A composite sulfonic acid modified polyisocyanate, preparation method and application thereof

Abstract

This patent relates to a method for preparing a composite sulfonic acid hydrophilic modified polyisocyanate, and its application in the fields of adhesives, coatings, etc. The modified polyisocyanate prepared by this method has the advantages of high production efficiency, low viscosity, good dispersibility, etc.

Description

Technical Field

[0001] The invention relates to the field of modified isocyanates, in particular to a composite sulfonic acid hydrophilic modified polyisocyanate. The invention also relates to the application of the prepared sulfonic acid hydrophilic modified polyisocyanate in the fields of coating agents, adhesives, sealants, etc. Background Art

[0002] With the development and changes of society, environmental issues have attracted more and more attention from people. Countries around the world pay more and more attention to the protection of the ecological environment, and enterprises are becoming more and more aware of environmental protection. There is an urgent need to transform from oil-based to water-based products in the fields of coatings and adhesives. Compared with oil-based products, the production process of water-based products and the introduction of hydrophilic groups determine that single-component water-based products have worse resistance and mechanical properties. The introduction of water-based isocyanate curing agents can effectively increase the molecular weight of water-based products, improve the resistance of water-based coatings and adhesives due to small molecular weight and strong hydrophilicity, and thus accelerate the process of oil-based coatings and adhesives to water-based products.

[0003] Water-based isocyanate curing agents can be divided into polyether hydrophilic modified curing agents and sulfonic acid hydrophilic modified curing agents according to the type of hydrophilic groups. Among them, polyether modified isocyanate has low viscosity and low cost and has been widely recognized by the market, but in order to obtain good hydrophilicity, a large amount of polyether needs to be introduced, resulting in low effective isocyanate content and poor resistance of the product. Sulfonic acid modified polyisocyanate curing agent has the advantages of high functionality and easy dispersion, but the high cost of sulfonic acid raw materials, slow reaction rate, high product viscosity and other disadvantages limit its application in coatings, adhesives and other fields. It usually requires a large amount of organic solvent dilution, which goes against the original intention of oil-based to water-based. How to minimize the viscosity and cost of the product while ensuring sufficient hydrophilicity has always been a pain point in the industry.

[0004] Patent CN1190450C uses 3-(cyclohexylamino)-propanesulfonic acid and 2-(cyclohexylamino)-ethanesulfonic acid solid powders to prepare sulfonic acid-modified polyisocyanates, and the resulting modified polyisocyanates can be evenly dispersed in water without high shear force. CN104448232B uses 4-(cyclohexylamino)-butanesulfonic acid solid powders to prepare sulfonic acid-modified polyisocyanates, and also obtains sulfonic acid-modified polyisocyanates with excellent performance. Both of the above patents use a single solid powder sulfonic acid to prepare a modified curing agent, and the prepared product has high viscosity, a large amount of sulfonic acid, and high cost.

[0005] The present invention has found through long-term experiments that by introducing a small amount of hydroxysulfonic acid into aminosulfonic acid, the same hydrophilic effect can be maintained while using less aminosulfonic acid, having low product viscosity and good dispersibility. Summary of the invention

[0006] The purpose of this patent is to provide a composite sulfonic acid modified polyisocyanate. The modified polyisocyanate prepared by this method has the advantages of high production efficiency, low viscosity, good dispersibility, etc., and accelerates the process of oil-based to water-based conversion in the field of coatings and adhesives.

[0007] In order to achieve the above invention object, the present invention provides the following technical solutions:

[0008] A composite sulfonic acid hydrophilic modified polyisocyanate, characterized in that the hydrophilic modified polyisocyanate is a reaction product obtained by reacting a component (a), a component (b) and an optional component (c):

[0009] (a) at least one aliphatic, cycloaliphatic, araliphatic and / or aromatic polyisocyanate or modified polyisocyanate;

[0010] (b) A composite sulfonic acid comprising aminosulfonic acid (b1) and hydroxysulfonic acid (b2) having the following structure:

[0011]

[0012] wherein R1 is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, and R2 is a straight chain or branched aliphatic group having 2 to 6 carbon atoms, such as ethylene, propylene, butylene;

[0013] OH-R3-SO3H(b2)

[0014] Wherein R3 is a straight chain or branched aliphatic group having 2 to 6 carbon atoms, such as ethylene, propylene, butylene;

[0015] (c) Tertiary amines.

[0016] In the present invention, the amount of the composite sulfonic acid (b) is 0.5%-10% of the total amount of the polyisocyanate (a) and the composite sulfonic acid (b), and the molar ratio of the tertiary amine (c) to the composite sulfonic acid (b) is 0.9-1.1%;

[0017] In the present invention, the component (a) polyisocyanate is one or more of aliphatic, alicyclic, and / or aromatic polyisocyanates or modified polyisocyanates having an average isocyanate functionality of 2.0-5.0 and an NCO content of 7.0-32.0 wt%.

[0018] In the present invention, the modified polyisocyanate is a modified polyisocyanate containing carbamate, allophanate, biuret, uretdione, isocyanurate, imino oxadiazinedione and / or oxadiazinedione structure, which can be prepared by modifying one or more of simple aliphatic, alicyclic, aromatic and / or aromatic aliphatic diisocyanates according to the methods described in DE1670666A, DE1954093A, DE2414413A, DE2452532A, DE2641380A, DE3700209A, DE3900053A, DE3928503A, EP0336205A, EP0339396A and EP0798299A;

[0019] In the present invention, suitable diisocyanates for preparing the above-mentioned modified polyisocyanates containing carbamate, allophanate, biuret, uretdione, isocyanurate, iminooxadiazinedione and / or oxadiazinedione structures are those that can be obtained by phosgene or non-phosgene methods, for example, any diisocyanate obtained by thermal decomposition of ethyl carbamate. Preferred diisocyanates are diisocyanates with a molecular weight of 100 to 500 and with aliphatic, cycloaliphatic and / or aromatic bonds, for example tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene-1,6-diisocyanate, dodecamethylene-1,12-diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 4,4′-dicyclohexylpropane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tetramethylxylyl diisocyanate and p-xylylene diisocyanate or mixtures of these diisocyanates.

[0020] In the present invention, the preferred polyisocyanates are based on hexamethylene-1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (HDI). 12 A modified polyisocyanate having an isocyanurate group selected from one or more of MDI and MDI.

[0021] In the present invention, the modified polyisocyanate containing uretdione, isocyanurate, carbamate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinedione structure can be added with auxiliary agents such as antioxidants, free radical scavengers, inhibitors, etc. during the preparation process.

[0022] In the present invention, the aminosulfonic acid b1 is selected from one or more of 2-cyclohexylaminoethanesulfonic acid, 3-cyclohexylaminopropanesulfonic acid, and 4-cyclohexylaminobutanesulfonic acid.

[0023] In the present invention, the hydroxysulfonic acid b2 is selected from one or more of hydroxyethanesulfonic acid, hydroxypropanesulfonic acid and hydroxybutanesulfonic acid.

[0024] In the present invention, the hydroxysulfonic acid (b2) in the composite sulfonic acid accounts for 0.005% to 1% of the total mass of the sulfonic acid (b), preferably 0.01% to 0.2%.

[0025] Preferably, the composite sulfonic acid (b) can be partially or completely neutralized by a tertiary amine to form a salt before, during and / or after the reaction.

[0026] The tertiary amine (c) is one or more of N,N-dimethylbutylamine, N,N-diethylmethylamine, N,N-diisopropylethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine and / or N-ethylmorpholine, which is used to neutralize the sulfonic acid groups in the composite sulfonic acid to form sulfonates, and to act as a phase transfer catalyst to catalyze the reaction between polyisocyanates and composite sulfonic acids.

[0027] The tertiary amine can also be mixed with a catalyst commonly used in polyurethane, such as other tertiary amine catalysts: pyridine, picoline, benzyldimethylamine, N,N-dimethylpiperazine; organic metal catalysts: tri(ethyl-acetyl acetate)aluminum, tin octanoate, zinc octanoate, 2-ethyl-1-hexanoate tin (II), dibutyltin dichloride (IV), dibutyltin diacetate (IV), dibutyltin dilaurate (IV), dioctyltin diacetate (IV) or a mixture of one or more of molybdenum glycolate. The amount of these conventional catalysts used is 10-2000ppm of the total weight of the reaction materials, preferably 100-500ppm.

[0028] In the method of the present invention, the polyisocyanate and the composite sulfonic acid can be reacted in the presence of a tertiary amine in a solvent inert to the NCO reaction, such as acetone, butanone, cyclopentanone, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, N-methylpyrrolidone, N-ethylpyrrolidone, toluene, xylene, chlorobenzene, propylene glycol methyl ether acetate, 1-methoxyprop-2-yl acetate, 3-methoxy-n-butyl acetate, aromatic compounds, dimethyl carbonate, diethyl carbonate, butyrolactone, caprolactone and methyl caprolactone, etc., or any mixture of multiple solvents.

[0029] On the other hand, the present invention also relates to a method for preparing a hydrophilic modified polyisocyanate, wherein polyisocyanate (a) and composite sulfonic acid (b) are reacted at 70-110° C. for 2-8 hours in the presence of a tertiary amine (c).

[0030] In the present invention, the polyisocyanate (a) may be added in one step or in multiple steps.

[0031] In the present invention, during the preparation process, an antioxidant can be added to reduce the color. The antioxidant is selected from compounds such as aromatic amines and hindered phenols that can eliminate free radicals and their derivatives, or antioxidants that can decompose hydroperoxides such as phosphorus-containing and sulfur-containing organic compounds, or a combination thereof.

[0032] In the present invention, the amount of the antioxidant added is 0%-1.5% of the total amount of the polyisocyanate (a) and the composite sulfonic acid (b);

[0033] The present invention also provides the use of the hydrophilic modified polyisocyanate and the hydrophilic modified polyisocyanate prepared by the method of the present invention as a crosslinking agent in water-dispersible two-component coatings and adhesives.

[0034] The present invention also provides the use of hydrophilically modified polyisocyanates as starting components in the preparation of water-dispersible or water-dispersible blocked polyisocyanates. Suitable blocking agents include, for example, one or more of methyl ethyl ketone oxime, 3,5-dimethylpyrazole, diethyl malonate, ethyl acetoacetate, imidazole, and ε-caprolactam.

[0035] The hydrophilic modified polyisocyanate of the present invention can be used as a crosslinking component in two-component coatings and adhesives, and can also be used as a crosslinking agent for fabric finishing, printing coating adhesives, and for crosslinking other aqueous dispersions or as an auxiliary agent for moisturizing paper.

[0036] The beneficial effect of the present invention is that by introducing a small amount of hydroxysulfonic acid into aminosulfonic acid, the same hydrophilic effect can be maintained while using a small amount of aminosulfonic acid, and the obtained hydrophilic modified polyisocyanate has lower viscosity, color number and better dispersibility. DETAILED DESCRIPTION

[0037] The present invention is further illustrated below in conjunction with the embodiments. It should be noted that the present invention is not limited to the following embodiments.

[0038] Polyisocyanate a1 (Wanhua Chemical Wannate○R HT-100, HDI-based polyisocyanate, NCO content = 21.7-22.2 wt %);

[0039] Aminosulfonic acid b1-1: 3-cyclohexylaminopropanesulfonic acid, purchased from J&K Reagent, purity 99%

[0040] Aminosulfonic acid b1-2: 4-cyclohexylaminobutanesulfonic acid, in dioxane solvent, reacted with cyclohexylamine and 1,4-butanesulfone at a molar ratio of 3:1 at 80°C for 6h, collected the solid, and washed with acetone until white.

[0041] Hydroxysulfonic acid b2-1: 3-Hydroxypropanesulfonic acid, purchased from Aladdin Reagent, 80% aqueous solution.

[0042] Hydroxysulfonic acid b2-2: 4-hydroxybutanesulfonic acid, purchased from J&K Reagents, purity 95%. Tertiary amine c1: N,N-dimethylcyclohexylamine, purchased from J&K Reagents, purity 99%.

[0043] Tertiary amine c2: N-ethylmorpholine, purchased from J&K Reagents, purity 99%.

[0044] Embodiment 1:

[0045] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 17 g (0.077 mol) of aminosulfonic acid b1-1, 0.19 (0.0011 mol) of hydroxysulfonic acid b2-1 and 9.91 g (0.078 mol) of tertiary amine c1 were added to the reaction system at 50°C and 300 rpm, mixed evenly, heated to 90°C for 3 h, stopped the reaction, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0046] Solid content: 100%

[0047] NCO content: 19.70wt%

[0048] Viscosity (25°C): 4800 mPa·s

[0049] SO3- content: 1.54wt%

[0050] Color: 16

[0051] Embodiment 2:

[0052] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 18.08 g (0.077 mol) of aminosulfonic acid b1-2, 0.043 g (2.4×10-4 mol) of hydroxysulfonic acid b2-1 and 9.77 g (0.077 mol) of tertiary amine c1 were added to the reaction system at 50°C and 300 rpm with stirring, mixed evenly, heated to 110°C for reaction for 3 h, the reaction was stopped, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0053] Solid content: 100%

[0054] NCO content: 19.65wt%

[0055] Viscosity (25°C): 4400mPa·s

[0056] SO3- content: 1.51wt%

[0057] Color: 6

[0058] Embodiment 3:

[0059] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 18.08 g (0.077 mol) of aminosulfonic acid b1-2, 0.018 g (1.2×10-4 mol) of hydroxysulfonic acid b2-2 and 9.77 g (0.077 mol) of tertiary amine c1 were added to the reaction system at 50°C and 300 rpm, mixed evenly, heated to 100°C for reaction for 6 h, the reaction was stopped, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0060] Solid content: 100%

[0061] NCO content: 19.69wt%

[0062] Viscosity (25°C): 4900 mPa·s

[0063] SO3- content: 1.51wt%

[0064] Color: 9

[0065] Embodiment 4:

[0066] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 18.75 g (0.080 mol) of aminosulfonic acid b1-2, 0.001 g (6.5×10-6 mol) of hydroxysulfonic acid b2-2 and 10.13 g (0.080 mol) of tertiary amine c1 were added to the reaction system at 50°C and 300 rpm, mixed evenly, heated to 110°C for 3 h, stopped the reaction, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0067] Solid content: 100%

[0068] NCO content: 19.64wt%

[0069] Viscosity (25°C): 4900 mPa·s

[0070] SO3- content: 1.57wt%

[0071] Color: 22

[0072] Embodiment 5:

[0073] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 18.08 g (0.077 mol) of aminosulfonic acid b1-2, 0.002 g (2.6×10-5 mol) of hydroxysulfonic acid b2-2 and 9.77 g (0.077 mol) of tertiary amine c1 were added to the reaction system at 50°C and 300 rpm, mixed evenly, heated to 110°C for 3 h, stopped the reaction, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0074] Solid content: 100%

[0075] NCO content: 19.73wt%

[0076] Average NCO functionality: 3.41

[0077] Viscosity (25°C): 4200 mPa·s

[0078] SO3- content: 1.51wt%

[0079] Color: 12

[0080] Example 6

[0081] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 17 g (0.077 mol) of aminosulfonic acid b1-1, 0.018 (1.2×10-4 mol) g of hydroxysulfonic acid b2-2 and 8.86 g (0.077 mol) of tertiary amine c2 were added to the reaction system at 50°C and 300 rpm, mixed evenly, heated to 90°C for 3 h, stopped the reaction, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0082] Solid content: 100%

[0083] NCO content: 19.67wt%

[0084] Viscosity (25°C): 4300 mPa·s

[0085] SO3- content: 1.52wt%

[0086] Color: 10

[0087] Comparative Example 1:

[0088] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 17 g (0.077 mol) of aminosulfonic acid b1-1 and 9.77 g (0.077 mol) of tertiary amine c1 were added to the reaction system at 50°C and 300 rpm with stirring, mixed evenly, heated to 90°C for 3 h, stopped the reaction, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0089] Solid content: 100%

[0090] NCO content: 19.73wt%

[0091] Viscosity (25°C): 5100 mPa·s

[0092] SO3- content: 1.51wt%

[0093] Color: 58

[0094] Comparative Example 2:

[0095] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 19.74 g (0.084 mol) of aminosulfonic acid b1-2 and 10.67 g (0.084 mol) of tertiary amine c1 were added to the reaction system at 50°C and 300 rpm, mixed evenly, heated to 110°C for 3 h, stopped the reaction, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0096] Solid content: 100%

[0097] NCO content: 19.47wt%

[0098] Viscosity (25°C): 5900 mPa·s

[0099] SO3- content: 1.64wt%

[0100] Color: 86

[0101] Comparative Example 3

[0102] In a four-necked round-bottom flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a nitrogen inlet and outlet, 380 g (1.99 mol) of polyisocyanate a1, 17 g (0.077 mol) of aminosulfonic acid b1-1, 0.34 (0.0022 mol) of hydroxysulfonic acid b2-2 and 10.06 g (0.079 mol) of tertiary amine c1 were added to the reaction system at 50°C and 300 rpm, mixed evenly, heated to 90°C for 3 h, stopped the reaction, filtered through a 325-mesh filter, and cooled to room temperature to obtain an aminosulfonic acid-modified polyisocyanate having the following characteristic data:

[0103] Solid content: 100%

[0104] NCO content: 19.73wt%

[0105] Viscosity (25°C): 5200 mPa·s

[0106] SO3- content: 1.54wt%

[0107] Color: 43

[0108] Dispersibility test: Take 5g of the prepared hydrophilic modified polyisocyanate and put it into a 250ml beaker, then pour in 100ml of deionized water, stir with a glass rod, and score according to the difficulty of dispersing the polyisocyanate, 5 points for the easiest to stir, and 1 point for the most difficult to stir.

[0109] Hydrophilicity test: After diluting the polyisocyanate emulsion obtained from the dispersibility test 100 times, the particle size was tested. The results are shown in the following table

[0110] sample Dispersibility Particle size Example 1 4 82 Example 2 5 78 Example 3 5 75 Example 4 4 90 Example 5 5 80 Example 6 5 79 Comparative Example 1 3 115 Comparative Example 2 2 87 Comparative Example 3 3 77

[0111] It can be seen from Examples 1-6 and Comparative Examples 1 and 2 that the modified polyisocyanate prepared by combining aminosulfonic acid with a trace amount of hydroxysulfonic acid reduces the amount of sulfonic acid and the viscosity of the product while maintaining the hydrophilicity unchanged, and improves the product color and dispersion effect. It can be seen from Comparative Example 3 that when the amount of hydroxysulfonic acid exceeds the range of the present invention, the viscosity and color of the prepared product increase to varying degrees, and the dispersion effect deteriorates.

Claims

1. A composite sulfonic acid hydrophilic modified polyisocyanate, characterized in that: The hydrophilic modified polyisocyanate is a reaction product obtained by reacting component (a), component (b) and component (c): (a) at least one aliphatic, cycloaliphatic, araliphatic and / or aromatic polyisocyanate or modified polyisocyanate; (b) A composite sulfonic acid comprising aminosulfonic acid (b1) and hydroxysulfonic acid (b2) having the following structure: wherein R1 is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, and R2 is a straight chain or branched aliphatic group having 2 to 6 carbon atoms; OH-R3-SO3H(b2) wherein R3 is a straight chain or branched aliphatic group having 2 to 6 carbon atoms; the hydroxysulfonic acid (b2) in the composite sulfonic acid accounts for 0.005% to 1% of the total mass of the sulfonic acid (b); and the amount of the composite sulfonic acid (b) is 0.5% to 10% of the total amount of the polyisocyanate (a) and the composite sulfonic acid (b); (c) Tertiary amines.

2. The composite sulfonic acid hydrophilic modified polyisocyanate according to claim 1, characterized in that: R2 is ethylene, propylene or butylene; R3 is ethylene, propylene or butylene.

3. The composite sulfonic acid hydrophilic modified polyisocyanate according to claim 1, characterized in that: The polyisocyanate component a) is one or more of aliphatic, alicyclic, and / or aromatic polyisocyanates or modified polyisocyanates having an average isocyanate functionality of 2.0-5.0 and an NCO content of 7.0-32.0 wt%.

4. The composite sulfonic acid hydrophilic modified polyisocyanate according to claim 3, characterized in that: The polyisocyanate component a) is a polyisocyanate prepared based on one or more of hexamethylene-1,6-diisocyanate, 3-isocyanatomethylene-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

5. The composite sulfonic acid hydrophilic modified polyisocyanate according to claim 1, characterized in that: The polyisocyanate component (a) is a polyisocyanate having a urethane, allophanate, biuret, uretdione, isocyanurate, iminooxadiazinedione and / or oxadiazinedione structure.

6. The composite sulfonic acid hydrophilic modified polyisocyanate according to any one of claims 1 to 5, characterized in that: The aminosulfonic acid b1 is one or more of 2-cyclohexylaminoethanesulfonic acid, 3-cyclohexylaminopropanesulfonic acid, and 4-cyclohexylaminobutanesulfonic acid.

7. The composite sulfonic acid hydrophilic modified polyisocyanate according to any one of claims 1 to 5, characterized in that: The hydroxysulfonic acid b2 is one or more of hydroxyethanesulfonic acid, hydroxypropanesulfonic acid, and hydroxybutanesulfonic acid.

8. The composite sulfonic acid hydrophilic modified polyisocyanate according to any one of claims 1 to 5, characterized in that: In the composite sulfonic acid, the hydroxysulfonic acid (b2) accounts for 0.01% to 0.2% of the total mass of the sulfonic acid (b).

9. The composite sulfonic acid hydrophilic modified polyisocyanate according to any one of claims 1 to 5, characterized in that: The tertiary amine c) is one or more of N,N-dimethylbutylamine, N,N-diethylmethylamine, N,N-diisopropylethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine and / or N-ethylmorpholine.

10. The method for preparing the composite sulfonic acid hydrophilic modified polyisocyanate according to any one of claims 1 to 5, comprising the following steps: reacting the polyisocyanate (a) and the composite sulfonic acid (b) at 70-110°C in the presence of a tertiary amine (c).

11. The preparation method according to claim 10, characterized in that: During the preparation process, an antioxidant is also added, and the antioxidant is selected from aromatic amines and hindered phenol compounds and their derivatives that can eliminate free radicals, or antioxidants that can decompose hydroperoxides, or a combination thereof.

12. The preparation method according to claim 11, characterized in that: The antioxidant capable of decomposing hydroperoxides is selected from phosphorus-containing and sulfur-containing organic compounds.

13. Use of the composite sulfonic acid hydrophilic modified polyisocyanate according to any one of claims 1 to 9 or the composite sulfonic acid hydrophilic modified polyisocyanate prepared by the method according to any one of claims 10 to 12 in the preparation of coating agents, adhesives and sealants.

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