CN111499835B - Preparation method and application of nonionic aqueous isocyanate curing agent - Google Patents

Preparation method and application of nonionic aqueous isocyanate curing agent Download PDF

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CN111499835B
CN111499835B CN202010367758.4A CN202010367758A CN111499835B CN 111499835 B CN111499835 B CN 111499835B CN 202010367758 A CN202010367758 A CN 202010367758A CN 111499835 B CN111499835 B CN 111499835B
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curing agent
isocyanate curing
primary amine
nonionic
polyethylene glycol
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CN111499835A (en
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杨轩
易松
徐涛
龙绪俭
熊东路
肖增钧
李斌仁
鲁晓东
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Shenzhen Feiyang Xingye Technology Co ltd
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Shenzhen Qianhai Feiyang Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/808—Monoamines
    • 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
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a preparation method and application of a nonionic aqueous isocyanate curing agent, and relates to the technical field of isocyanate curing agents. According to the invention, primary amine is introduced as a synthesis bridge in the synthesis process, and two hydrogen atoms on the primary amine are used as active sites to connect a hydrophilic group and an isocyanate group. The use of solvent is reduced in the synthesis process, the safety is high, the process is simple, and products with different hydrophilic properties can be obtained by adjusting the number of molecules of secondary amine groups and the number of molecules of isocyanate groups. The paint provided by the invention is beneficial to improving the hardness and water resistance of the paint by adding the nonionic water-based isocyanate curing agent, the auxiliary agent and the cross-linking agent.

Description

Preparation method and application of nonionic aqueous isocyanate curing agent
Technical Field
The invention relates to the technical field of isocyanate curing agents, in particular to a preparation method of a nonionic water-based isocyanate curing agent and application of the nonionic water-based isocyanate curing agent in the field of coatings.
Background
The traditional paint generally adopts an oily organic solvent, and the organic solvent often contains volatile solvents, even toxic and harmful substances such as benzene, toluene, xylene, formaldehyde, free TDI and the like, so that the paint brings more or less harm to the environment and brings harm to the health of people. After the organic solvent is replaced by water, the cleaning agent has the advantages of cleanness and environmental protection, and can effectively protect the health of constructors and users. The waterborne polyurethane coating has the advantages of low VOC, non-flammability, environmental protection and the like of the waterborne coating, and is developed rapidly in the field of waterborne coatings in recent years. Aqueous polyaspartate polyurea coatings have not been reported at present.
The isocyanate is a curing agent widely applied to the two-component polyurethane coating, and the prior curing agent is mainly used in the following ways: toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI). These materials are all oily and difficult to disperse in water.
At present, there are two main methods for isocyanate hydration:
the first method is a method of grafting an anionic group, which is generally carried out by grafting a hydrophilic group having a sulfonic acid group into an isocyanate curing agent. As described in some patents and publications (ginger, zuccani, & singapa. (0.) a process for anionic synthesis of the isocyanate component of waterborne two-component polyurethane coatings; CN 110484118A). The paint synthesized by the method has good dispersion and paint film properties, but the anionic hydrophilic group has the following two disadvantages: 1) the hard water resistance is poor, and the emulsion breaking is easy to occur in hard water; 2) can not be used with a cationic solvent or an auxiliary agent, thereby limiting the application range of the cationic solvent or the auxiliary agent.
Another approach is to introduce nonionic hydrophilic groups into the curing agent molecule. The nonionic hydrophilic groups mainly include two kinds; polyethylene glycols polymerized from ethylene oxide and polypropylene glycols polymerized from propylene oxide. This method is also reported more. For example, the solvent synthesis method (CN 105062188A, CN102816294A) needs acetone, butanone and the like as solvents, and has the problems of complex production process, solvent impurities in the final product, harm to the health of users and the like.
Disclosure of Invention
The invention aims to solve the technical problem of at least one defect mentioned in the background technology, and provides a novel isocyanate waterborne synthesis method.
Specifically, the invention provides the following technical scheme:
a preparation method of a nonionic water-based isocyanate curing agent comprises the following steps:
s1, reacting primary amine with the double-bond-containing nonionic hydrophilic molecule to obtain an intermediate containing secondary amine, wherein the ratio of the amount of the substances of the primary amine and the double-bond-containing nonionic hydrophilic molecule is 1: 0.5 to 1;
s2, reacting the intermediate with an isocyanate polymer, and finishing the reaction to obtain the non-ionic water-based isocyanate curing agent, wherein the ratio of the number of molecules of secondary amino groups to the number of molecules of isocyanate groups is 1: 1-100.
The further technical proposal is that the non-ionic hydrophilic molecule containing double bonds is selected from polyethylene glycol series or polypropylene glycol series.
The further technical scheme is that the double-bond-containing nonionic hydrophilic molecule is at least one selected from polyethylene glycol diacrylate, polyethylene glycol acrylate, polyethylene glycol monomethyl ether acrylate, polyethylene glycol monoethyl ether acrylate, polyethylene glycol dimethacrylate, polyethylene glycol methacrylate, polyethylene glycol monomethyl ether methacrylate, polyethylene glycol monoethyl ether methacrylate, polypropylene glycol dimethacrylate, polypropylene glycol methacrylate, polypropylene glycol diacrylate, polypropylene glycol acrylate, polypropylene glycol monomethyl ether acrylate, polypropylene glycol monoethyl ether acrylate, polypropylene glycol monomethyl ether methacrylate and polypropylene glycol monoethyl ether methacrylate. The number average molecular weight of the polymer is 180-.
The further technical scheme is that the primary amine is at least one selected from ethylamine, propylamine, dodecylamine, hexadecylamine, octadecylamine, ethylenediamine, diethylenetriamine, triethylene tetramine, aromatic primary amine, aliphatic monoprimary amine or cycloaliphatic primary amine.
The further technical proposal is that the aromatic primary amine is selected from aniline or phenylenediamine; the cycloaliphatic primary amine is at least one selected from cyclohexylamine, 2-methylcyclohexylamine, 4-methylcyclohexylamine and cyclohexanediamine.
The further technical scheme is that the isocyanate polymer is selected from at least one of TDI, IPDI, HDI, HMDI, MDI and LDI.
The method further comprises a step of removing excess unreacted primary amine if the primary amine is excessive after the reaction is finished in the step S1.
In a further embodiment, in the step S2, the reaction completion is determined by the following step, and if it is detected that the reaction does not release heat, the reaction is determined to be completed after 0.5 to 3 hours.
The invention also provides application of the nonionic water-based isocyanate curing agent in the field of coatings.
The invention also provides a coating comprising an auxiliary agent, a cross-linking agent and the non-ionic aqueous isocyanate curing agent as defined in any one of claims 1 to 8; the auxiliary agent is selected from carborundum and/or silica sol; the cross-linking agent is selected from substances corresponding to the following general formula (1) or general formula (2):
general formula (1):
Figure BDA0002477090900000031
wherein R is1＝H or CH3；
General formula (2):
Figure BDA0002477090900000032
wherein x + y + z is 5-6.
Among the crosslinking agents used in the following examples, a substance corresponding to the structure of the general formula (1) is abbreviated as "F520"; the substance corresponding to the structure of the general formula (2) is abbreviated as "F330".
Compared with the prior art, the invention can achieve the following technical effects:
in the synthesis process, primary amine is introduced as a synthesis bridge, and two hydrogen atoms on the primary amine are used as active sites to connect a hydrophilic group and an isocyanate group. In the step S1, primary amine is converted into secondary amine in the reaction process, and the secondary amine has reduced reaction activity due to the influence of steric hindrance and is difficult to continue to react with double bonds in the nonionic hydrophilic molecules containing the double bonds, so that the reaction selectivity is high and the conversion rate is high.
The preparation method of the nonionic aqueous isocyanate curing agent provided by the invention has the advantages that the use of solvents is reduced in the synthesis process, the safety is high, the process is simple, and products with different hydrophilic properties can be obtained by adjusting the number of molecules of secondary amine groups and the number of molecules of isocyanate groups.
The paint provided by the invention is beneficial to improving the hardness and water resistance of the paint by adding the nonionic water-based isocyanate curing agent, the auxiliary agent and the cross-linking agent.
Detailed Description
The technical solution will be clearly and completely described below with reference to the embodiments of the present invention. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
General description of the synthetic method
The innovative method provided by the invention is to combine a nonionic hydrophilic molecule containing double bonds with an isocyanate curing agent molecule by taking primary amine as a bridge to form a hydrophilic compound. The amine is converted into secondary amine in the reaction process, the secondary amine has reduced reaction activity due to the influence of steric hindrance, and is difficult to continue to react with double bonds, and the primary amine reaction selectivity in the step is high. After the completion of the reaction, if the amount of unreacted primary amine is large, the unreacted primary amine can be removed by distillation under reduced pressure by heating. In the research, if the primary amine is added in an excess of 50%, the excess primary amine needs to be removed by heating and reducing the pressure after the reaction is finished, the conversion rate is more than 97%, and the selectivity is more than 95%. If the added primary amine has a high boiling point and is difficult to remove, the ratio of 1:1 proportion of the two substances are added, the reaction time is properly prolonged, the vacuum rectification is not needed after the reaction, and the conversion rate can also reach 90 percent.
Such hydrophilic molecules with secondary amines react very readily with isocyanates (polymers). According to the experimental results, the ratio of the number of molecules of the secondary amine groups to the number of molecules of the isocyanate groups was adjusted to 1: 100-1: 1, isocyanate curing agents with different hydrophilic properties can be synthesized. The optimum ratio varies with the molecular weight of the hydrophilic nonionic substance in the starting materials for the first reaction. If polyethylene glycol diacrylate with a molecular weight of 400 is used as the raw material in the first step of the reaction, the optimal ratio is 1: 5; if the first reaction step uses polyethylene glycol diacrylate with a molecular weight of 3000 as a raw material, the optimal ratio is 1: 15.
after the materials are put in proper proportion, the reaction time is different according to different types of the selected isocyanates and different types of the selected primary amines. In general, the reaction rates for the different starting materials are as follows: TDI > IPDI > HDI > HMDI > MDI > LDI; ethylenediamine, methylamine, ethylamine, aniline, cyclohexylamine, 2-methylcyclohexylamine and 4-methylcyclohexylamine. The reaction speed is mainly influenced by the activity and the steric hindrance of the isocyanic acid radicals in different raw materials. The reaction of the raw materials is completed within about 30min, and the reaction is completed within about 10 h. Since the reaction process is strongly exothermic, the reaction end point is 2 hours after the reaction process no longer releases heat obviously.
Effect of B hydrophilic groups on curing agent Performance
Different hydrophilic groups have a significant influence on the hydrophilic properties of the final product as well as on the coating properties. In the invention, the molecular hydrophilicity is mainly derived from O atoms in polyether, and the O atoms in products of polyethylene glycol series have larger number than that of polypropylene glycol series, so the hydrophilicity of the former is larger than that of the latter. In order to impart good hydrophilicity to the latter product, the molecular weight of polypropylene glycol may be increased appropriately. Experiments show that under the same conditions, the emulsifying performance of the polypropylene glycol ester with the molecular weight of 3000 as the raw material is equivalent to that of the polyethylene glycol ester with the molecular weight of 350. Because the molecular bond of the polypropylene glycol is softer, the extensibility is better after the final coating is prepared.
Effect of C-amino Compounds on products
The invention mainly utilizes two hydrogen atoms on primary amine as active sites to connect a hydrophilic group and an isocyanate group, and different primary amines have influence on the production process, the emulsifying property and the application property.
Primary aromatic amines, such as aniline, phenylenediamine. The hardness of the final coating film is high due to the rigidity of the benzene ring. However, aniline and phenylenediamine are easily oxidized by oxygen in the air, and the product is easily yellowed.
The synthesis conditions and the performances of the ring aliphatic primary amine such as cyclohexylamine and methylcyclohexylamine are equivalent to those of aliphatic monoprimary amine.
The following are specific examples:
example 1
A synthesis method of a nonionic water-based isocyanate curing agent (WHDI-III) comprises the following steps:
150g (1.5mol) of cyclohexylamine is taken, slowly added to 300g of polyethylene glycol monomethyl ether acrylate (average molecular weight is 380) dropwise, heated to about 80 ℃ under the condition of introducing argon, and reacted for 10 hours to obtain an intermediate. The unreacted cyclohexylamine was removed by heating to 110 ℃ under reduced pressure. The conversion was about 95% by gas chromatography. Less than 3% of cyclohexylamine remained. And then mixing the intermediate and the HDI trimer according to the mass ratio of 3: 1, adding into HDI tripolymer, and stirring the reaction for about 2h under the protection of argon. After the reaction is finished, the nonionic water-based isocyanate curing agent (WHDI-III) is obtained.
The main properties of the non-ionic aqueous isocyanate curing agent (WHDI-III) were determined as follows:
appearance: a viscous liquid;
color: colorless and transparent;
viscosity: 8000-;
NCO value: 16-17.
Example 2
A synthetic method of a nonionic water-based isocyanate curing agent (WHDI-V) comprises the following steps:
150g (1.5mol) of cyclohexylamine is taken, slowly added to 300g of polyethylene glycol monomethyl ether acrylate (average molecular weight is 380) dropwise, heated to about 80 ℃ under the condition of introducing argon, and reacted for 10 hours to obtain an intermediate. The conversion was about 95% by gas chromatography. Less than 3% of cyclohexylamine remained. And (3) mixing the intermediate with the HDI pentamer according to a mass ratio of 3: 1, adding into HDI pentamer, and stirring the reaction for about 2h under the protection of argon. After the reaction is finished, the nonionic water-based isocyanate curing agent (WHDI-V) is obtained.
The main properties of the non-ionic aqueous isocyanate curing agent (WHDI-V) were determined as follows:
appearance: a viscous liquid;
color: colorless and transparent;
viscosity: 10000-;
NCO value: 16-17.
Example 3
A synthetic method of a nonionic water-based isocyanate curing agent (WTDI) comprises the following steps:
150g (1.5mol) of cyclohexylamine is taken, slowly added to 300g of polyethylene glycol monomethyl ether acrylate (average molecular weight is 380) dropwise, heated to about 80 ℃ under the condition of introducing argon, and reacted for 10 hours to obtain an intermediate. The conversion was about 95% by gas chromatography. Less than 3% of cyclohexylamine remained. The intermediate was then reacted with TDI as 2.5: 1, adding TDI, and stirring and reacting for about 3 hours under the protection of argon. And obtaining the nonionic water-based isocyanate curing agent WTDI after the reaction is finished.
The main properties of the nonionic aqueous isocyanate curing agent WTDI were determined as follows:
appearance: a viscous liquid;
color: yellow;
viscosity: 10000-;
NCO value: 21.
example 4
Formulation and performance testing of a coating, in particular an aqueous polyurethane coating (WHDI-VW):
6g of WHDI-V, 6g of water-based hydroxyl acrylic resin, 10g of water and 3g of wetting agent (glycerol methyl ether) are uniformly mixed, and then the mixture is coated on the surface of stainless steel, and the performance of the stainless steel is tested after about 3 days. The performance results are as follows:
and (3) activation period: 4h, surface dry time: and 3 h. The actual drying time is as follows: and (5) 15 h. Surface properties: and (4) smoothing. Heat resistance: no color change at 140 ℃ for 2 h. Water resistance: the temperature is constant for 1 day. Acetone resistance: no change occurred during 20 min. Impact resistance: and (4) passing. Apparent hardness: HB.
Example 5
Formulation and performance testing of a coating, in particular an aqueous polyurethane coating (WHDI-III):
6g of WHDI-III, 6g of water-based hydroxyl acrylic resin, 10g of water and 3g of wetting agent (glycerol methyl ether) are uniformly mixed, and then the mixture is coated on the surface of stainless steel, and the performance of the stainless steel is tested after about 3 days. The performance results are as follows:
and (3) activation period: 4h, surface dry time: and (5) 10 h. The actual drying time is as follows: and (7) 36 h. Surface properties: and (4) smoothing. Heat resistance: no color change at 140 ℃ for 2 h. Water resistance: the temperature is constant for 1 day. Acetone resistance: no change was observed for 5 min. Impact resistance: and (4) passing. Apparent hardness: 2B
The apparent hardness, acetone resistance was lower than example 4, while the open and solid times were higher than example 4.
Example 6
Formulation and performance testing of a coating, in particular a waterborne Asparagus coating (III):
6g of WHDI-III, 6g of F520 and 4g of water are uniformly mixed, and then the mixture is coated on the surface of stainless steel, and the performance of the stainless steel is tested after about 3 days. WHDI-III coatings performance was as follows:
and (3) activation period: 4h, surface dry time: and (5) 15 h. The actual drying time is as follows: and (7) 36 h. Surface properties: and (4) smoothing. Heat resistance: no color change at 140 ℃ for 2 h. Water resistance: no change at normal temperature for 2 days. Acetone resistance: no change was observed for 5 min. Impact resistance: and (4) passing. Apparent hardness: 2B.
Example 7
Formulation and performance testing of a coating, in particular a waterborne Asparagus coating (V):
after 7g of WHDI-V, 6g of F520 and 4g of water are uniformly mixed, a film is coated on the surface of the stainless steel, and the performance of the stainless steel is tested after about 3 days. WHDI-V coating Properties:
and (3) activation period: 4h, surface dry time: and 8 h. The actual drying time is as follows: and (5) 24 h. Surface properties: and (4) smoothing. Heat resistance: no color change at 140 ℃ for 2 h. Water resistance: no change at normal temperature for 3 days. Acetone resistance: no change was observed for 5 min. Impact resistance: and (4) passing. Apparent hardness: HB.
As can be seen from the comparison of the coating properties of examples 6 to 7, WHDI-V is superior to WHDI-III in tack-free time, tack-free time and hardness.
Example 8
A coating, in particular to a high-hardness water-based asparagus coating (V) formula and a performance test
After 7g of WHDI-V, 6g of F520, 4g of water and 0.3g of carborundum were mixed uniformly, the stainless steel surface was coated with a film, and the performance was tested after about 3 days. The properties were as follows:
the hardness was 2H, the rest being the same as in example 7. After the addition of the carborundum, the coating hardness was significantly improved over example 7.
Example 9
A coating, in particular to a water-resistant waterborne asparagus coating (V) formula and performance test
7g of WHDI-V, 6g of F330, 4g of water, 0.3g of organic silica sol and 0.2g of nano titanium dioxide are uniformly mixed and coated on the surface of stainless steel. The performance was tested after about 3 days. The properties were as follows:
and (3) activation period: 4h, surface dry time: and 8 h. The actual drying time is as follows: and (5) 24 h. Surface properties: and (4) smoothing. Heat resistance: no color change at 140 ℃ for 2 h. Water resistance: the temperature was constant for 7 days. Impact resistance: and (4) passing. Apparent hardness: HB.
The water resistance of the coating after the silica sol is added is obviously improved compared with that of the coating of example 7.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. A preparation method of a nonionic water-based isocyanate curing agent is characterized by comprising the following steps:
s1, reacting primary amine with the double-bond-containing nonionic hydrophilic molecule to obtain an intermediate containing secondary amine, wherein the ratio of the amount of the substances of the primary amine and the double-bond-containing nonionic hydrophilic molecule is 1: 0.5 to 1;
s2, reacting the intermediate with an isocyanate polymer, and obtaining the non-ionic water-based isocyanate curing agent after the reaction is finished, wherein the ratio of the number of molecules of secondary amino groups to the number of molecules of isocyanate groups is 1: 1-100;
the double-bond-containing nonionic hydrophilic molecule is selected from at least one of polyethylene glycol diacrylate, polyethylene glycol acrylate, polyethylene glycol monomethyl ether acrylate, polyethylene glycol monoethyl ether acrylate, polyethylene glycol dimethacrylate, polyethylene glycol methacrylate, polyethylene glycol monomethyl ether methacrylate, polyethylene glycol monoethyl ether methacrylate, polypropylene glycol dimethacrylate, polypropylene glycol methacrylate, polypropylene glycol diacrylate, polypropylene glycol acrylate, polypropylene glycol monomethyl ether acrylate, polypropylene glycol monoethyl ether acrylate, polypropylene glycol monomethyl ether methacrylate and polypropylene glycol monoethyl ether methacrylate.
2. The method for preparing a nonionic aqueous isocyanate curing agent according to claim 1, wherein the primary amine is at least one selected from the group consisting of ethylamine, propylamine, dodecylamine, hexadecylamine, octadecylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, aromatic primary amine and cycloaliphatic primary amine.
3. The method for producing a nonionic aqueous isocyanate curing agent according to claim 2, wherein the primary aromatic amine is selected from aniline or phenylenediamine; the cycloaliphatic primary amine is at least one selected from cyclohexylamine, 2-methylcyclohexylamine, 4-methylcyclohexylamine and cyclohexanediamine.
4. The method for preparing a nonionic aqueous isocyanate curing agent according to claim 1, wherein the isocyanate polymer is at least one selected from the group consisting of TDI, IPDI, HDI, HMDI, MDI, LDI.
5. The method for preparing a nonionic aqueous isocyanate curing agent according to claim 1, wherein the step S1 further comprises a step of removing excess unreacted primary amine when the primary amine is in excess after completion of the reaction.
6. The method for producing a nonionic aqueous isocyanate curing agent according to claim 1, wherein the completion of the reaction in step S2 is determined by the following steps,
if the reaction is detected to be no longer exothermic, and the reaction is judged to be finished after 0.5 to 3 hours.
7. Use of a curing agent obtained by the method for preparing a nonionic aqueous isocyanate curing agent according to any one of claims 1 to 6 in the field of coatings.
8. A coating material, which is characterized by comprising an auxiliary agent, a cross-linking agent and a curing agent, wherein the curing agent is prepared by the preparation method of the non-ionic water-based isocyanate curing agent according to any one of claims 1 to 6; the auxiliary agent is selected from carborundum and/or silica sol; the cross-linking agent is selected from substances corresponding to the following general formula (1) or general formula (2):
general formula (1):
Figure FDA0003230407270000021
wherein R is1＝H or CH3；
General formula (2):
Figure FDA0003230407270000022
wherein x + y + z is 5-6.
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KR101887243B1 (en) * 2011-07-13 2018-08-09 에이지씨 세이미 케미칼 가부시키가이샤 Curable resin composition and use thereof
EP2612846A1 (en) * 2012-01-09 2013-07-10 Bayer MaterialScience AG Beta amino acid esters and use of same
US9493670B2 (en) * 2013-04-18 2016-11-15 Empire Technology Development Llc Coatings that provide hydrophilic surface
CN105001621A (en) * 2015-07-22 2015-10-28 东莞市雄林新材料科技股份有限公司 Temperature-sensitive intelligent waterproof and moisture permeable TPU film and preparation method thereof
CN109608605A (en) * 2017-12-19 2019-04-12 传化智联股份有限公司 A kind of ion-non-ion aqueous polyurethane dispersion preparation
CN109721698B (en) * 2018-12-27 2021-03-30 传化智联股份有限公司 Hydrophilic chain extender suitable for synthesis of waterborne polyurethane and preparation method and application thereof
CN110437089A (en) * 2019-08-08 2019-11-12 深圳市前海博扬研究院有限公司 A kind of UV monomer and preparation method and application

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