CN115449284A - Preparation method of antibacterial and mildewproof leather finishing agent containing plant source-based functional factors - Google Patents
Preparation method of antibacterial and mildewproof leather finishing agent containing plant source-based functional factors Download PDFInfo
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- CN115449284A CN115449284A CN202211231673.9A CN202211231673A CN115449284A CN 115449284 A CN115449284 A CN 115449284A CN 202211231673 A CN202211231673 A CN 202211231673A CN 115449284 A CN115449284 A CN 115449284A
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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
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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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- 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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- 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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- 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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Abstract
The invention discloses a preparation method of an antibacterial and mildewproof leather finishing agent containing plant source-based efficacy factors. The method is characterized in that firstly, menthol with an antibacterial adhesion function on the surface is chemically modified, dihydroxy with reaction activity 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 finishing film-forming material containing a complete menthol molecular structure. The modified menthol prepared by the method has good antibacterial and mildewproof adhesion, and the dihydroxy on the structure can be subjected to addition polymerization reaction with diisocyanate, so that the modified menthol can be introduced into a polyurethane matrix on a molecular level, and finally the leather finishing agent with a lasting antibacterial and mildewproof effect is prepared.
Description
Technical Field
The invention relates to the research field of antibacterial and mildewproof materials and the development field of waterborne polymer-based leather finishing materials, in particular to a preparation method of an antibacterial and mildewproof leather finishing agent containing plant source-based efficacy factors.
Background
The leather surface finishing is an important working section for improving the appearance and physical properties of leather, endowing the leather with the functions of protection such as antibiosis, mildew prevention and the like and high added value. Waterborne Polyurethane (WPU) has become the dominant film-forming material in the leather finishing section due to excellent comprehensive performance and environmental friendliness. Among the existing finished leather mildew-proofing methods, the most effective and most important method is to add a bactericidal mildew-proofing agent to the WPU emulsion for leather finishing. But the physical blending method is only suitable for short-term protection, and the micromolecular bactericidal mildew preventive on the surface of the leather gradually migrates and dissociates to lose the efficacy in the using process; most disadvantageously, the release of the antimicrobial and antifungal agents induces microbial resistance and presents potential environmental and health risks. The new crown epidemic outburst into the new crown epidemic situation in 2020 has already knocked out the alarm for the abuse of antibiotics and is imminent to restrain the drug resistance of microorganisms. With the increasing attention on environmental protection and sustainable development in the world, many leather mildew-proof chemicals with toxic and side effects are listed in the directive of the European Union to be forbidden or used in limited quantity, and are not suitable for leather products in close contact with human bodies. The most important mildew-proof chemicals in the leather market at present, namely thiocyanomethylthio-benzothiazole (TCMTB) and n-octyl isothiazolinone (OTT), have been reported to have environmental health risks, and the International environmental protection and textile Association has set a limit requirement (both are 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 and mildewproof material are increasingly prominent, and the antibacterial and mildewproof material gradually becomes a bottleneck restricting the development of the antibacterial and mildewproof material. The WPU antibacterial and mildewproof finishing agent which is special for the novel leather, efficient, lasting, safe and universal has important application value.
Essentially, microbial adhesion at the material surface interface is based on the interaction between the two. Microorganisms are also a living organism, and chirality is an essential feature of living organisms. Research finds that when microbial cells contact with the external surface, different chiral structures (stereochemical structures) on the surface of the material can be perceived and distinguished, so that obvious adhesion differences are shown, and the finding provides a new visual angle for the design and development of novel antibacterial adhesion coating agents. The antibacterial adhesion strategy focuses on prevention-prevention of infection from the source, killing the earliest adhesion of microorganisms on the surface of the material in the cradle; the strategy is different from the traditional sterilization strategy, and the used antibacterial adsorption monomer does not need to have killing activity, so that the antibacterial adsorption monomer is generally low in toxicity or even non-toxic, is safe to life bodies/human bodies, and is very suitable for mildew prevention of the leather surface in daily contact with the human bodies.
Considering that plants are an important treasury of compounds with natural biological activity and China has rich plant resources, finding out safe and nontoxic natural active compounds compatible with natural environment from plants also becomes a new hotspot for research and development of antibacterial materials. The menthol compound belongs to a plant source natural compound, the existence of a hydrophobic structure of the menthol compound is favorable for improving the wet rubbing resistance of a leather coating, the safety and water resistance requirements of the leather industry on the antibacterial and mildewproof finishing agent are met, and the antibacterial adhesion performance of the menthol compound is realized due to the stereochemical structure (three chiral carbon atoms).
Based on the preparation method, the invention discloses a preparation method of an antibacterial and mildewproof leather finishing agent containing plant source-based functional factors, wherein menthol is introduced into a polyurethane matrix from a molecular level, and the lasting antibacterial and mildewproof adhesion performance is endowed. At present, the method is not reported in documents and patents.
Disclosure of Invention
The invention aims to provide a preparation method of an antibacterial and mildewproof leather finishing agent containing plant source-based functional factors, which is characterized by comprising the following steps:
(1) Adding diisocyanate and polymer diol into a reactor according to the molar ratio of (2-5) to 1, wherein the temperature is 50-90 ℃, the stirring speed is 500-1000 rpm, and the stirring reaction is carried out for 40-60 min to obtain a polyurethane prepolymer;
(2) Adding modified menthol with dihydroxy into a reaction bottle, wherein the molar ratio of the modified menthol with dihydroxy to polymer dihydric alcohol is (1-4) to 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 a catalyst;
(3) Adding dimethylolpropionic acid with a certain mass into a reaction bottle, wherein the dimethylolpropionic acid accounts for 4 to 6 percent of the total mass of four reactants of diisocyanate, polymer diol, modified menthol containing dihydroxy and dimethylolpropionic acid, the system temperature is 60 to 100 ℃, the stirring speed is 100 to 2000rpm, and the reaction is carried out for 1 to 2 hours under the condition of a catalyst;
(4) Adding triethylamine serving as a neutralizing agent into a reaction bottle, regulating the temperature to be 20-40 ℃, stirring at the speed of 500-1000 rpm, neutralizing for 0.5-1 h, regulating the pH value to be 8-10, then adding a reaction product into a certain amount of deionized water, stirring at a high speed of 10-30min at the speed of 7000-20000 rpm, stirring at a low speed of 1-2h at the speed of 1000-3000 rpm, and concentrating the product until the solid content is 15-35% to obtain the antibacterial and mildewproof waterborne polymer leather finishing agent containing the plant-derived functional factors;
the preparation method of the modified menthol with the dihydroxy comprises the following two steps:
the first step is as follows: dissolving a certain mass of menthol in dichloromethane (the volume concentration of the solution is 30 to 50%), adding 1,3, 5-triazine and 2,4, 6-trimethyl-3-aminopyridine into the solution, wherein the molar ratio of the 1,3, 5-triazine to the menthol is 1:1, stirring the reaction system under bathing for 8 to 12 hours; after the reaction, washing the reaction product with water for 3 to 5 times, removing dichloromethane by rotary evaporation, and finally purifying the concentrated solution by using a silica gel chromatographic column (200 to 300 sieves) to obtain an intermediate product A;
the second step: adding an intermediate product A and ethanolamine in a molar ratio of 1:1 into a reaction bottle at the same time, adding a certain mass of solvent dichloromethane (the volume concentration of the reaction solution is controlled to be 20 to 30%), reacting at the temperature of 60 to 100 ℃ for 4 to 8 hours in a reaction system, washing with water for 3 times, filtering, performing rotary evaporation to remove the solvent dichloromethane, and drying in an oven at the temperature of 40 ℃ for 24 hours to obtain the modified menthol containing dihydroxy.
The preparation method of the antibacterial and mildewproof waterborne polymer leather finishing agent containing the plant source based efficacy factor 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 and mildewproof leather finishing agent containing the plant-derived functional 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 and mildewproof leather finishing agent containing plant source-based efficacy factors. The method is characterized in that firstly, menthol with an antibacterial adhesion function on the surface is chemically modified, dihydroxy with reaction activity 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 finishing film-forming material containing a complete menthol molecular structure. The modified menthol prepared by the method has good antibacterial and mildewproof adhesion, and the dihydroxy on the structure can be subjected to addition polymerization reaction with diisocyanate, so that the modified menthol can be introduced into a polyurethane matrix on a molecular level, and finally the leather finishing agent with a lasting antibacterial and mildewproof effect is prepared.
Detailed Description
Four examples of the present invention are given below to specifically illustrate the preparation of the antibacterial and antifungal leather finishing agent containing the plant-derived functional factor.
Example 1
The specific operation method for preparing the modified menthol containing the dihydroxy comprises the following steps: weighing 9.4 g of menthol, dissolving the menthol in 20mL of dichloromethane, adding 5.5g of 1,3, 5-triazine and 4 mL of 2,4, 6-trimethyl-3-aminopyridine, and stirring for reaction for 12 h under ice bath; after the reaction, washing the reaction product with water for 3 times, removing dichloromethane by rotary evaporation, and finally purifying the concentrated solution through a silica gel chromatographic column (200-300 sieve) to obtain an intermediate product A; and then adding 1.8 g of the intermediate product A and 3.66g of ethanolamine into a reaction bottle, adding 20mL of solvent dichloromethane, reacting the reaction system at the temperature of 80 ℃ for 8 hours, washing with water for 3 times, filtering, performing rotary evaporation to remove the organic solvent, and drying in an oven at the temperature of 40 ℃ for 24 hours to obtain the modified menthol containing the dihydroxy.
15.00 g of polycarbonate diol (M) was weighed n = 1000) in a reactor, 6.96 g of toluene diisocyanate and 250mL of tetrahydrofuran solvent are added to the reactor, mechanically stirred under nitrogen protection, and reacted at 60 ℃ for 30min. 1.34g dimethylolpropionic acid was added and the reaction was catalyzed with stirring at 80 ℃ for 2h. Adding 4.45 g of modified menthol containing dihydroxy and a catalyst, and reacting for 2 hours at 80 ℃. Adding neutralizer at 40 deg.C, stirring at 1000rpm for 40min, and adjusting pH to 9. Adding the reactants into high-purity deionized water, stirring at a high speed of 10000rpm for emulsification for 0.5h to obtain an aqueous polyurethane emulsion, and concentrating the reaction product until the solid content is 30%.
Example 2
The specific operation method for preparing the modified menthol containing the dihydroxy comprises the following steps: weighing 9.4 g of menthol, dissolving the menthol in 20mL of dichloromethane, adding 5.5g of 1,3, 5-triazine and 4 mL of 2,4, 6-trimethyl-3-aminopyridine, and stirring for reaction for 12 h under ice bath; after the reaction, washing the reaction product for 3 times, removing dichloromethane by rotary evaporation, and finally purifying the concentrated solution by a silica gel chromatographic column (200-300 sieves) to obtain an intermediate product A; and then adding 1.8 g of the intermediate product A and 3.66g of ethanolamine into a reaction bottle, adding 20mL of solvent dichloromethane, reacting the reaction system at the temperature of 80 ℃ for 8 hours, washing with water for 3 times, filtering, performing rotary evaporation to remove the organic solvent, and drying in an oven at the temperature of 40 ℃ for 24 hours to obtain the modified menthol containing the dihydroxy.
30.00 g of polytetrahydrofuran ether (M) are weighed out n = 2000) was added to a 500ml three-necked flask, vacuum dehydration was performed for 2h, the temperature was reduced to 60 ℃, 10.08 g of diphenylmethane diisocyanate was added, 300ml of tetrahydrofuran solvent was added, mechanical stirring was performed under nitrogen protection, and reaction was performed at 60 ℃ for 30min. 1.52g dimethylolpropionic acid was added and the reaction stirred at 80 ℃ for 2h. Adding 398 g of modified menthol containing dihydroxy groups and a catalyst, and reacting at 80 ℃ for 2 hours. Adding neutralizer at 40 deg.C under stirring speed of 1000rpm for 40min, and adjusting pH to 9. Adding the reactant into high-purity deionized water, stirring at a high speed of 15000rpm for emulsification for 0.5h to obtain the waterborne polyurethane emulsion, and concentrating the reaction product until the solid content is 20%.
Example 3
The specific operation method for preparing the modified menthol containing the dihydroxy comprises the following steps: weighing 9.4 g of menthol, dissolving the menthol in 20mL of dichloromethane, adding 5.5g of 1,3, 5-triazine and 4 mL of 2,4, 6-trimethyl-3-aminopyridine, and stirring for reaction for 12 h under ice bath; after the reaction, washing the reaction product with water for 3 times, removing dichloromethane by rotary evaporation, and finally purifying the concentrated solution through a silica gel chromatographic column (200-300 sieve) to obtain an intermediate product A; and then adding 1.8 g of the intermediate product A and 3.66g of ethanolamine into a reaction bottle, adding 20mL of solvent dichloromethane, reacting the reaction system at the temperature of 80 ℃ for 8 hours, washing with water for 3 times, filtering, performing rotary evaporation to remove the organic solvent, and drying in an oven at the temperature of 40 ℃ for 24 hours to obtain the modified menthol containing dihydroxy.
30.00 g polycaprolactone diol (M) was weighed n = 2000), adding into a 500ml three-neck flask, dehydrating in vacuum for 2h, reducing the temperature to 60 ℃, adding 8.89 g isophorone diisocyanate, adding 300ml THF, mechanically stirring under nitrogen protection, and reacting at 60 ℃ for 30min. 1.34g dimethylolpropionic acid was added and the reaction was stirred at 80 ℃ for 2h. Adding 4.45 g of modified menthol containing dihydroxy and a catalyst, and reacting for 2 hours at 80 ℃. Adding neutralizer at 40 deg.C, stirring at 1000rpm for 40min, and adjusting pH to 9. Adding the reactants into high-purity deionized water, stirring at a high speed of 10000rpm for emulsification for 0.5h to obtain an aqueous polyurethane emulsion, and concentrating the reaction product until the solid content is 30%.
Claims (3)
1. The preparation method of the antibacterial and mildewproof leather finishing agent containing the plant source based efficacy factor is characterized by comprising the following steps:
(1) Adding diisocyanate and polymer diol into a reactor according to the molar ratio of (2-5) to 1, wherein the temperature is 50-90 ℃, the stirring speed is 500-1000 rpm, and the stirring reaction is carried out for 40-60 min to obtain a polyurethane prepolymer;
(2) Adding modified menthol containing dihydroxy into a reaction bottle, wherein the molar ratio of the modified menthol containing dihydroxy to polymer dihydric alcohol is (1-3) to 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 a catalyst;
(3) Adding dimethylolpropionic acid with a certain mass into a reaction bottle, wherein the dimethylolpropionic acid accounts for 4-6% of the total mass of four reactants, namely diisocyanate, polymer dihydric alcohol, modified menthol containing dihydroxy and dimethylolpropionic acid, controlling the temperature of a system to be 60-100 ℃, stirring at a speed of 100-2000 rpm, and reacting for 1-2 hours under the condition of a catalyst;
(4) Adding triethylamine serving as a neutralizing agent into a reaction bottle, regulating the temperature to be 20-40 ℃, stirring at the speed of 500-1000 rpm, neutralizing for 0.5-1 h, regulating the pH value to be 8-10, then adding a reaction product into a certain amount of deionized water, stirring at a high speed of 7000-20000 rpm for 10-30 min, stirring at a low speed of 1-2h at the stirring speed of 1000-3000 rpm, and concentrating the product until the solid content is 15-35% to obtain the antibacterial and mildewproof leather finishing agent containing the plant-derived functional factors;
the preparation method of the modified menthol containing dihydroxy comprises the following two steps:
the first step is as follows: dissolving a certain mass of menthol in dichloromethane (the volume concentration of the solution is 30 to 50%), and then adding 1,3, 5-triazine and 2,4, 6-trimethyl-3-aminopyridine into the solution respectively, wherein the molar ratio of the 1,3, 5-triazine to the menthol is 1:1, stirring the reaction system under bathing for 8 to 12 hours; after the reaction, washing the reaction product with water for 3 to 5 times, removing dichloromethane by rotary evaporation, and finally purifying the concentrated solution by using a silica gel chromatographic column (200 to 300 sieves) to obtain an intermediate product A;
the second step is that: adding an intermediate product A and ethanolamine in a molar ratio of 1:1 into a reaction bottle at the same time, adding a certain mass of solvent dichloromethane (the volume concentration of the reaction solution is controlled to be 20 to 30%), reacting at 60 to 100 ℃ for 4 to 8 hours in a reaction system, washing with water for 3 times, filtering, performing rotary evaporation to remove the solvent dichloromethane, and drying in an oven at 40 ℃ for 24 hours to obtain the modified menthol containing dihydroxy.
2. The method for preparing the antibacterial and mildewproof leather finishing agent containing the plant-derived functional factor according to claim 1, wherein the polymer diol is one of polycarbonate diol, polyether diol, polycaprolactone diol, hydroxyl-terminated polysiloxane and hydroxyl-terminated polylactic acid with the molecular weight of 1000-6000.
3. The method for preparing the antibacterial and mildewproof leather finishing agent containing the plant-derived functional factor according to claim 1, wherein the diisocyanate is one or a mixture of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
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