CN116444763B - High-water-resistance waterborne polyurethane curing agent and preparation method and application thereof - Google Patents
High-water-resistance waterborne polyurethane curing agent and preparation method and application thereofInfo
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- CN116444763B CN116444763B CN202310304824.7A CN202310304824A CN116444763B CN 116444763 B CN116444763 B CN 116444763B CN 202310304824 A CN202310304824 A CN 202310304824A CN 116444763 B CN116444763 B CN 116444763B
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of coatings, and particularly discloses a high-water-resistance waterborne polyurethane curing agent, and a preparation method and application thereof. The raw material components of the waterborne polyurethane curing agent comprise, by weight, 1.5-5 parts of sulfamate, 95.0-97.5 parts of hexamethylene diisocyanate trimer, 6-16 parts of silane coupling agent, 0.15-0.5 part of catalyst, and the silane coupling agent comprises 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane. The invention synthesizes sulfamate and hexamethylene diisocyanate trimer to ensure that the aqueous polyisocyanate curing agent has excellent dispersibility without solvent dilution, and then generates chemical reaction with partial isocyanate groups by the 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane under the action of a catalyst of a raw aqueous polyisocyanate system so as to graft the siloxane groups onto a molecular chain to obtain the aqueous polyurethane curing agent with high water resistance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a high-water-resistance waterborne polyurethane curing agent, and a preparation method and application thereof.
Background
In recent years, the environmental protection requirements of the state are continuously improved, and the water-based paint is undoubtedly one of the important development directions of the current paint technology. Among them, films obtained by using an aqueous polyurethane-based coating material crosslinked with an isocyanate-based compound can have very excellent abrasion resistance, drug resistance, stain resistance.
The aqueous isocyanate curing agent has excellent performance, and can be crosslinked and cured with polymers with active hydrogen atoms such as alcohols, amines and the like at room temperature due to the high reactivity of isocyanate groups, but has certain difference from oily polyurethane in terms of water resistance after the later film formation due to the introduction of a large amount of hydrophilic groups, so that the application and popularization of polyurethane technology are greatly limited. In order to solve the technical problem, the high-water-resistance aqueous polyurethane curing agent is generated, and the siloxane group is introduced into the aqueous polyurethane curing agent, so that the biting force of polyurethane with a base material is greatly increased when the polyurethane is formed into a film, and finally, the aim of greatly improving the water resistance of a paint film is fulfilled.
At present, in order to improve the water resistance of the water-based polyurethane curing agent in the market, N-aminoethyl-gamma-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane is mostly used as an additive, and the water-based polyurethane curing agent needs to be mixed with a polyurethane system for immediate use. Although the water resistance is improved to a certain extent, the use activation period and the appearance of a paint film are greatly influenced.
Therefore, development of an aqueous polyurethane curing agent is needed to effectively avoid the influence of the aqueous polyurethane curing agent on the activation period of a system and the appearance of a paint film, and improve the water resistance of the paint film.
Disclosure of Invention
The invention aims to solve the technical problems that the existing waterborne polyurethane curing agent needs to be prepared and used at present, and the activation period of a system is short, and the appearance and the water resistance of a paint film are poor. Therefore, the invention provides a high-water-resistance waterborne polyurethane curing agent, and a preparation method and application thereof.
The invention is characterized in that sulfamate and hexamethylene diisocyanate trimer are firstly used for synthesis to provide hydrophilic performance for polyisocyanate, so that the water-based polyisocyanate curing agent is ensured to have excellent dispersibility without solvent dilution, and then 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane are subjected to chemical reaction with partial isocyanate groups under the action of a catalyst of a raw water-based polyisocyanate system, so that the silicon groups are grafted onto a molecular chain to obtain the water-based polyurethane curing agent with high water resistance.
In order to solve the technical problems, the first aspect of the invention provides an aqueous polyurethane curing agent, which comprises the following raw material components in parts by weight:
the silane coupling agent comprises 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane.
The invention is characterized in that sulfamate and hexamethylene diisocyanate trimer are synthesized, sulfonic acid groups are used as extremely hydrophilic groups, and can be combined on isocyanate trimer to serve as inner emulsified hydrophilic groups, so that hydrophilicity is provided for a system, and further, the water-based polyisocyanate curing agent is ensured to have excellent dispersibility without solvent dilution, then, 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane are used for introducing-SH groups, and hydrogen in the water-based polyisocyanate curing agent reacts with isocyanate under the influence of a catalyst of a raw water-based polyisocyanate system, so that the silicon oxygen groups are connected to a molecular chain, and the water resistance of the water-based polyurethane curing agent is improved.
Meanwhile, the catalyst of the original system can promote the quick grafting of the two silane coupling agents, namely 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane, on an isocyanate molecular chain without adding any additional catalyst, silicon atoms are enriched to the surface in the film forming process, silicon oxygen groups are easier to hydrolyze into silicon hydroxyl groups in the process of dispersing polyurethane in water, a silicon three-dimensional cross-linked network is formed by dehydration in the film forming process, and the silicon three-dimensional cross-linked network is tightly meshed with a substrate on the surface of a paint film, so that the mechanical property, the water resistance and the weather resistance of the paint film are greatly improved.
Therefore, the invention takes sulfamate, hexamethylene diisocyanate trimer and specific silane coupling agent as main raw materials, and can prepare the water-based polyurethane curing agent with high water resistance, good mechanical property and long-term stable storage under specific raw material proportion.
As a further improvement to the above, the hexamethylene diisocyanate trimer has an NCO content of 21 to 24%.
As a further improvement of the above scheme, the mass ratio of the 3-mercaptopropyl triethoxysilane to the mercaptopropyl trimethoxysilane is (0.3-2.7): 1.
Preferably, the 3-mercaptopropyl triethoxysilane is added in an amount of 3 to 8 parts by weight.
Further preferably, the 3-mercaptopropyl triethoxysilane is added in an amount of 4 to 6 parts by weight.
Preferably, the mercaptopropyl trimethoxysilane is added in an amount of 3 to 8 parts by weight.
Further preferably, the mercaptopropyl trimethoxysilane is added in an amount of 4 to 6 parts by weight.
Preferably, the sulfamate is selected from at least one of sodium 2-tert-butyl-4- (cyclohexylamino) -1-butane sulfonate, sodium 2-tert-butyl-3- (cyclohexylamino) -1-propane sulfonate and sodium 2-isopentyl-3- (cyclohexylamino) -1-propane sulfonate.
Preferably, the catalyst is azotemyl benzyl amine.
The second aspect of the invention provides a preparation method of the aqueous polyurethane curing agent, which is used for preparing the aqueous polyurethane curing agent according to the first aspect of the invention, and comprises the following steps:
(1) Mixing sulfamate, hexamethylene diisocyanate trimer and a catalyst, and reacting to obtain a reactant;
(2) And adding a siloxane compound into the reactant, and performing secondary reaction to obtain the waterborne polyurethane curing agent.
As a further improvement of the scheme, in the step (1), the reaction temperature is 80-100 ℃ and the reaction time is 3-10 hours.
As a further improvement of the above scheme, in the step (2), the temperature of the secondary reaction is 40-80 ℃ and the NCO content is 15-18%.
Specifically, the reaction end point of the preparation of the high-water-resistance waterborne polyurethane curing agent is based on the fact that the isocyanate content is reduced to a theoretical value, and the difference between the isocyanate content of the isocyanate and the theoretical isocyanate content is less than 0.05wt% measured by a toluene-di-n-butylamine titration method.
As a further improvement of the scheme, the step (1) and the step (2) are both carried out under the protection of inert gas.
Preferably, the inert gas is nitrogen.
As a further improvement of the scheme, the solid content of the aqueous polyurethane curing agent is 99-100%.
The third aspect of the invention provides a waterborne polyurethane coating, which comprises the waterborne polyurethane curing agent disclosed in the first aspect of the invention.
Compared with the prior art, the technical scheme of the invention has at least the following technical effects or advantages:
(1) The aqueous polyurethane curing agent disclosed by the invention is prepared by modifying an aqueous polyisocyanate curing agent obtained by reacting sulfamate with hexamethylene diisocyanate trimer by using 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane, and the prepared aqueous polyurethane curing agent has high water resistance.
(2) In the preparation process, the catalyst existing in the water-based polyisocyanate system of the prior reaction is used as the catalyst of 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane to modify the isocyanate groups of the water-based polyisocyanate, the reaction condition is mild, no additional catalyst is needed, and the system is more stable in later storage.
(3) The waterborne polyurethane curing agent prepared by the invention has high glossiness, is hard but not brittle in the whole paint film, has high wear resistance, greatly improves the final water resistance of the paint film, and can be applied to various industrial coatings.
Detailed Description
The present invention is described in detail below with reference to examples to facilitate understanding of the present invention by those skilled in the art. It is specifically pointed out that the examples are given solely for the purpose of illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and variations of the invention will be within the scope of the invention, as described above, will become apparent to those skilled in the art. While the raw materials mentioned below are not specified, they are all commercial products, and the process steps or preparation methods not specified are all known to the person skilled in the art.
Example 1
The aqueous polyurethane curing agent comprises the following raw materials in parts by weight:
The preparation method of the aqueous polyurethane curing agent comprises the following steps:
(1) Adding hexamethylene diisocyanate trimer into a four-neck flask with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃ under the protection of nitrogen, adding 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt and nitrogen dimethylbenzylamine while stirring, reacting for 6 hours at 80 ℃, and sampling to detect the isocyanate content to be close to a theoretical value (the difference between the isocyanate content and the theoretical value is not more than 0.5 percent);
(2) And (3) adding 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane into the reactant prepared in the step (1), reacting for 5 hours at 45 ℃, and sampling and detecting the isocyanate content to reach a theoretical value (17.5 wt%) to prepare the waterborne polyurethane curing agent of the embodiment. Wherein the determination of the isocyanate content adopts a toluene-di-n-butylamine titration method in HGT 2409-1992.
Example 2
The aqueous polyurethane curing agent comprises the following raw materials in parts by weight:
The preparation method of the aqueous polyurethane curing agent comprises the following steps:
(1) Adding hexamethylene diisocyanate trimer into a four-neck flask with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃ under the protection of nitrogen, adding 2-tertiary butyl-3- (cyclohexylamino) -1-propane sodium sulfonate and nitrogen dimethylbenzylamine while stirring, reacting for 4.5 hours at 90 ℃, and sampling to detect the isocyanate content to be close to a theoretical value (the difference between the isocyanate content and the theoretical value is not more than 0.5 percent);
(2) And (3) adding 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane into the reactant prepared in the step (1), reacting for 5 hours at 80 ℃, and sampling and detecting that the isocyanate content reaches a theoretical value (18.5 wt%) to prepare the waterborne polyurethane curing agent of the embodiment. Wherein the determination of the isocyanate content adopts a toluene-di-n-butylamine titration method in HGT 2409-1992.
Example 3
The aqueous polyurethane curing agent comprises the following raw materials in parts by weight:
The preparation method of the aqueous polyurethane curing agent comprises the following steps:
(1) Adding hexamethylene diisocyanate trimer into a four-neck flask with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃ under the protection of nitrogen, adding 2-isopentyl-3- (cyclohexylamino) -1-propane sodium sulfonate and nitrogen dimethylbenzylamine while stirring, reacting for 5.5 hours at 80 ℃, and sampling to detect the content of isocyanate until the content is close to a theoretical value (the difference between the content and the theoretical value is not more than 0.5 percent);
(2) And (3) adding 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane into the reactant prepared in the step (1), reacting for 5 hours at 80 ℃, and sampling and detecting the isocyanate content to reach a theoretical value (16.5 wt%) to prepare the waterborne polyurethane curing agent of the embodiment. Wherein the determination of the isocyanate content adopts a toluene-di-n-butylamine titration method in HGT 2409-1992.
Comparative example 1
The aqueous polyurethane curing agent comprises the following raw materials in parts by weight:
The preparation method of the aqueous polyurethane curing agent comprises the following steps:
(1) Adding hexamethylene diisocyanate trimer into a four-neck flask with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃ under the protection of nitrogen, adding 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt and nitrogen dimethylbenzylamine while stirring, reacting for 5.5 hours at 80 ℃, and sampling to detect the isocyanate content to be close to a theoretical value (the difference between the isocyanate content and the theoretical value is not more than 0.5 percent);
(2) And (3) adding 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane into the reactant prepared in the step (1), reacting for 5 hours at 80 ℃, and sampling and detecting that the isocyanate content reaches a theoretical value (16.5 wt%) to prepare the waterborne polyurethane curing agent of the comparative example. Wherein the determination of the isocyanate content adopts a toluene-di-n-butylamine titration method in HGT 2409-1992.
Comparative example 1 differs from example 3 in that mercaptopropyl trimethoxysilane was not added to the raw material components of the aqueous polyurethane curing agent, and the total addition amount of the catalyst was unchanged.
Comparative example 2
Commercially available waterborne polyurethane curing agent is Colorum XP2655.
Performance testing
1. Preparation of aqueous polyurethane paint
The aqueous polyurethane paint is prepared by taking the aqueous polyurethane curing agents of examples 1-3 and comparative examples 1-2 as a component B, and the preparation steps are as follows:
(1) Taking 80% aqueous polyurethane dispersion Bayhydrol@2470 and 0.25% wetting agent by mass percent Twain 4100, 0.15% wetting agentTwain 810, 2.5% dipropylene glycol butyl ether, 2.5% dipropylene glycol monomethyl ether, 0.25% thickener COAPUR XS, 0.35% aqueous leveling agent BYK-333 and 14% water, and mixing to obtain a component A;
(2) And (3) weighing the component A and the component B prepared in the step (1) according to the mass ratio of A, B components of 8:1, adding the component B into the component A, and uniformly mixing to prepare the water-based polyurethane coating.
2. Paint Performance test
The aqueous polyurethane coatings prepared using the aqueous polyurethane curing agents of examples 1 to 3 and comparative examples 1 to 2 as component B were subjected to performance test, and the test results are shown in Table 1. Wherein:
The water resistance test comprises the steps of preparing a paint film on a substrate by using a 100 mu m wet film preparation device, maintaining at 23 ℃ and 60% humidity for 7 days after surface drying, sealing edges, soaking in clear water at 25 ℃, and observing whether paint film defects such as blushing, pitting and the like appear;
Testing in an activation period, namely mixing A, B components, and placing the mixture in an environment of 35 ℃ without doubling the viscosity to obtain a paint film with no degradation;
Hardness test according to GBT6739-1996;
Storage stability test-viscosity rise <5% and NCO drop <2.5% after storage at normal temperature, 50 ℃.
TABLE 1 comparison of waterborne polyurethane coating Properties
As can be seen from Table 1, the aqueous polyurethane curing agents prepared in examples 1-3 of the present invention have excellent water solubility under the influence of hydrophilic groups, and tend to form very fine particles after being dispersed in water, thereby improving the transparency and gloss of polyurethane, and meanwhile, 3-mercaptopropyl triethoxysilane and mercaptopropyl trimethoxysilane are adopted as addition materials, so that the polyurethane paint film has proper crosslinking density and excellent biting force with a substrate, thereby greatly improving the excellent water resistance, mechanical properties and storage stability of the paint film.
The waterborne polyurethane curing agents of examples 1-3 were significantly improved in gloss, water resistance, pot life, hardness, and storage stability over conventional polyisocyanate curing agents commercially available in comparative example 2.
Comparative example 1 was found to have lower water resistance and hardness than examples 1 to 3 because only 3-mercaptopropyl triethoxysilane was used as a silane coupling agent.
It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the inventive concept. Accordingly, it is intended that all such modifications as would be within the scope of this invention be included within the scope of this invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent modifications are intended to fall within the scope of the present invention.
Claims (9)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050223A (en) * | 2007-05-14 | 2007-10-10 | 张群朝 | Tripolymer in isocyanic ester class modified by silicane or functional polusiloxane, preparation method |
| CN107880270A (en) * | 2017-11-21 | 2018-04-06 | 广东拓普合成科技股份有限公司 | A kind of preparation method of the water-based isocyanate type curing agent containing silicone segments |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123092A (en) * | 1999-10-28 | 2001-05-08 | Sekisui Chem Co Ltd | Primer composition |
| EP3085720A1 (en) * | 2015-04-21 | 2016-10-26 | Covestro Deutschland AG | Hydrophilic modified polyisocyanurate plastic and method for producing the same |
| US10774239B2 (en) * | 2015-09-09 | 2020-09-15 | Covestro Deutschland Ag | Scratch-resistant two-component polyurethane coatings |
| EP3604372B1 (en) * | 2017-03-30 | 2022-12-14 | Asahi Kasei Kabushiki Kaisha | Polyisocyanate curing agent, aqueous coating composition, coating film, and coated article |
| CN111393612B (en) * | 2020-03-20 | 2021-11-12 | 嘉宝莉化工集团股份有限公司 | Sulfonate type waterborne polyurethane curing agent and preparation method and application thereof |
| CN114230764B (en) * | 2021-12-20 | 2023-06-13 | 嘉宝莉化工集团股份有限公司 | A kind of water-based blocked polyisocyanate curing agent and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050223A (en) * | 2007-05-14 | 2007-10-10 | 张群朝 | Tripolymer in isocyanic ester class modified by silicane or functional polusiloxane, preparation method |
| CN107880270A (en) * | 2017-11-21 | 2018-04-06 | 广东拓普合成科技股份有限公司 | A kind of preparation method of the water-based isocyanate type curing agent containing silicone segments |
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