion. Then, 10% of the total mass of the oil and aqueous phases of the amphiphilic template agent F127 is added, and shearing is continued for 30 min until a stable water-in-oil dispersion is formed.

[0103] S5. Transfer the dispersion to a high-pressure reactor and carry out a suspension polymerization reaction at 60℃ and 10MPa for 20h. During the reaction, stir at a low speed of 50rpm to ensure the uniformity of the system. After the reaction, recover the scCO2 solvent under normal pressure to obtain wet microcapsules. Freeze-dry at -30℃ and 10Pa for 20h to obtain a chromium-free retanning agent.

[0104] The composite crosslinking agent is prepared by compounding trimethylolpropane trimethacrylate and polyethylene glycol dimethacrylate in a mass ratio of 1:1.

[0105] The composite initiator is prepared by compounding 2,2'-azobisisobutyronitrile and potassium persulfate in a mass ratio of 3:1.

[0106] The preparation method of the functional monomer includes the following steps:

[0107] S1. Dissolve 45g of 2-pyridinecarboxaldehyde and 20g of 4-aminopyridine in 100g of anhydrous ethanol, add 1g of lanthanum trifluoromethanesulfonate and reflux the reaction. After cooling the reaction solution, wash and filter to obtain the intermediate.

[0108] S2. Dissolve 7g of intermediate in 35g of tetrahydrofuran, and add 18g of 28wt% tetrahydrofuran solution of phenylphosphonic dichlorophenate dropwise under ice bath conditions, maintaining the temperature at -5℃ during the dropwise addition process. After the dropwise addition is completed, raise the temperature to 25℃ and continue the reaction for 10h. After the reaction is completed, adjust the pH to 7 with saturated sodium bicarbonate solution, then extract, dry the organic phase with anhydrous sodium sulfate, filter, distill under reduced pressure and wash, and finally dry under vacuum to obtain the functional monomer.

[0109] Preparation Example 6

[0110] The preparation method of the chromium-free retanning agent includes the following steps:

[0111] S1. Weigh out the following components by weight: 60 parts of functional monomer, 20 parts of carboxymethyl cellulose, 4 parts of composite crosslinking agent, and 1 part of composite initiator.

[0112] S2. Add 80% of the total volume of supercritical carbon dioxide (scCO2) as a solvent to the oil phase and disperse it for 30 min at 10000 rpm using a high-pressure homogenizer at 35-40℃ and 10MPa to form a homogeneous and transparent oil phase solution.

[0113] S3. Add 25 parts by weight of ferric sulfate, 10 parts by weight of zirconium sulfate, 10 parts by weight of aluminum sulfate and 8 parts by weight of Tween-80 to 45 parts by weight of water, and dissolve at a stirring speed of 200 rpm for 60 min to obtain an aqueous solution.

[0114] S4. Under high-speed shearing conditions of 14000 rpm, the aqueous phase is added dropwise to the oil phase at a rate of 5 mL / min to form a primary emulsion. Then, 10% of the total mass of the oil and aqueous phases of the amphiphilic template agent F127 is added, and shearing is continued for 30 min until a stable water-in-oil dispersion is formed.

[0115] S5. Transfer the dispersion to a high-pressure reactor and carry out a suspension polymerization reaction at 60℃ and 10MPa for 20h. During the reaction, stir at a low speed of 50rpm to ensure the uniformity of the system. After the reaction, recover the scCO2 solvent under normal pressure to obtain wet microcapsules. Freeze-dry at -30℃ and 10Pa for 20h to obtain a chromium-free retanning agent.

[0116] The composite crosslinking agent is prepared by compounding trimethylolpropane trimethacrylate and polyethylene glycol dimethacrylate in a mass ratio of 1:1.

[0117] The composite initiator is prepared by compounding 2,2'-azobisisobutyronitrile and potassium persulfate in a mass ratio of 3:1.

[0118] The preparation method of the functional monomer includes the following steps:

[0119] S1. Dissolve 45g of 2-pyridinecarboxaldehyde and 20g of 4-aminopyridine in 100g of anhydrous ethanol, add 1g of lanthanum trifluoromethanesulfonate and reflux the reaction. After cooling the reaction solution, wash and filter to obtain the intermediate.

[0120] S2. Dissolve 7g of intermediate in 35g of tetrahydrofuran, and add 18g of 30wt% tetrahydrofuran solution of phenylphosphonic dichloride dropwise under ice bath conditions, maintaining the temperature at -6℃ during the dropwise addition process. After the dropwise addition is completed, raise the temperature to 25℃ and continue the reaction for 10h. After the reaction is completed, adjust the pH to 7 with saturated sodium bicarbonate solution, then extract, dry the organic phase with anhydrous sodium sulfate, filter, distill under reduced pressure and wash, and finally dry under vacuum to obtain the functional monomer.

[0121] Example 1

[0122] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0123] S1 Soak in water and remove meat:

[0124] Soak 50g of raw cattle hide in 100g of deionized water and add 7g of compound degreasing agent to remove the meat;

[0125] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 7:1:1.3.

[0126] S2 hair removal with swelling and graying:

[0127] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 10g of sodium sulfide and 5g of quicklime are added to remove hair, expand and re-ash; then the hide is ash-removed, meat is removed and the hide is ash-sliced.

[0128] S3 decolorization and bleaching:

[0129] Add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 5g of formaldehyde and 5g of titanium dioxide for decolorization and bleaching.

[0130] S4 pickling treatment:

[0131] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 8g of sodium chloride and 13g of sulfuric acid for acid treatment.

[0132] S5 chrome-free tanning, dewatering after drum extrusion:

[0133] After the leather has been pickled, add 5g of hexamethylenetetramine and 8g of polyaluminum chloride for 1 hour to fix it. Then add 7g of chromium-free zirconium tanning agent and control the temperature at 35℃ for 4 hours. Add chlorine acetate for 1 hour to fix it. Finally, let it stand for 1 day to complete the tanning process.

[0134] The ZrO2 content in the chromium-free zirconium tanning agent is 32%;

[0135] S6. Peel the skin evenly, rinse, and neutralize:

[0136] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 30g of deionized water and 8g of sodium bicarbonate are added for rinsing and neutralization.

[0137] S7, Fat-added retanning:

[0138] The washed and neutralized leather was added to 5g of the chromium-free retanning agent prepared in Example 1 and 5g of castor oil phosphate for fat addition retanning.

[0139] S8. Hang to dry and soften:

[0140] After the leather is retanned, it is hung to dry until dry, then hung to soften, with a vacuum degree of -0.07MPa, temperature control of 40℃, and a softening time of 3 hours. Then it is trimmed, graded, and the finished products are put into storage.

[0141] Example 2

[0142] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0143] S1 Soak in water and remove meat:

[0144] Soak 50g of raw cattle hide in 100g of deionized water and add 7g of compound degreasing agent to remove the meat;

[0145] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 8:1:1.3.

[0146] S2 hair removal with swelling and graying:

[0147] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 8g of sodium sulfide and 6g of quicklime are added to remove hair, expand and re-ash; then the hide is processed by removing the meat and slicing the ash hide.

[0148] S3 decolorization and bleaching:

[0149] Add 100g of deionized water and 13g of oxalic acid for deashing and softening, and add 6g of formaldehyde and 6g of titanium dioxide for decolorization and bleaching.

[0150] S4 pickling treatment:

[0151] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 10g of sodium chloride and 14g of sulfuric acid for acid treatment.

[0152] S5 chrome-free tanning, dewatering after drum extrusion:

[0153] After the leather was pickled, 6g of hexamethylenetetramine and 10g of polyaluminum chloride were added for 1 hour to fix the leather. Then, 8g of chromium-free zirconium tanning agent was added and the temperature was controlled at 35℃ for 4 hours. Acetic acid chloride was added for 1 hour to fix the leather. Finally, the leather was left to stand for 1 day to complete the tanning process.

[0154] The ZrO2 content in the chromium-free zirconium tanning agent is 32%;

[0155] S6. Peel the skin evenly, rinse, and neutralize:

[0156] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 40g of deionized water and 10g of sodium bicarbonate are added for rinsing and neutralization.

[0157] S7, Fat-added retanning:

[0158] The rinsed and neutralized leather was added to 5g of the chromium-free retanning agent prepared in Example 2 and 5g of castor oil phosphate for fat addition retanning.

[0159] S8. Hang to dry and soften:

[0160] After the leather is retanned, it is hung out to dry until dry, and then hung to soften. The vacuum degree is -0.08MPa, the temperature is controlled at 45℃, and the softening time is 3 hours. Then it is trimmed, graded, and the finished products are put into storage.

[0161] Example 3

[0162] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0163] S1 Soak in water and remove meat:

[0164] Soak 50g of raw cattle hide in 100g of deionized water and add 8g of compound degreasing agent to remove the meat;

[0165] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 9:1:1.3.

[0166] S2 hair removal with swelling and graying:

[0167] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 12g of sodium sulfide and 8g of quicklime are added to remove hair, expand and re-ash; then the hide is processed by removing the meat and slicing the ash hide.

[0168] S3 decolorization and bleaching:

[0169] Add 100g of deionized water and 16g of oxalic acid for deashing and softening, and add 6g of formaldehyde and 8g of titanium dioxide for decolorization and bleaching.

[0170] S4 pickling treatment:

[0171] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 11g of sodium chloride and 15g of sulfuric acid for acid treatment.

[0172] S5 chrome-free tanning, dewatering after drum extrusion:

[0173] After the leather has been pickled, add 5g of hexamethylenetetramine and 8g of polyaluminum chloride for 1 hour to fix it. Then add 7g of chromium-free zirconium tanning agent and control the temperature at 35℃ for 4 hours. Add chlorine acetate for 1 hour to fix it. Finally, let it stand for 1 day to complete the tanning process.

[0174] The ZrO2 content in the chromium-free zirconium tanning agent is 32%;

[0175] S6. Peel the skin evenly, rinse, and neutralize:

[0176] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 30g of deionized water and 8g of sodium bicarbonate are added for rinsing and neutralization.

[0177] S7, Fat-added retanning:

[0178] The washed and neutralized leather was added to 5g of the chromium-free retanning agent prepared in Example 3 and 5g of castor oil phosphate for fat addition retanning.

[0179] S8. Hang to dry and soften:

[0180] After the leather is retanned, it is hung to dry until dry, then hung to soften, with a vacuum degree of -0.07MPa, temperature control of 40℃, and a softening time of 3 hours. Then it is trimmed, graded, and the finished products are put into storage.

[0181] Example 4

[0182] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0183] S1 Soak in water and remove meat:

[0184] Soak 50g of raw cattle hide in 100g of deionized water and add 7g of compound degreasing agent to remove the meat;

[0185] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 10:1:1.3.

[0186] S2 hair removal with swelling and graying:

[0187] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 10g of sodium sulfide and 5g of quicklime are added to remove hair, expand and re-ash; then the hide is ash-removed, meat is removed and the hide is ash-sliced.

[0188] S3 decolorization and bleaching:

[0189] Add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 5g of formaldehyde and 5g of titanium dioxide for decolorization and bleaching.

[0190] S4 pickling treatment:

[0191] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 8g of sodium chloride and 13g of sulfuric acid for acid treatment.

[0192] S5 chrome-free tanning, dewatering after drum extrusion:

[0193] After the leather has been pickled, add 5g of hexamethylenetetramine and 8g of polyaluminum chloride for 1 hour to fix it. Then add 7g of chromium-free zirconium tanning agent and control the temperature at 35℃ for 4 hours. Add chlorine acetate for 1 hour to fix it. Finally, let it stand for 1 day to complete the tanning process.

[0194] The ZrO2 content in the chromium-free zirconium tanning agent is 32%;

[0195] S6. Peel the skin evenly, rinse, and neutralize:

[0196] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 30g of deionized water and 8g of sodium bicarbonate are added for rinsing and neutralization.

[0197] S7, Fat-added retanning:

[0198] The rinsed and neutralized leather was added to 5g of the chromium-free retanning agent prepared in Example 1 and 5g of sulfite-treated cow hoof oil for fatliquoring retanning.

[0199] S8. Hang to dry and soften:

[0200] After the leather is retanned, it is hung to dry until dry, then hung to soften, with a vacuum degree of -0.09MPa, temperature control of 50℃, and a softening time of 4 hours. Finally, it is trimmed, graded, and the finished product is put into storage.

[0201] Example 5

[0202] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0203] S1 Soak in water and remove meat:

[0204] Soak 50g of raw cattle hide in 100g of deionized water and add 7g of compound degreasing agent to remove the meat;

[0205] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 7:1:1.3.

[0206] S2 hair removal with swelling and graying:

[0207] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 10g of sodium sulfide and 8g of quicklime are added to remove hair, expand and re-ash; then the hide is ash-removed, meat is removed and the hide is ash-sliced.

[0208] S3 decolorization and bleaching:

[0209] Add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 8g of formaldehyde and 7g of titanium dioxide for decolorization and bleaching.

[0210] S4 pickling treatment:

[0211] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 9g of sodium chloride and 13g of sulfuric acid for acid treatment.

[0212] S5 chrome-free tanning, dewatering after drum extrusion:

[0213] After the leather was pickled, 6g of hexamethylenetetramine and 10g of polyaluminum chloride were added for 1 hour to fix the leather. Then, 8g of chromium-free zirconium tanning agent was added and the temperature was controlled at 35℃ for 4 hours. Acetic acid chloride was added for 1 hour to fix the leather. Finally, the leather was left to stand for 1 day to complete the tanning process.

[0214] The ZrO2 content in the chromium-free zirconium tanning agent is 32%;

[0215] S6. Peel the skin evenly, rinse, and neutralize:

[0216] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 40g of deionized water and 10g of sodium bicarbonate are added for rinsing and neutralization.

[0217] S7, Fat-added retanning:

[0218] The washed and neutralized leather was added to 8g of the chromium-free retanning agent prepared in Example 2 and 7g of sulfonated oil for fatliquoring retanning.

[0219] S8. Hang to dry and soften:

[0220] After the leather is retanned, it is hung to dry until dry, then hung to soften, with a vacuum degree of -0.09MPa, temperature control of 50℃, and a softening time of 4 hours. Finally, it is trimmed, graded, and the finished product is put into storage.

[0221] Example 6

[0222] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0223] S1 Soak in water and remove meat:

[0224] Soak 50g of raw cattle hide in 100g of deionized water and add 8g of compound degreasing agent to remove the meat;

[0225] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 8:1:1.3.

[0226] S2 hair removal with swelling and graying:

[0227] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 11g of sodium sulfide and 7g of quicklime are added to remove hair, expand and re-ash; then the hide is ash-removed, meat is removed and the hide is ash-sliced.

[0228] S3 decolorization and bleaching:

[0229] Add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 6g of formaldehyde and 8g of titanium dioxide for decolorization and bleaching.

[0230] S4 pickling treatment:

[0231] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 9g of sodium chloride and 13g of sulfuric acid for acid treatment.

[0232] S5 chrome-free tanning, dewatering after drum extrusion:

[0233] After the leather has been pickled, add 5g of hexamethylenetetramine and 8g of polyaluminum chloride for 1 hour to fix it. Then add 7g of chromium-free zirconium tanning agent and control the temperature at 35℃ for 4 hours. Add chlorine acetate for 1 hour to fix it. Finally, let it stand for 1 day to complete the tanning process.

[0234] The ZrO2 content in the chromium-free zirconium tanning agent is 34%;

[0235] S6. Peel the skin evenly, rinse, and neutralize:

[0236] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 40g of deionized water and 10g of sodium bicarbonate are added for rinsing and neutralization.

[0237] S7, Fat-added retanning:

[0238] The rinsed and neutralized leather was added to 5g of the chromium-free retanning agent prepared in Example 3 and 5g of sulfite-treated cow hoof oil for fatliquoring retanning.

[0239] S8. Hang to dry and soften:

[0240] After the leather is retanned, it is hung to dry until dry, then hung to soften, with a vacuum degree of -0.09MPa, temperature control of 50℃, and a softening time of 4 hours. Finally, it is trimmed, graded, and the finished product is put into storage.

[0241] Example 7

[0242] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0243] S1 Soak in water and remove meat:

[0244] Soak 50g of raw cattle hide in 100g of deionized water and add 7g of compound degreasing agent to remove the meat;

[0245] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 8:1:1.3.

[0246] S2 hair removal with swelling and graying:

[0247] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 10g of sodium sulfide and 5g of quicklime are added to remove hair, expand and re-ash; then the hide is ash-removed, meat is removed and the hide is ash-sliced.

[0248] S3 decolorization and bleaching:

[0249] Add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 5g of formaldehyde and 5g of titanium dioxide for decolorization and bleaching.

[0250] S4 pickling treatment:

[0251] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 8g of sodium chloride and 13g of sulfuric acid for acid treatment.

[0252] S5 chrome-free tanning, dewatering after drum extrusion:

[0253] After the leather has been pickled, add 5g of hexamethylenetetramine and 8g of polyaluminum chloride for 1 hour to fix it. Then add 7g of chromium-free zirconium tanning agent and control the temperature at 35℃ for 4 hours. Add chlorine acetate for 1 hour to fix it. Finally, let it stand for 1 day to complete the tanning process.

[0254] The ZrO2 content in the chromium-free zirconium tanning agent is 32%;

[0255] S6. Peel the skin evenly, rinse, and neutralize:

[0256] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 30g of deionized water and 8g of sodium bicarbonate are added for rinsing and neutralization.

[0257] S7, Fat-added retanning:

[0258] The washed and neutralized leather was added to 5g of the chromium-free retanning agent prepared in Example 4 and 5g of castor oil phosphate for fat addition retanning.

[0259] S8. Hang to dry and soften:

[0260] After the leather is retanned, it is hung to dry until dry, then hung to soften, with a vacuum degree of -0.07MPa, temperature control of 40℃, and a softening time of 3 hours. Then it is trimmed, graded, and the finished products are put into storage.

[0261] Example 8

[0262] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0263] S1 Soak in water and remove meat:

[0264] Soak 50g of raw cattle hide in 100g of deionized water and add 9g of compound degreasing agent to remove the meat;

[0265] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 9:1:1.3.

[0266] S2 hair removal with swelling and graying:

[0267] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 8g of sodium sulfide and 6g of quicklime are added to remove hair, expand and re-ash; then the hide is processed by removing the meat and slicing the ash hide.

[0268] S3 decolorization and bleaching:

[0269] Add 100g of deionized water and 13g of oxalic acid for deashing and softening, and add 6g of formaldehyde and 6g of titanium dioxide for decolorization and bleaching.

[0270] S4 pickling treatment:

[0271] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 8g of sodium chloride and 15g of sulfuric acid for acid treatment.

[0272] S5 chrome-free tanning, dewatering after drum extrusion:

[0273] After the leather was pickled, 6g of hexamethylenetetramine and 10g of polyaluminum chloride were added for 1 hour to fix the leather. Then, 8g of chromium-free zirconium tanning agent was added and the temperature was controlled at 35℃ for 4 hours. Acetic acid chloride was added for 1 hour to fix the leather. Finally, the leather was left to stand for 1 day to complete the tanning process.

[0274] The ZrO2 content in the chromium-free zirconium tanning agent is 32%;

[0275] S6. Peel the skin evenly, rinse, and neutralize:

[0276] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 40g of deionized water and 10g of sodium bicarbonate are added for rinsing and neutralization.

[0277] S7, Fat-added retanning:

[0278] The washed and neutralized leather was added to 5g of the chromium-free retanning agent prepared in Example 5 and 5g of castor oil phosphate for fat addition retanning.

[0279] S8. Hang to dry and soften:

[0280] After the leather is retanned, it is hung out to dry until dry, and then hung to soften. The vacuum degree is -0.08MPa, the temperature is controlled at 45℃, and the softening time is 3 hours. Then it is trimmed, graded, and the finished products are put into storage.

[0281] Example 9

[0282] Reference Figure 1 A wear-resistant and stain-resistant baseball leather treatment process includes the following steps:

[0283] S1 Soak in water and remove meat:

[0284] Soak 50g of raw cattle hide in 100g of deionized water and add 10g of compound degreasing agent to remove the meat;

[0285] The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of 9:1:1.3.

[0286] S2 hair removal with swelling and graying:

[0287] After the raw hide of the yellow cattle is processed by removing the meat, 100g of deionized water, 12g of sodium sulfide and 8g of quicklime are added to remove hair, expand and re-ash; then the hide is processed by removing the meat and slicing the ash hide.

[0288] S3 decolorization and bleaching:

[0289] Add 100g of deionized water and 16g of oxalic acid for deashing and softening, and add 6g of formaldehyde and 8g of titanium dioxide for decolorization and bleaching.

[0290] S4 pickling treatment:

[0291] After the cowhide is decolorized and bleached, it is soaked in 100g of deionized water, 9g of sodium chloride and 14g of sulfuric acid for acid treatment.

[0292] S5 chrome-free tanning, dewatering after drum extrusion:

[0293] After the leather has been pickled, add 5g of hexamethylenetetramine and 8g of polyaluminum chloride for 1 hour to fix it. Then add 7g of chromium-free zirconium tanning agent and control the temperature at 35℃ for 4 hours. Add chlorine acetate for 1 hour to fix it. Finally, let it stand for 1 day to complete the tanning process.

[0294] The ZrO2 content in the chromium-free zirconium tanning agent is 33%;

[0295] S6. Peel the skin evenly, rinse, and neutralize:

[0296] After the tanning process is completed, the hides are sliced ​​and shaved evenly, then 30g of deionized water and 8g of sodium bicarbonate are added for rinsing and neutralization.

[0297] S7, Fat-added retanning:

[0298] The washed and neutralized leather was added to 5g of the chromium-free retanning agent prepared in Example 6 and 5g of castor oil phosphate for fat addition retanning.

[0299] S8. Hang to dry and soften:

[0300] After the leather is retanned, it is hung to dry until dry, then hung to soften, with a vacuum degree of -0.07MPa, temperature control of 40℃, and a softening time of 3 hours. Then it is trimmed, graded, and the finished products are put into storage.

[0301] Comparative Example 1

[0302] The difference between this comparative example and Example 1 is that the compound degreasing agent was replaced with a commercially available degreasing agent purchased from Jinan Baoliyuan Chemical Co., Ltd., CAS number 68439-39-4.

[0303] Comparative Example 2

[0304] The difference between this comparative example and Example 1 is that no alkyl glycosides are added during the preparation of the composite degreasing agent.

[0305] Comparative Example 3

[0306] The difference between this comparative example and Example 1 is that the chromium-free retanning agent prepared in Example 1 is replaced with a commercially available acrylic retanning agent, Shandong Lihou Light Industry New Material Co., Ltd., model TJ-R5054.

[0307] Comparative Example 4

[0308] The difference between this comparative example and Example 1 is that the functional monomer in the preparation of the chromium-free retanning agent in Example 1 was replaced with ethyl acrylate, which was purchased from Aladdin, CAS No.: 140-88-5.

[0309] The leathers obtained in Examples 1-9 and Comparative Examples 1-4 were subjected to tests for water repellency, oil repellency, abrasion resistance, and weather resistance. The test results are shown in Table 1.

[0310] Water repellency test: The water repellency test is conducted using a GT-7033N water repellency meter (standard ASTM-D1913-2000); Precautions: 1. 250mL of water must be sprayed out within 25-30s; 2. The sample holder is at a 45° angle to the horizontal plane; 3. The center of the lower surface of the nozzle and the center of the sample surface should be 152.4mm apart; 4. Avoid touching the testing instrument by hand during the test to avoid affecting the experimental results.

[0311] Oil Repellency Test: Tested according to the American 3M Company AATCC 118 (oil repellency) standard. Using the standard oil in AATCC 118 as the test oil, droplets of the test oil are applied to the leather surface using a dropper. The leather area is 20cm x 20cm, and the droplet diameter is 3mm. Three drops are applied to different parts of the leather, and observed for 30 seconds. If two drops from each part are not absorbed, the test is passed. Lower-grade oils are tested first, then higher-grade oils, until the test fails.

[0312] Abrasion resistance test: The abrasion test was conducted on the sample in an environment of 25℃ and 50%RH using an abrasion tester with a load of 500g and a rotation speed of 500 rpm. The condition of the artificial leather surface after abrasion was observed.

[0313] Weather resistance test: The sample was placed in a constant temperature and humidity test chamber at 85℃ and 90%RH for 24 hours for aging. Then, the sample was subjected to abrasion test using an abrasion tester at 25℃ and 50%RH with a load of 500g and a rotation speed of 500 rpm. The condition of the artificial leather surface after abrasion was observed.

[0314] Table 1

[0315]

[0316]

[0317] As can be seen from the table above, the dynamic waterproof and oil-resistant properties of Examples 1-9 are improved compared to Comparative Examples 1-4. Furthermore, the baseball leather prepared in Examples 1-9 all exhibit good abrasion resistance and weather resistance, and retains its abrasion resistance even after wet heat aging, indicating excellent performance in both high temperature and moisture resistance, resulting in superior overall application performance. Simultaneously, the baseball leather prepared in Examples 1-9 all demonstrate strong impact resistance, significantly superior to Comparative Examples 1-4. Baseballs made from leather tanned using the process described in this invention remain firm even after more than 3000 hits, demonstrating outstanding overall performance.

[0318] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A wear-resistant and stain-resistant baseball leather treatment process, characterized in that, The following steps are involved: S1 Soak in water and remove meat: The raw hide of the yellow cattle is soaked in deionized water and a compound degreasing agent is added to remove the meat. S2 hair removal with swelling and graying: After the raw hide of the yellow cattle is processed by removing the meat, deionized water, sodium sulfide and quicklime are added to remove hair, expand and re-ash it; then the hide is processed by removing the meat and peeling the ash hide. S3 decolorization and bleaching: Then add deionized water and oxalic acid for deashing and softening, and add formaldehyde and titanium dioxide for decolorization and bleaching; S4 acid immersion treatment: After the cowhide is decolorized and bleached, it is soaked in deionized water, sodium chloride and sulfuric acid for acid treatment. S5 chrome-free tanning, dewatering after drum extrusion: After the leather has been pickled, add hexamethylenetetramine and polyaluminum chloride for 1 hour to fix it. Then add chromium-free zirconium tanning agent and control the temperature at 35-42℃ for 4-6 hours. Add chlorine acetate for 1 hour to fix it. Finally, let it stand for 1 day to complete the tanning process. S6. Peel the skin evenly, rinse, and neutralize: After the tanning process is completed, the hides are sliced ​​and shaved evenly, and then rinsed and neutralized with deionized water and sodium bicarbonate. S7, Fat-added retanning: After rinsing and neutralizing, the leather is added to a chromium-free retanning agent and a fatliquoring agent for fatliquoring retanning. S8. Hang to dry and soften: After the leather is retanned with fat, it is hung to dry until it is completely dry. It is then hung to soften, trimmed, graded, and the finished product is put into storage.

2. The wear-resistant and stain-resistant baseball leather treatment process according to claim 1, characterized in that: The composite degreasing agent is a mixture of lipase, fatty alcohol polyoxyethylene ether, and alkyl glycoside in a mass ratio of (7-10):1:1.

3.

3. The wear-resistant and stain-resistant baseball leather treatment process according to claim 1, characterized in that: The mass ratio of the composite degreasing agent to deionized water in S1 is 7-10:

100.

4. The wear-resistant and stain-resistant baseball leather treatment process according to claim 1, characterized in that: The fatliquoring agent is one or more of sulfonated oil, castor oil, castor oil phosphate, and sulfite-treated cow hoof oil.

5. The wear-resistant and stain-resistant baseball leather treatment process according to claim 1, characterized in that: The mass ratio of deionized water, sodium chloride, and sulfuric acid in S4 is 100:8-11:13-15.

6. The wear-resistant and stain-resistant baseball leather treatment process according to claim 1, characterized in that: The ZrO2 content of the chromium-free zirconium tanning agent in S5 is 32%-34%.

7. The wear-resistant and stain-resistant baseball leather treatment process according to claim 1, characterized in that: The preparation method of the chromium-free retanning agent includes the following steps: S1. Weigh out the following components by weight: 50-60 parts of functional monomer, 20-30 parts of carboxymethyl cellulose, 3-5 parts of composite crosslinking agent, and 0.5-1.5 parts of composite initiator. S2. Add 75-80% of the total volume of supercritical carbon dioxide (scCO2) as a solvent to the oil phase and disperse it for 30 minutes at 10000 rpm using a high-pressure homogenizer at 35-40℃ and 10MPa to form a homogeneous and transparent oil phase solution. S3. Add 20-25 parts by weight of ferric sulfate, 10-15 parts by weight of zirconium sulfate, 10-15 parts by weight of aluminum sulfate and 5-10 parts by weight of Tween-80 to 45 parts by weight of water, and dissolve at a stirring speed of 200 rpm for 60 min to obtain an aqueous solution. S4. Under high-speed shearing conditions of 12000-15000 rpm, the aqueous phase is added dropwise to the oil phase at a rate of 5 mL / min to form a primary emulsion. Then, 10% of the total mass of the oil and aqueous phases of the amphiphilic template agent F127 is added, and shearing is continued for 30 min until a stable water-in-oil dispersion is formed. S5. Transfer the dispersion to a high-pressure reactor and carry out a suspension polymerization reaction at 60℃ and 10MPa for 20h. During the reaction, stir at a low speed of 50rpm to ensure the uniformity of the system. After the reaction, recover the scCO2 solvent under normal pressure to obtain wet microcapsules. Freeze-dry at -30℃ and 10Pa for 20-24h to obtain a chromium-free retanning agent.

8. The wear-resistant and stain-resistant baseball leather treatment process according to claim 7, characterized in that: The composite crosslinking agent is prepared by compounding trimethylolpropane trimethacrylate and polyethylene glycol dimethacrylate in a mass ratio of 1:

1.

9. The wear-resistant and stain-resistant baseball leather treatment process according to claim 7, characterized in that: The composite initiator is prepared by compounding 2,2'-azobisisobutyronitrile and potassium persulfate in a mass ratio of 3:

1.

10. The wear-resistant and stain-resistant baseball leather treatment process according to claim 7, characterized in that: The preparation method of the functional monomer in step S1 includes the following steps: S1. Dissolve 2-pyridinecarboxaldehyde and 4-aminopyridine in anhydrous ethanol, add lanthanum trifluoromethanesulfonate and reflux the reaction. After cooling the reaction solution, wash and filter to obtain the intermediate. S2. The intermediate was dissolved in tetrahydrofuran, and a tetrahydrofuran solution of phenylphosphonic dichloride was added dropwise under ice bath conditions. The reaction was maintained at a low temperature and then heated to continue the reaction. After adjusting the pH of the reaction solution, the product was extracted, dried, filtered, distilled under reduced pressure and washed, and then dried under vacuum to obtain the functional monomer.

11. The wear-resistant and stain-resistant baseball leather treatment process according to claim 10, characterized in that: The concentration of the tetrahydrofuran solution of phenylphosphonic dichloride is 25-35 wt%; the temperature during the dropwise addition process is maintained at -6 to -4 °C.

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