CN115449284B - Preparation method of antibacterial mildew-proof leather finishing agent containing plant-source-based efficacy factors - Google Patents
Preparation method of antibacterial mildew-proof leather finishing agent containing plant-source-based efficacy factors Download PDFInfo
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- CN115449284B CN115449284B CN202211231673.9A CN202211231673A CN115449284B CN 115449284 B CN115449284 B CN 115449284B CN 202211231673 A CN202211231673 A CN 202211231673A CN 115449284 B CN115449284 B CN 115449284B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a preparation method of an antibacterial mildew-proof leather finishing agent containing plant-based efficacy factors. The preparation method is characterized in that menthol with an antibacterial adhesion function on the surface is subjected to chemical modification, the dihydroxyl with reactivity is introduced into the molecular structure of the menthol to prepare modified menthol, and then the modified menthol is introduced into a polyurethane matrix through polymerization reaction to prepare the polyurethane leather coating film-forming material containing the complete menthol molecular structure. The modified menthol prepared by the method provided by the invention has good antibacterial and mildew-proof adhesion, and the structural dihydroxyl can be subjected to addition polymerization reaction with diisocyanate, so that the modified menthol can be introduced into a polyurethane matrix at a molecular level, and finally the leather finishing agent with lasting antibacterial and mildew-proof effects is prepared.
Description
Technical Field
The invention relates to the fields of antibacterial and mildew-proof material research and water-based polymer-based leather finishing material development, in particular to a preparation method of an antibacterial and mildew-proof leather finishing agent containing plant-source-based efficacy factors.
Background
The leather surface coating is an important section for improving the appearance and physical properties of leather and endowing the leather with the functions of antibiosis, mildew resistance and the like, protection and high added value. Waterborne Polyurethane (WPU) has become the dominant film forming material in leather finishing stations with its excellent combination of properties and environmental friendliness. Among the existing mould-proof methods for finished leather, the most effective and main method is to add a sterilizing mould inhibitor to the WPU emulsion for leather finishing. However, the physical blending method is only suitable for short-term protection, and the micromolecule sterilization mildew preventive on the leather surface can gradually migrate and dissociate in the use process to lose efficacy; the least beneficial is that release of the antimicrobial mildew inhibitor induces resistance to the microorganism and presents potential environmental and health risks. With the increasing importance of global environmental protection and sustainable development, many leather mildew-proof chemicals with toxic and side effects have been banned or limited in use by the european union directive and are not suitable for leather products in close contact with human bodies. The most dominant mildew-proof chemicals in the leather market at present, thiocyanomethylthio-benzothiazole (TCMTB) and n-octyl isothiazolinone (OTT), have also been reported to have environmental health risks, and the International environmental protection textile Association has set limit requirements (both less than or equal to 2500 mg/kg) on TCMTB and OTT in leather products. The problems of biological safety and environmental friendliness of the antibacterial mildew-proof material are increasingly remarkable, and the antibacterial mildew-proof material becomes a bottleneck for restricting the development of the antibacterial mildew-proof material. The novel WPU antibacterial mildew-proof finishing agent special for leather, which is efficient, durable, safe and universal, has important application value.
Essentially, the adhesion of microorganisms at the surface interface of a material is based on the interaction between the two. Microorganisms are also a living body, and chirality is an essential feature of a living body. The research shows that when the microbial cells are contacted with the external surface, different chiral structures (stereochemical structures) on the surface of the material can be perceived and distinguished, so that obvious adhesion difference is displayed, and a new view is provided for the design and development of novel antibacterial adhesion finishing agents. The antibacterial adhesion strategy is important in preventing and preventing infection from the source, and the earliest adhesion of microorganisms on the surface of the material is killed in the cradle; the strategy is different from the traditional sterilization strategy, and the used antibacterial adsorption monomer does not need to have sterilization activity, so that the antibacterial adsorption monomer is generally low in toxicity and even nontoxic, is safe to a living body/human body, and is very suitable for mildew prevention of the leather surface in daily contact with the human body.
Considering that plants are important treasury with natural bioactive compounds, china has rich plant resources, so that the natural bioactive compounds which are compatible with natural environment, safe and nontoxic are searched from the plants, and the natural bioactive compounds also become new hot spots for developing antibacterial materials. The menthol compound belongs to a plant source natural compound, the existence of the hydrophobic structure of the menthol compound is beneficial to improving the wet-rubbing resistance of the leather coating, the safety and water resistance requirements of the leather industry on the antibacterial mildew-proof finishing agent are very met, and the stereochemical structure (three chiral carbon atoms) of the menthol enables the menthol compound to have antibacterial adhesion performance.
Based on the above, the invention discloses a preparation method of an antibacterial mildew-proof leather finishing agent containing plant-based efficacy factors, menthol is introduced into a polyurethane matrix from the molecular level, and the durable antibacterial mildew-proof adhesion performance is endowed. At present, the method is not reported in the literature and patents.
Disclosure of Invention
The invention aims to provide a preparation method of an antibacterial mildew-proof leather finishing agent containing plant-source-based efficacy factors, which is characterized by comprising the following steps:
(1) 1, adding diisocyanate and polymer dihydric alcohol into a reactor according to the mol ratio of (2-5), wherein the temperature is 50-90 ℃, the stirring speed is 500-1000 rpm, and stirring and reacting for 40-60 min to obtain polyurethane prepolymer;
(2) Adding dihydroxyl modified menthol into a reaction bottle, wherein the molar ratio of dihydroxyl modified menthol to polymer dihydric alcohol is (1-4) 1, the temperature is 80-100 ℃, the stirring speed is 500-1000 rpm, and the reaction is carried out for 1-3 h under the condition of catalyst;
(3) Adding certain mass of dimethylolpropionic acid into a reaction bottle, wherein the dimethylolpropionic acid accounts for 4-6% of the total mass of four reactants of diisocyanate, polymer dihydric alcohol and modified menthol containing dihydroxyl and dimethylolpropionic acid, the system temperature is 60-100 ℃, the stirring speed is 100-2000 rpm, and the reaction is carried out for 1-2 h under the condition of a catalyst;
(4) Adding a neutralizing agent triethylamine into a reaction bottle, wherein the temperature is 20-40 ℃, the stirring speed is 500-1000 rpm, the neutralization is carried out for 0.5-1 h, the pH value is regulated to 8-10, then adding the reaction product into a certain amount of deionized water, stirring at a high speed for 10-30 min, the stirring speed is 7000-20000 rpm, then stirring at a low speed for 1-2 h, the stirring speed is 1000-3000 rpm, and concentrating the product until the solid content is 15% -35%, thus obtaining the antibacterial mildew-proof aqueous polymer leather finishing agent containing plant-based efficacy factors;
the preparation method of the modified menthol with the double hydroxyl groups comprises the following two steps:
the first step: dissolving menthol with a certain mass into methylene dichloride, wherein the volume concentration of the solution is 30-50%, and then adding 1,3, 5-triazine and 2,4, 6-trimethyl-3-aminopyridine into the solution, wherein the mol ratio of 1,3, 5-triazine to menthol is 1:1,1,3, 5-triazine to 2,4, 6-trimethyl-3-aminopyridine is (0.5-0.75): 1, stirring and reacting a reaction system for 8-12 hours under bath; washing the reaction product with water for 3-5 times, removing dichloromethane by rotary evaporation, and purifying the concentrated solution through a silica gel chromatographic column to obtain an intermediate product A, wherein the granularity of silica gel is 200-300 meshes;
and a second step of: and (3) adding the intermediate product A and the ethanolamine in a molar ratio of 1:1 into a reaction bottle simultaneously, then adding a certain mass of solvent dichloromethane, controlling the volume concentration of the reaction solution to be 20-30%, reacting the reaction system at 60-100 ℃ for 4-8 h, washing with water for 3 times, filtering, removing the solvent dichloromethane by rotary evaporation, and drying in a baking oven at 40 ℃ for 24h to obtain the modified menthol containing the dihydroxyl.
The preparation method of the antibacterial mildew-proof water-based polymer leather finishing agent containing the plant-based efficacy factors is characterized in that the polymer dihydric alcohol is one of polycarbonate diol, polyether dihydric alcohol, polycaprolactone dihydric alcohol, hydroxyl-terminated polysiloxane and hydroxyl-terminated polylactic acid with the molecular weight of 1000-6000.
The preparation method of the antibacterial mildew-proof leather finishing agent containing the plant-based efficacy factors is characterized in that the diisocyanate is one of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
The invention discloses a preparation method of an antibacterial mildew-proof leather finishing agent containing plant-based efficacy factors. The preparation method is characterized in that menthol with an antibacterial adhesion function on the surface is subjected to chemical modification, the dihydroxyl with reactivity is introduced into the molecular structure of the menthol to prepare modified menthol, and then the modified menthol is introduced into a polyurethane matrix through polymerization reaction to prepare the polyurethane leather coating film-forming material containing the complete menthol molecular structure. The modified menthol prepared by the method provided by the invention has good antibacterial and mildew-proof adhesion, and the structural dihydroxyl can be subjected to addition polymerization reaction with diisocyanate, so that the modified menthol can be introduced into a polyurethane matrix at a molecular level, and finally the leather finishing agent with lasting antibacterial and mildew-proof effects is prepared.
Description of the embodiments
Four examples of the present invention are given below to illustrate in detail the preparation of an antimicrobial and mildew-resistant leather finish containing plant-based efficacy factors.
Example 1
The specific operation method for preparing the modified menthol containing the dihydroxyl is as follows: 9.4. 9.4 g menthol was weighed and dissolved in 20mL of methylene chloride, then 5.5g of 1,3, 5-triazine and 4 mL of 2,4, 6-trimethyl-3-aminopyridine were added thereto, and the mixture was stirred under ice bath to react 12 h; washing the reaction product with water for 3 times after the reaction, removing dichloromethane by rotary evaporation, and purifying the concentrated solution through a silica gel chromatographic column (200-300 sieves) to obtain an intermediate product A; then 1.8 g intermediate A and 3.66g of ethanolamine are taken and added into a reaction bottle, 20mL solvent methylene dichloride is added, the reaction system reacts at 80 ℃ for 8 h, water washing is carried out for 3 times, the organic solvent is removed by rotary evaporation after filtration, and the modified menthol containing dihydroxyl can be prepared after drying in a baking oven at 40 ℃ for 24 hours.
15.00. 15.00 g polycarbonate diol (M) n =1000) in a reactor, 6.96, g toluene diisocyanate and 250mL of tetrahydrofuran solvent were added to the reactor, and the mixture was mechanically stirred under nitrogen protection and reacted at 60 ℃ for 30min. 1.34g of dimethylolpropionic acid was added thereto and the reaction was catalyzed at 80℃for 2 hours with stirring. Modified menthol containing dihydroxyl and catalyst were added to 4.45. 4.45 g, and reacted at 80℃for 2h. Adding neutralizing agent at 40deg.C with stirring speed of 1000rpm for 40min, and adjusting pH to 9. Adding the reactant into high-purity deionized water, and stirring at high speedEmulsifying 0.5. 0.5h, stirring at 10000rpm to obtain aqueous polyurethane emulsion, and concentrating the reaction product to 30% of solid content.
Example 2
The specific operation method for preparing the modified menthol containing the dihydroxyl is as follows: 9.4. 9.4 g menthol was weighed and dissolved in 20mL of methylene chloride, then 5.5g of 1,3, 5-triazine and 4 mL of 2,4, 6-trimethyl-3-aminopyridine were added thereto, and the mixture was stirred under ice bath to react 12 h; washing the reaction product with water for 3 times after the reaction, removing dichloromethane by rotary evaporation, and purifying the concentrated solution through a silica gel chromatographic column (200-300 sieves) to obtain an intermediate product A; then 1.8 g intermediate A and 3.66g of ethanolamine are taken and added into a reaction bottle, 20mL solvent methylene dichloride is added, the reaction system reacts at 80 ℃ for 8 h, water washing is carried out for 3 times, the organic solvent is removed by rotary evaporation after filtration, and the modified menthol containing dihydroxyl can be prepared after drying in a baking oven at 40 ℃ for 24 hours.
30.00. 30.00 g polytetrahydrofuran ether (M) n =2000) was added to a 500ml three-necked flask, dehydrated in vacuo for 2 hours, cooled to 60 ℃, 10.08, g, diphenylmethane diisocyanate was added, 300ml of tetrahydrofuran solvent was added, and the mixture was mechanically stirred under nitrogen protection, and reacted at 60 ℃ for 30 minutes. 1.52g of dimethylolpropionic acid was added thereto and the reaction was stirred at 80℃for 2 hours. 3.98 portions g portions of modified menthol containing double hydroxyl groups and catalyst are added to react at 80 ℃ for 2h. Adding neutralizing agent at 40deg.C with stirring speed of 1000rpm for 40min, and adjusting pH to 9. The reactant is added into high-purity deionized water, stirred and emulsified at high speed for 0.5h, the stirring speed is 15000rpm, the aqueous polyurethane emulsion is obtained, and the reaction product is concentrated to the solid content of 20%.
Example 3
The specific operation method for preparing the modified menthol containing the dihydroxyl is as follows: 9.4. 9.4 g menthol was weighed and dissolved in 20mL of methylene chloride, then 5.5g of 1,3, 5-triazine and 4 mL of 2,4, 6-trimethyl-3-aminopyridine were added thereto, and the mixture was stirred under ice bath to react 12 h; washing the reaction product with water for 3 times after the reaction, removing dichloromethane by rotary evaporation, and purifying the concentrated solution through a silica gel chromatographic column (200-300 sieves) to obtain an intermediate product A; then 1.8 g intermediate A and 3.66g of ethanolamine are taken and added into a reaction bottle, 20mL solvent methylene dichloride is added, the reaction system reacts at 80 ℃ for 8 h, water washing is carried out for 3 times, the organic solvent is removed by rotary evaporation after filtration, and the dihydroxyl-containing modified menthol can be prepared by drying in a baking oven at 40 ℃ for 24 hours.
30.00. 30.00 g polycaprolactone diol (M) n =2000), and the mixture was put into a 500ml three-necked flask, dehydrated in vacuo for 2 hours, cooled to 60. 60℃, and then 8.89 g isophorone diisocyanate was added, 300ml THF was added, and the mixture was mechanically stirred under nitrogen protection, and reacted at 60 ℃ for 30 minutes. 1.34g of dimethylolpropionic acid was added thereto, and the reaction was stirred at 80℃for 2h. Modified menthol containing dihydroxyl and catalyst were added to 4.45. 4.45 g, and reacted at 80℃for 2h. Adding neutralizing agent at 40deg.C with stirring speed of 1000rpm for 40min, and adjusting pH to 9. Adding the reactant into high-purity deionized water, stirring at high speed to emulsify 0.5. 0.5h, stirring at 10000rpm to obtain aqueous polyurethane emulsion, and concentrating the reaction product until the solid content is 30%.
Claims (3)
1. The preparation method of the antibacterial mildew-proof leather finishing agent containing the plant-source-based efficacy factors is characterized by comprising the following steps:
(1) 1, adding diisocyanate and polymer dihydric alcohol into a reactor according to the mol ratio of (2-5), wherein the temperature is 50-90 ℃, the stirring speed is 500-1000 rpm, and stirring and reacting for 40-60 min to obtain polyurethane prepolymer;
(2) Adding dihydroxyl-containing modified menthol into a reaction bottle, wherein the molar ratio of the dihydroxyl-containing modified menthol to the polymer dihydric alcohol is (1-3) 1, the temperature is 80-100 ℃, the stirring speed is 500-1000 rpm, and the reaction is 1-3 h under the condition of a catalyst;
(3) Adding certain mass of dimethylolpropionic acid into a reaction bottle, wherein the dimethylolpropionic acid accounts for 4-6% of the total mass of four reactants including diisocyanate, polymer dihydric alcohol, modified menthol containing dihydroxyl and dimethylolpropionic acid, controlling the temperature of a system to be 60-100 ℃, and reacting for 1-2 h under the condition of a catalyst at the stirring speed of 100-2000 rpm;
(4) Adding a neutralizing agent triethylamine into a reaction bottle, wherein the temperature is 20-40 ℃, the stirring speed is 500-1000 rpm, the neutralization is carried out for 0.5-1 h, the pH value is regulated to 8-10, then adding the reaction product into a certain amount of deionized water, stirring at a high speed for 10-30 min, the stirring speed is 7000-20000 rpm, then stirring at a low speed for 1-2 h, the stirring speed is 1000-3000 rpm, and concentrating the product until the solid content is 15% -35%, thereby obtaining the antibacterial and mildew-proof leather finishing agent containing plant-based functional factors;
the preparation method of the modified menthol containing the dihydroxyl comprises the following two steps:
the first step: dissolving menthol with a certain mass into dichloromethane, wherein the volume concentration of the solution is 30-50%, and then adding 1,3, 5-triazine and 2,4, 6-trimethyl-3-aminopyridine into the solution respectively, wherein the mol ratio of 1,3, 5-triazine to menthol is 1:1,1,3, 5-triazine to 2,4, 6-trimethyl-3-aminopyridine is (0.5-0.75): 1, stirring and reacting a reaction system for 8-12 hours under bath; washing the reaction product with water for 3-5 times, removing dichloromethane by rotary evaporation, and purifying the concentrated solution through a silica gel chromatographic column to obtain an intermediate product A, wherein the granularity of the silica gel is 200-300 meshes;
and a second step of: and (3) adding the intermediate product A and the ethanolamine in a molar ratio of 1:1 into a reaction bottle simultaneously, then adding a certain mass of solvent dichloromethane, controlling the volume concentration of the reaction solution to be 20-30%, reacting the reaction system at 60-100 ℃ for 4-8 h, washing with water for 3 times, filtering, removing the solvent dichloromethane by rotary evaporation, and drying in a baking oven at 40 ℃ for 24h to obtain the modified menthol containing the dihydroxyl.
2. The method for preparing the antibacterial and mildew-proof leather finishing agent containing plant-based efficacy factors according to claim 1, wherein the polymer dihydric alcohol is one of polycarbonate diol, polyether dihydric alcohol, polycaprolactone dihydric alcohol, hydroxyl-terminated polysiloxane and hydroxyl-terminated polylactic acid with the molecular weight of 1000-6000.
3. The method for preparing the antibacterial and mildew-proof leather finishing agent containing plant-based functional factors according to claim 1, wherein the diisocyanate is one or a mixture of more of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
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