Multi-component silicon-free leather waterproofing and fatliquoring agent and method for its preparation

Abstract

This invention relates to the field of leather chemical technology and discloses a multi-component silicone-free leather waterproofing and fatliquoring agent and its preparation method. The method includes: neutralizing maleic anhydride-grafted polyisobutylene with an alkali to obtain waterproof component A; emulsifying and polymerizing acrylate or methacrylate formed from C12-C26 fatty alcohols, alkenyl succinic anhydride, 1-octadecene, oleic acid, and acrylic acid in the presence of an initiator and then neutralizing with an alkali to obtain waterproof component B; reacting higher alcohols, isocyanates, dihydroxyethylmaleimide, dihydroxymethylacetic acid, and dihydroxymethylpropionic acid, followed by neutralization with triethylamine and water dispersion to obtain waterproof component C; and mixing the three waterproof components with an emulsifier and solvent in specified amounts, controlling the solid content to be 48%-52%. This invention, by compounding silicone-free waterproof components, imparts dynamic waterproofing properties to leather without adding organosilicon waterproof components, while also considering water dispersibility and leather fatliquoring requirements.

Description

Technical Field

[0001] This invention relates to the field of leather chemical technology, and more specifically, to a multi-component silicone-free leather waterproofing and fatliquoring agent and its preparation method. Background Technology

[0002] Fat grafting is an important step in leather processing. By introducing fat grafting materials between leather fibers, friction between the fibers can be reduced, improving the leather's softness, elasticity, and mechanical properties. For shoe uppers, suede, and outdoor leathers, the fat grafting process also imparts water-repellent properties.

[0003] Existing waterproofing fatliquoring agents typically use mineral oil, wax, long-chain aliphatic compounds, acrylate polymers, or organosilicon materials as waterproofing components. Among these, organosilicon materials have low surface energy and good hydrophobicity, and are therefore used in the processing of waterproof leather. CN108265135A discloses a waterproofing fatliquoring agent and its preparation method. The method involves first modifying a long-chain compound containing primary amine groups with a carboxylating agent, then mixing the resulting long-chain amine carboxyl compound with an alkanolamide phosphate, maleic anhydride-grafted hydrocarbon polymer, and a compatibilizer, followed by alkali neutralization and water dispersion to obtain the waterproofing fatliquoring agent. Some embodiments of this method use amino-polydimethylsiloxane, and the resulting product still belongs to a silicone-containing waterproofing system.

[0004] When long-chain acrylate polymers or maleic anhydride-modified hydrocarbon polymers are used to replace silicone materials, the dispersion state of different structural components in water and their mode of action in leather processing differ. Therefore, it is necessary to provide a waterproofing and fatliquoring agent that does not use silicone waterproofing components and can meet the requirements of leather fatliquoring and waterproofing treatment. Summary of the Invention

[0005] The purpose of this invention is to provide a multi-component silicone-free leather waterproofing and fatliquoring agent and its preparation method to solve the above-mentioned technical problems.

[0006] To achieve the above objectives, the present invention provides the following solution: On one hand, the present invention provides a method for preparing a multi-component silicone-free leather waterproofing and fatliquoring agent, comprising: Maleic anhydride-grafted polyisobutylene was neutralized with alkali in the presence of a solvent to obtain waterproof component A. Acrylic esters or methacrylates formed from C12-C26 fatty alcohols are mixed with alkenyl succinic anhydride, 1-octadecene and oleic acid, and water is added under alkaline conditions to form an emulsion. Acrylic acid is added to the emulsion in the presence of an initiator to carry out a polymerization reaction. After the reaction is completed, alkali neutralization is carried out to obtain waterproof component B. The higher alcohol was reacted with isocyanate, and then dihydroxyethylmaleamic acid, dihydroxymethylacetic acid and dihydroxymethylpropionic acid were added to continue the reaction. After the reaction was completed, triethylamine was used to neutralize the reaction and water was added to obtain waterproof component C. Mix 30-40 parts by weight of the waterproof component A, 15-20 parts by weight of the waterproof component B, 10-15 parts by weight of the waterproof component C, 10-15 parts by weight of the emulsifier and 5-15 parts by weight of the solvent, and control the solid content to be 48%-52% to obtain the silicone-free leather waterproof fatliquoring agent.

[0007] Preferably, in preparing the waterproof component A, 100 parts by weight of maleic anhydride-grafted polyisobutylene and 20 parts by weight of solvent are added to a reaction vessel, the temperature is raised to 80°C, 5 parts by weight of alkali are added dropwise over a period of 1 hour, the reaction is carried out for 2 hours after the addition is completed, the pH value is controlled at 6.5 to 8.5, and 80 parts by weight of distilled water is added to obtain the waterproof component A.

[0008] According to the preparation method of claim 2, the solvent used to prepare the waterproof component A is one or more of ethylene glycol butyl ether, propylene glycol butyl ether, propylene glycol methyl ether and dipropylene glycol monomethyl ether; and the base used is one or more of sodium hydroxide, potassium hydroxide, monoethanolamine, triethanolamine and 2-amino-2-methyl-1-propanol.

[0009] Preferably, in preparing the waterproof component B, 90 parts by weight of acrylate or methacrylate formed from C12-C26 fatty alcohol, 10 parts by weight of alkenyl succinic anhydride, 10 parts by weight of 1-octadecene, 10 parts by weight of oleic acid, and 20 parts by weight of solvent are added to a reaction vessel, heated to 80°C, 3 parts by weight of alkali are added, and the reaction is carried out for 2 hours; 350 parts by weight of water are added and stirred to form an emulsion, while 30 parts by weight of acrylic acid and 10 parts by weight of an initiator solution with a mass concentration of 20% are added dropwise, each dropwise over 2 hours; after the dropwise addition is completed, the temperature is raised to 90°C and reacted for 2 hours, then cooled to 50°C, 20 parts by weight of alkali are added, and the reaction is carried out for 1 hour, controlling the pH value to be 6.0-8.0, and 50 parts by weight of distilled water are added to obtain the waterproof component B.

[0010] Preferably, the acrylate or methacrylate is one or more of lauryl acrylate, lauryl methacrylate, octadecyl acrylate, and octadecyl methacrylate; the alkenyl succinic anhydride is one or more of dodecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, and C16-C18 alkenyl succinic anhydride; and the initiator is ammonium persulfate.

[0011] Preferably, the solvent used to prepare the waterproof component B is one or more of ethylene glycol butyl ether, propylene glycol butyl ether, propylene glycol methyl ether, and dipropylene glycol monomethyl ether; the base used is selected from one or more of sodium hydroxide, monoethanolamine, and morpholine.

[0012] Preferably, in preparing the waterproof component C, 60 parts by weight of higher alcohol and 30 parts by weight of isocyanate are added to a reaction vessel, heated to 70°C and reacted for 2 hours; 5 parts by weight of dihydroxyethyl maleamic acid, 1 part by weight of dihydroxymethyl acetic acid, 1 part by weight of dihydroxymethyl propionic acid and 0.01 parts by weight of catalyst are added, the temperature is raised to 85°C and reacted for 2 hours; the temperature is lowered to 40°C, 15 parts by weight of triethylamine are added and reacted for 1 hour, the pH value is controlled at 8.0-9.0, and then 110 parts by weight of distilled water is added to obtain the waterproof component C.

[0013] Preferably, the higher alcohol is one or more of C12-C14 fatty alcohols, C16-C18 fatty alcohols, and fatty alcohols with more than 20 carbon atoms; the isocyanate is isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate; and the catalyst is dibutyltin dilaurate.

[0014] Preferably, the emulsifier is one or more of sodium oleate, potassium oleate, triethanolamine oleate soap, monoethanolamine oleate soap, sodium oleyl sarcosinate, potassium oleyl sarcosinate, triethanolamine oleyl sarcosinate soap, monoethanolamine oleyl sarcosinate soap, and N-oleyl sarcosinate-octadecylamine salt; and the solvent mixed with the waterproofing component A, waterproofing component B, and waterproofing component C is one or more of ethylene glycol butyl ether, propylene glycol butyl ether, propylene glycol methyl ether, and dipropylene glycol monomethyl ether.

[0015] On the other hand, the present invention provides a multi-component silicone-free waterproof fatliquoring agent for leather, comprising 30-40 parts by weight of waterproof component A, 15-20 parts by weight of waterproof component B, 10-15 parts by weight of waterproof component C, 10-15 parts by weight of emulsifier, and 5-15 parts by weight of solvent, with a solid content of 48%-52%; wherein waterproof component A is an alkali-neutralized product of maleic anhydride grafted polyisobutylene; wherein waterproof component B is an aqueous dispersion obtained by polymerization and alkali neutralization of acrylate or methacrylate formed from C12-C26 fatty alcohols, alkenyl succinic anhydride, 1-octadecene, oleic acid, and acrylic acid; wherein waterproof component C is an aqueous dispersion obtained by neutralization of a reaction product formed from higher alcohols, isocyanates, dihydroxyethyl maleamic acid, dihydroxymethyl acetic acid, and dihydroxymethyl propionic acid with triethylamine.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention involves preparing waterproofing components A, B, and C separately, and then mixing these three components with an emulsifier and solvent in defined amounts to obtain a silicone-free waterproofing fatliquoring agent. Waterproofing component A is formed by neutralizing polyisobutylene maleic anhydride with alkali, enabling it to disperse in the aqueous phase and penetrate between leather fibers. Waterproofing component B contains a polymer structure formed from acrylates or methacrylates formed from C12-C26 fatty alcohols, alkenyl succinic anhydride, octadecene, oleic acid, and acrylic acid. Its long-chain hydrophobic groups reduce the affinity of leather fibers for water, and the carboxyl groups after alkali neutralization facilitate polymer dispersion in water. Waterproofing component C is formed by reacting higher alcohols, isocyanates, dihydroxyethyl maleic acid, dihydroxymethylacetic acid, and dihydroxymethylpropionic acid, and then neutralizing with triethylamine to form an aqueous dispersion, which supplements the waterproofing effect on the leather surface and between fibers. The combination of these three waterproofing components allows for fatliquoring and waterproofing treatment of leather without the use of silicone waterproofing components. The dynamic waterproofing cycles of the leather treated in Examples 1 and 2 reached 18,200–18,422 and 19,754–19,954 respectively, which are close to the 20,136–20,336 cycles of the comparative example of the silicone-containing waterproofing fatliquoring agent. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] It should be noted that "silicone-free" means that the raw materials for preparing waterproofing and fatliquoring agents do not contain polysiloxanes, modified silicone oils, silane coupling agents, or other silicone-containing waterproofing components. Acrylates or methacrylates formed from C12-C26 fatty alcohols refer to esters formed from acrylic acid or methacrylic acid and fatty alcohols with 12-26 carbon atoms; they can also be called long-chain alkyl (meth)acrylates. The 1-octadecene referred to in this article is a straight-chain α-olefin.

[0019] Solid content was determined by gravimetric method: a certain mass of sample was weighed and placed in a pre-weighed weighing dish, dried at 105℃±2℃ to constant weight, and the solid content was calculated as the ratio of the mass of the residue to the mass of the sample after drying. If the solid content after compounding was higher than 52%, distilled water was added; if the solid content was lower than 48%, some water was removed under reduced pressure at a temperature not exceeding 60℃; the determination was repeated and the solid content was controlled between 48% and 52%.

[0020] Example 1

[0021] This embodiment provides a multi-component silicone-free leather waterproofing and fatliquoring agent, the preparation process of which is as follows.

[0022] 1. Preparation of waterproof component A

[0023] Maleic anhydride-grafted polyisobutylene with a number average molecular weight of 1200 and an acid value of 95 mg KOH / g was selected. 100 g of maleic anhydride-grafted polyisobutylene and 20 g of dipropylene glycol monomethyl ether were added to a reaction vessel equipped with a stirrer, thermometer, condenser and dropping device, and stirred at 200 r / min while heating to 80 °C.

[0024] Add 5g of a 50% sodium hydroxide aqueous solution dropwise at a uniform rate over 1 hour, maintaining a temperature of 80℃±2℃ during the addition. After the addition is complete, continue the reaction at 80℃ for 2 hours. After the reaction is complete, take a sample to measure the pH value, and adjust the pH value to 7.2 using a 10% sodium hydroxide aqueous solution or a 10% acetic acid aqueous solution. Stir for 5 minutes after each addition of the adjusting solution, and then take a sample again for measurement.

[0025] Add 80g of distilled water, adjust the stirring speed to 300r / min, and continue stirring for 30 minutes to obtain a yellow-brown, transparent, viscous waterproof component A.

[0026] 2. Preparation of Waterproofing Component B

[0027] Octadecyl methacrylate, octadecenylsuccinic anhydride, and 1-octadecene were used. 90g of octadecyl methacrylate, 10g of octadecenylsuccinic anhydride, 10g of 1-octadecene, 10g of oleic acid, and 20g of dipropylene glycol monomethyl ether were added to a reactor equipped with a stirrer, thermometer, condenser, and two dropping devices. The mixture was stirred at 200 rpm and heated to 80°C. 3g of monoethanolamine was then added, and the reaction was carried out at 80°C for 2 hours.

[0028] Add 350g of distilled water, adjust the stirring speed to 500r / min, and continue stirring for 30 minutes to form a uniform emulsion without a visible oil layer. Add 30g of acrylic acid to the first dropping device; dissolve 2g of ammonium persulfate in 8g of distilled water to obtain 10g of ammonium persulfate aqueous solution with a mass concentration of 20%, and add it to the second dropping device.

[0029] Maintain the reaction system temperature at 80℃±2℃, and simultaneously add acrylic acid and ammonium persulfate aqueous solutions through two inlets. Both are added dropwise at a uniform rate over 2 hours, with continuous stirring at 300 r / min during the addition. After the addition is complete, raise the temperature to 90℃ and continue the reaction for 2 hours.

[0030] Cool to 50°C, add 20g of monoethanolamine and react for 1 hour. Adjust the pH to 7.0 using a 10% (w / w) aqueous solution of monoethanolamine or a 10% (w / w) aqueous solution of acetic acid. Add 50g of distilled water and stir at 300 rpm for 30 minutes to obtain a beige to yellowish-brown viscous waterproof component B.

[0031] 3. Preparation of waterproof component C

[0032] Cetyl alcohol was used as the higher alcohol, and isophorone diisocyanate was used as the isocyanate. 60g of cetyl alcohol and 30g of isophorone diisocyanate were added to a dry reaction vessel, nitrogen was introduced to replace the air, the mixture was stirred at 200r / min and heated to 70℃, and reacted at 70℃ for 2 hours.

[0033] Add 5g of dihydroxyethyl maleamic acid, 1g of dihydroxymethyl acetic acid, 1g of dihydroxymethyl propionic acid, and 0.01g of dibutyltin dilaurate. Heat to 85°C and continue the reaction for 2 hours. Cool to 40°C, add 15g of triethylamine, and react for 1 hour. Adjust the pH to 8.5 using a 10% aqueous solution of triethylamine or a 10% aqueous solution of acetic acid.

[0034] Adjust the stirring speed to 500 r / min, add 110g of distilled water in 5 batches of 22g each, with a 5-minute interval between each batch; after the water is added, continue stirring for 30 minutes to obtain a uniform white emulsion of waterproof component C.

[0035] 4. Compound formulation of silicone-free leather waterproofing and fatliquoring agent

[0036] Weigh 30g of waterproofing component A, 20g of waterproofing component B, and 15g of waterproofing component C and add them to the reactor. Stir at 200 rpm and heat to 80°C. Add 10g of potassium oleate, 5g of potassium oleoyl sarcosinate, and 10g of dipropylene glycol monomethyl ether. Adjust the stirring speed to 300 rpm and stir at 80°C for 60 minutes.

[0037] The solid content was determined by the aforementioned gravimetric method, and distilled water was added or some water was removed under reduced pressure according to the determination results to bring the solid content to 48%–52%. After adjustment, stirring was continued for 20 minutes, and the mixture was cooled to room temperature to obtain the multi-component silicone-free leather waterproofing and fatliquoring agent of Example 1.

[0038] Example 2

[0039] This embodiment provides a multi-component silicone-free leather waterproofing and fatliquoring agent, the preparation process of which is as follows.

[0040] 1. Preparation of waterproof component A

[0041] Maleic anhydride-grafted polyisobutylene with a number average molecular weight of 1800 and an acid value of 85 mg KOH / g was selected. 100 g of maleic anhydride-grafted polyisobutylene and 20 g of propylene glycol butyl ether were added to a reaction vessel, stirred at 200 r / min, and heated to 80 °C.

[0042] 5g of a 50% potassium hydroxide aqueous solution was added dropwise at a uniform rate over 1 hour, maintaining a temperature of 80℃±2℃ during the addition. After the addition was complete, the reaction continued for 2 hours. The pH was adjusted to 7.5 using a 10% potassium hydroxide aqueous solution or a 10% acetic acid aqueous solution. 80g of distilled water was added, and the mixture was stirred at 300 rpm for 30 minutes to obtain waterproof component A.

[0043] 2. Preparation of Waterproofing Component B

[0044] Add 90g lauryl acrylate, 10g hexadecenylsuccinic anhydride, 10g 1-octadecene, 10g oleic acid, and 20g propylene glycol butyl ether to a reaction vessel, stir at 200 rpm, and heat to 80°C. Add 3g morpholine and react at 80°C for 2 hours. Add 350g distilled water and stir at 500 rpm for 30 minutes to form a homogeneous emulsion.

[0045] 30g of acrylic acid and 10g of a 20% ammonium persulfate aqueous solution were simultaneously added dropwise through two inlets over a period of 2 hours each. During the addition, the temperature was maintained at 80℃±2℃ and the mixture was stirred at 300 rpm. After the addition was complete, the temperature was raised to 90℃ and the reaction was allowed to proceed for 2 hours.

[0046] Cool to 50℃, add 20g of morpholine and react for 1 hour. Adjust the pH to 7.0 using a 10% morpholine aqueous solution or a 10% acetic acid aqueous solution. Add 50g of distilled water and stir at 300 rpm for 30 minutes to obtain waterproof component B.

[0047] 3. Preparation of waterproof component C

[0048] Docosyl alcohol was used as the higher alcohol, and hydrogenated diphenylmethane diisocyanate was used as the isocyanate. 60g of docosyl alcohol and 30g of hydrogenated diphenylmethane diisocyanate were added to a dry reaction vessel, nitrogen was introduced to replace the air, the mixture was stirred at 200 rpm and heated to 70°C, and reacted at 70°C for 2 hours.

[0049] Add 5g of dihydroxyethyl maleamic acid, 1g of dihydroxymethyl acetic acid, 1g of dihydroxymethyl propionic acid, and 0.01g of dibutyltin dilaurate. Heat to 85℃ and react for 2 hours. Cool to 40℃, add 15g of triethylamine, and react for 1 hour. Adjust the pH to 8.5 using a 10% aqueous solution of triethylamine or a 10% aqueous solution of acetic acid.

[0050] Add 110g of distilled water in 5 batches, 22g each, with a 5-minute interval between each batch; after the water is added, continue stirring at 500r / min for 30 minutes to obtain waterproof component C.

[0051] 4. Compound formulation of silicone-free leather waterproofing and fatliquoring agent

[0052] Weigh 40g of waterproofing component A, 15g of waterproofing component B, and 10g of waterproofing component C and add them to the reactor. Stir at 200 rpm and heat to 80°C. Add 5g of triethanolamine oleate soap, 5g of oleylsarcosine monoethanolamine soap, 5g of N-oleylsarcosine-octadecylamine salt, and 15g of propylene glycol butyl ether. Adjust the stirring speed to 300 rpm and stir at 80°C for 90 minutes.

[0053] The solid content was determined by the aforementioned gravimetric method, and distilled water was added or some water was removed under reduced pressure according to the determination results to bring the solid content to 48%–52%. After adjustment, stirring was continued for 20 minutes, and the mixture was cooled to room temperature to obtain the multi-component silicone-free leather waterproofing and fatliquoring agent of Example 2.

[0054] Comparative Example 1

[0055] The commercially available silicone-containing waterproofing and grease-adding agent LUTAPOL LWR was used as Comparative Example 1. This product was manufactured by Qihe Lihou Chemical Co., Ltd.

[0056] Application examples

[0057] Three samples were cut from the same part of the same piece of wet blue cowhide and treated with the fatliquoring agents of Example 1, Example 2, and Comparative Example 1, respectively. Each sample underwent softening, chrome retanning, and neutralization retanning in sequence. After neutralization retanning and drainage, the samples proceeded to the fatliquoring process.

[0058] Each fatliquoring agent was added at 10% of the mass of wet blue leather, and the mixture was treated in a drum at 50°C for 1.5 hours. After fatliquoring, 1.2% formic acid (by mass of wet blue leather) was added for fixation. The formic acid was diluted with three times its weight of water and added in three portions, each 10 minutes apart. Subsequently, 1.5% chromium powder (by mass of wet blue leather) was added, and treatment continued for another 1.5 hours. After treatment, the samples were washed with water, removed, and then subjected to air drying, rehydration, and softening by tumbling.

[0059] The dynamic water resistance of leather was tested according to GB / T 22890.2—2024 "Determination of water resistance of soft leather - Part 2: Repeated angular compression method (Meize method)". The tests were conducted using dynamic water resistance testing machines manufactured by Ningbo Dahe Instrument Co., Ltd. and Dongguan Gaoxin Testing Equipment Co., Ltd., respectively. The results are shown in Table 1.

[0060] Table 1

[0061] The test results show that after treatment with the silicone-free waterproofing fatliquoring agent prepared in Example 1, the dynamic waterproofing cycles of the leather were 18,200 and 18,422; after treatment with the silicone-free waterproofing fatliquoring agent prepared in Example 2, the dynamic waterproofing cycles were 19,754 and 19,954; and after treatment with the silicone-containing waterproofing fatliquoring agent, the dynamic waterproofing cycles were 20,136 and 20,336. Table 1 shows that treating leather with the silicone-free leather waterproofing fatliquoring agent provided by this invention can achieve a dynamic waterproofing effect close to that of the silicone-containing waterproofing fatliquoring agent LUTAPOL LWR.

[0062] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the present invention.

Claims

1. A method for preparing a multi-component silicone-free leather waterproofing and fatliquoring agent, characterized in that, include: Maleic anhydride-grafted polyisobutylene was neutralized with alkali in the presence of a solvent to obtain waterproof component A. Acrylic esters or methacrylates formed from C12-C26 fatty alcohols are mixed with alkenyl succinic anhydride, 1-octadecene and oleic acid, and water is added under alkaline conditions to form an emulsion. Acrylic acid is added to the emulsion in the presence of an initiator to carry out a polymerization reaction. After the reaction is completed, alkali neutralization is carried out to obtain waterproof component B. The higher alcohol was reacted with isocyanate, and then dihydroxyethylmaleamic acid, dihydroxymethylacetic acid and dihydroxymethylpropionic acid were added to continue the reaction. After the reaction was completed, triethylamine was used to neutralize the reaction and water was added to obtain waterproof component C. Mix 30-40 parts by weight of the waterproof component A, 15-20 parts by weight of the waterproof component B, 10-15 parts by weight of the waterproof component C, 10-15 parts by weight of the emulsifier and 5-15 parts by weight of the solvent, and control the solid content to be 48%-52% to obtain the silicone-free leather waterproof fatliquoring agent.

2. The preparation method according to claim 1, characterized in that, To prepare the waterproof component A, 100 parts by weight of maleic anhydride-grafted polyisobutylene and 20 parts by weight of solvent are added to a reaction vessel, the temperature is raised to 80°C, 5 parts by weight of alkali are added dropwise over a period of 1 hour, and the reaction is carried out for 2 hours after the addition is completed. The pH value is controlled at 6.5 to 8.5, and 80 parts by weight of distilled water is added to obtain the waterproof component A.

3. The preparation method according to claim 2, characterized in that, The solvent used to prepare the waterproof component A is one or more of ethylene glycol butyl ether, propylene glycol butyl ether, propylene glycol methyl ether, and dipropylene glycol monomethyl ether; the base used is one or more of sodium hydroxide, potassium hydroxide, monoethanolamine, triethanolamine, and 2-amino-2-methyl-1-propanol.

4. The preparation method according to claim 1, characterized in that, In preparing the waterproof component B, 90 parts by weight of acrylate or methacrylate formed from C12-C26 fatty alcohols, 10 parts by weight of alkenyl succinic anhydride, 10 parts by weight of 1-octadecene, 10 parts by weight of oleic acid, and 20 parts by weight of solvent are added to a reaction vessel. The temperature is raised to 80°C, 3 parts by weight of alkali are added, and the reaction is carried out for 2 hours. 350 parts by weight of water are added and stirred to form an emulsion. At the same time, 30 parts by weight of acrylic acid and 10 parts by weight of an initiator solution with a mass concentration of 20% are added dropwise, with each dropwise addition taking 2 hours. After the dropwise addition is completed, the temperature is raised to 90°C and the reaction is carried out for 2 hours. The temperature is then lowered to 50°C, 20 parts by weight of alkali are added, and the reaction is carried out for 1 hour. The pH value is controlled at 6.0-8.

0. 50 parts by weight of distilled water are added to obtain the waterproof component B.

5. The preparation method according to claim 4, characterized in that, The acrylate or methacrylate is one or more of lauryl acrylate, lauryl methacrylate, octadecyl acrylate, and octadecyl methacrylate; the alkenyl succinic anhydride is one or more of dodecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, and C16-C18 alkenyl succinic anhydride; the initiator is ammonium persulfate.

6. The preparation method according to claim 4, characterized in that, The solvent used to prepare the waterproof component B is one or more of ethylene glycol butyl ether, propylene glycol butyl ether, propylene glycol methyl ether, and dipropylene glycol monomethyl ether; the base used is selected from one or more of sodium hydroxide, monoethanolamine, and morpholine.

7. The preparation method according to claim 1, characterized in that, To prepare the waterproof component C, 60 parts by weight of higher alcohol and 30 parts by weight of isocyanate were added to a reaction vessel, heated to 70°C and reacted for 2 hours; 5 parts by weight of dihydroxyethyl maleamic acid, 1 part by weight of dihydroxymethyl acetic acid, 1 part by weight of dihydroxymethyl propionic acid and 0.01 parts by weight of catalyst were added, the temperature was raised to 85°C and reacted for 2 hours; the temperature was lowered to 40°C, 15 parts by weight of triethylamine were added and reacted for 1 hour, the pH was controlled at 8.0-9.0, and then 110 parts by weight of distilled water were added to obtain the waterproof component C.

8. The preparation method according to claim 7, characterized in that, The higher alcohol is one or more of C12-C14 fatty alcohols, C16-C18 fatty alcohols, and fatty alcohols with more than 20 carbon atoms; the isocyanate is isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate; the catalyst is dibutyltin dilaurate.

9. The preparation method according to claim 1, characterized in that, The emulsifier is one or more of sodium oleate, potassium oleate, triethanolamine oleate soap, monoethanolamine oleate soap, sodium oleoyl sarcosinate, potassium oleoyl sarcosinate, triethanolamine oleoyl sarcosinate soap, monoethanolamine oleoyl sarcosinate soap, and N-oleoyl sarcosinate-octadecylamine salt; the solvent mixed with the waterproofing component A, waterproofing component B, and waterproofing component C is one or more of ethylene glycol butyl ether, propylene glycol butyl ether, propylene glycol methyl ether, and dipropylene glycol monomethyl ether.

10. A multi-component silicone-free leather waterproofing and fatliquoring agent, characterized in that, It comprises 30-40 parts by weight of waterproof component A, 15-20 parts by weight of waterproof component B, 10-15 parts by weight of waterproof component C, 10-15 parts by weight of emulsifier, and 5-15 parts by weight of solvent, with a solid content of 48%-52%; wherein the waterproof component A is an alkali neutralization product of maleic anhydride grafted polyisobutylene. The waterproof component B is an aqueous dispersion obtained by polymerization and alkali neutralization of acrylate or methacrylate formed from C12-C26 fatty alcohols, alkenyl succinic anhydride, 1-octadecene, oleic acid and acrylic acid; the waterproof component C is an aqueous dispersion obtained by neutralization of the reaction product formed from higher alcohols, isocyanates, dihydroxyethyl maleamic acid, dihydroxymethyl acetic acid and dihydroxymethyl propionic acid with triethylamine.

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