CN110563923A - Water-dispersible isocyanate curing agent composition with high water resistance and preparation method thereof - Google Patents
Water-dispersible isocyanate curing agent composition with high water resistance and preparation method thereof Download PDFInfo
- Publication number
- CN110563923A CN110563923A CN201910899193.1A CN201910899193A CN110563923A CN 110563923 A CN110563923 A CN 110563923A CN 201910899193 A CN201910899193 A CN 201910899193A CN 110563923 A CN110563923 A CN 110563923A
- Authority
- CN
- China
- Prior art keywords
- curing agent
- agent composition
- isocyanate curing
- water resistance
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08G18/28—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
- C08G18/61—Polysiloxanes
-
- 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
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- 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
Landscapes
- 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)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of isocyanate curing agents, and discloses a water-dispersible isocyanate curing agent composition with particularly high water resistance and a preparation method thereof. The curing agent composition is obtained by heating and reacting 40-99 parts by weight of aliphatic polyisocyanate, 5-40 parts by weight of sulfamic acid containing organosilicon chain segments and 0.1-5 parts by weight of tertiary amine; the molecular structure of the sulfamic acid containing the organosilicon chain segment is as follows:Wherein R is1、R2、R3、R4Identical or different, respectively, monovalent, unsubstituted or substituted aryl radicals or C1-C20 alkanyl radicals; r5Is a divalent, unsubstituted or substituted alkylene radical of C1-C20; n is more than 5; and m is 0-2. The water dispersible isocyanate curing agent composition has good compatibility with water-based hydroxyl resin, and can obtain a coating with particularly high water resistance by curing with the water-based resin containing hydroxyl.
Description
Technical Field
The invention belongs to the technical field of isocyanate curing agents, and particularly relates to a water-dispersible isocyanate curing agent composition with high water resistance and a preparation method thereof.
Background
At present, the water-based two-component polyurethane is widely used in the field covered by solvent-based two-component polyurethane, and is successfully applied to the industries of water-based industrial paint, wood paint, floor paint and the like. The aqueous two-component polyurethane has good physical and mechanical properties, is comparable to solvent-based two-component polyurethane in gloss, hardness and chemical resistance, and has great advantages in environmental protection compared with solvent systems due to low solvent content of the aqueous systems. However, the water resistance of the water-based two-component polyurethane coating is far inferior to that of the solvent-based two-component polyurethane coating, which seriously restricts the further popularization of the water-based two-component polyurethane coating. The reason is that the waterborne hydroxyl acrylic resin and the water dispersible isocyanate curing agent used in the waterborne two-component polyurethane coating both contain a large amount of hydrophilic groups, such as carboxylic acid, sulfonic acid, polyether and the like, so as to ensure the emulsification and dispersion of the resin and the curing agent in water. After the coating film is completely cured, a large number of hydrophilic groups do not participate in the crosslinking reaction and remain in the coating film, thereby seriously affecting the water resistance of the coating film.
The patents US6767958, US4433095 modify isocyanate with sulfonic acid containing amino group and polyethylene glycol monoalkyl ether as hydrophilic components respectively to obtain ionic or nonionic water-emulsifiable isocyanate component, and commercial products synthesized by such methods are Bayhydur2655, Bayhydur 3100 and the like, which are created by koste, and have been widely used in aqueous two-component polyurethane coating. However, the water resistance of the coating film of the water-based two-component polyurethane coating using the hydrophilic polyisocyanate is still a great difference compared with the water resistance of the coating film of the traditional oil-based system, and the water-based two-component polyurethane coating cannot meet the higher and higher water resistance requirement at present.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks and disadvantages of the prior art, it is a primary object of the present invention to provide a water dispersible isocyanate curing agent composition having particularly high water resistance.
The water dispersible isocyanate curing agent composition of the present invention is obtained by reacting polyisocyanate with sulfamic acid and tertiary amine containing an organosilicon segment, is easily dispersed in water, and can obtain a coating layer having particularly high water resistance by curing with a hydroxyl group-containing aqueous resin.
Another object of the present invention is to provide a process for producing the above water-dispersible isocyanate curing agent composition having particularly high water resistance.
The purpose of the invention is realized by the following scheme:
A water-dispersible isocyanate curing agent composition having particularly high water resistance is obtained by reacting 40 to 99 parts by weight of an aliphatic polyisocyanate (A), 5 to 40 parts by weight of an organosilicon-segment-containing sulfamic acid (B), and 0.1 to 5 parts by weight of a tertiary amine (C) with heating.
In the present invention, the molecular structure of the aminosulfonic acid (B) containing an organosilicon segment is as follows:
Wherein R is1、R2、R3、R4Identical or different, respectively, monovalent, unsubstituted or substituted aryl radicals or C1-C20 alkanyl radicals, preferably methyl or phenyl radicals, more preferably methyl radicals; r5Is a divalent, unsubstituted or substituted alkylene radical of C1-C20, preferably C2-C5, more preferably-CH2CH2CH2-; n > 5, preferably n>10, particularly preferably n-20 to 100; m is 0 to 2, preferably m is 1.
In the present invention, the aminosulfonic acid (B) having a silicone segment can be obtained by reacting a silicone resin having a primary amino group (B1) with sultone (B2).
The structural formula of the primary amino group-containing silicone resin (B1) is shown as follows:
The structural formula of the sultone (B2) is shown as follows:
The above reaction equation is shown below:
The molar ratio of the primary amino group-containing silicone resin (B1) to sultone (B2) is preferably 1:0.9 to 1: 1.1. The reaction conditions are preferably 40-80 ℃ for 4-10 h.
The reaction is preferably carried out in an organic solvent (B3); the organic solvent (B3) may be an alcohol, ketone, ester, hydrocarbon solvent, preferably an alcohol solvent, more preferably methanol or ethanol.
In the present invention, the aliphatic polyisocyanate (a) has an NCO functionality of greater than 2.5, preferably greater than or equal to 3; preferably at least one of HDI, IPDI and other trimer type polyisocyanates.
In the present invention, the tertiary amine (C) is a trialkylamine having no hydroxyl group or amino group, and may be at least one of triethylamine, triisopropylamine, tributylamine, diisopropylethylamine, N-dimethylcyclohexylamine, and the like.
In the present invention, the molar ratio of the aminosulfonic acid (B) having an organosilicon segment to the tertiary amine (C) is preferably 1:0.8 to 1:1.5, more preferably 1:1.
In the present invention, the heating reaction is preferably carried out in a solvent system; the solvent may be used in an amount of 0 to 40 parts by weight. The solvent is a solvent such as ethers, esters, hydrocarbons, etc. which do not contain active hydrogen which reacts with isocyanate, and is preferably at least one of propylene glycol methyl ether acetate, diethyl malonate, propylene glycol dimethyl ether, ethyl acetate, butyl acetate, etc.
In the present invention, the temperature of the heating reaction may be 50 to 120 ℃, preferably 70 to 100 ℃. In the invention, the reaction temperature is too high, which can cause the product to generate negative effects such as yellowing, high viscosity and the like, and the reaction is too slow when the temperature is too low. The heating reaction time can be 3-10 h; the reaction is preferably carried out until the NCO content has reached the theoretical value.
In the water dispersible isocyanate curing agent composition, the hydrophilic sulfonic acid chain segment is grafted with the organic silicon resin, so that the water dispersible isocyanate curing agent composition has good compatibility with the water-based hydroxyl resin, and the hydrophobic organic silicon chain segment reduces the hydrophilicity of sulfonic acid groups, so that the water resistance of a coating is greatly improved.
The invention also provides a preparation method of the water dispersible isocyanate curing agent composition with particularly high water resistance, which is obtained by mixing 40-99 parts by weight of aliphatic polyisocyanate (A), 5-40 parts by weight of sulfamic acid (B) containing organosilicon segments and 0.1-5 parts by weight of tertiary amine (C) and heating and reacting at 50-120 ℃ for 3-10 h.
The water dispersible isocyanate curing agent composition is prepared by reacting sulfamic acid containing an organic silicon chain segment with aliphatic polyisocyanate, the hydrophilicity of a sulfonic acid group is reduced by utilizing a hydrophobic organic silicon chain segment, the water resistance of a coating is greatly improved, and the water dispersible isocyanate curing agent composition can be cured with water-based resin containing hydroxyl to obtain a coating with particularly high water resistance.
Drawings
FIG. 1 is a reaction scheme of the preparation method of the present invention, taking HDI trimer as the raw material of polyisocyanate as an example.
Detailed Description
the present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
the materials referred to in the following examples are commercially available.
Example 1
The primary amino group-containing silicone resin X1 was synthesized according to the method described in the literature (silicone synthesis process and product application, Beijing: chemical industry Press, 2000.9, Happy Sonmin, Wangyijilu): 10mL of n-butyllithium (nBu-Li) were added under an argon atmosphere to a charge of 7.4g of (Me)2SiO)4After stirring for 30min, 44g (Me) was added to the reaction flask2SiO)3And 200g of dried tetrahydrofuran, stirring at room temperature for 18H, and adding 3.4g of H2NC3H6Me2SiF blocking agent (consisting of (H)2NC3H6Me2Si)2O and NH4F) and the viscosity of the reaction mass rapidly decreased, after stirring for 2 hours, the solvent was removed under reduced pressure, and lithium fluoride was filtered off by cooling to give 50g of a transparent, colorless silicone resin X1 (n-BuMe) containing primary amino groups2SiO(Me2SiO)nSiMe2C3H6NH2) Having a theoretical molecular weight of 2000.
Synthesis of sulfamic acid Y1 containing organosilicon segments: 200.0 parts by mass of the synthesized organic silicon resin X1 (molecular weight is 2000) containing primary amino, 12.21 parts by mass of 1, 3-propane sultone and 500 parts by mass of methanol are put into a reaction kettle, nitrogen is introduced for protection, the reaction kettle is heated to 60 ℃, a large amount of white solid is separated out after 4 hours of reaction, the white solid is cooled to room temperature, and after suction filtration, methanol is used for washing for three times and drying, 205g of white solid Y1 with theoretical molecular weight of 2122 is obtained.
84.37 parts by mass of Desmodur N3900 (Corsikon solvent-free HDI trimer with NCO content of 23.5 +/-0.3%), 14.89 parts by mass of the synthesized sulfamic acid Y1 (with the theoretical molecular weight of 2122) containing the organic silicon chain segment and 0.75 part by mass of triethylamine are added into a reaction kettle, and after the addition is finished, the temperature is raised to 90 ℃, and the stirring reaction is continued for 8 hours under the condition of heat preservation and nitrogen atmosphere. After cooling to room temperature, the resulting 100% solids hydrophilically-modified polyisocyanate was a nearly colorless transparent viscous liquid having an NCO value of 19.5% and a viscosity (25 ℃ C.) of 1400 cps.
FIG. 1 is a reaction scheme of the preparation method of the present invention, taking HDI trimer as the raw material of polyisocyanate as an example.
Example 2
91.52 parts by mass of Desmodur N3900 (Corsikon solvent-free HDI trimer with NCO content of 23.5 +/-0.3%), 8.08 parts by mass of sulfamic acid Y1 containing organosilicon chain segments synthesized in example 1 and 0.40 part by mass of triethylamine are added into a reaction kettle, the temperature is raised to 90 ℃ after the addition is finished, and the mixture is kept warm in a nitrogen atmosphere and is continuously stirred for reaction for 8 hours. After cooling to room temperature, the resulting 100% solids hydrophilically-modified polyisocyanate was a nearly colorless transparent viscous liquid having an NCO value of 21.3% and a viscosity (25 ℃ C.) of 1300 cps.
Example 3
63.85 parts by mass of Desmodur N3900 (Colesine solvent-free HDI trimer with NCO content of 23.5 +/-0.3%), 34.43 parts by mass of the sulfamic acid Y1 (synthesized by the method in example 1 and with the theoretical molecular weight of 2122) containing the organosilicon chain segment and 1.72 parts by mass of triethylamine are added into a reaction kettle, and after the addition is finished, the temperature is raised to 90 ℃, and the stirring is continued for 8 hours under the condition of heat preservation and nitrogen atmosphere. After cooling to room temperature, the resulting 100% solids hydrophilically-modified polyisocyanate was a nearly colorless transparent viscous liquid having an NCO value of 14.3% and a viscosity (25 ℃ C.) of 1500 cps.
Example 4
67.36 parts by mass of Desmodur N3300 (Colesine solvent-free HDI trimer with NCO content of 23.5 +/-0.3%), 11.89 parts by mass of sulfamic acid Y1 containing organosilicon chain segments synthesized in example 1, 0.75 part by mass of N, N-dimethylcyclohexylamine and 20.0 parts by mass of propylene glycol monomethyl ether acetate were put into a reaction vessel, and after the addition, the temperature was raised to 80 ℃ and the reaction was continued with stirring under a nitrogen atmosphere. After cooling to room temperature, the resulting 80% solids hydrophilically-modified polyisocyanate was a nearly colorless transparent viscous liquid having an NCO value of 14.4% and a viscosity (25 ℃ C.) of 200 cps.
Example 5
67.58 parts by mass of Desmodur Z4470 MPA/X (Corsikon solvent-free IPDI trimer with NCO content of 11.8 +/-0.4%) and 11.93 parts by mass of sulfamic acid Y1 containing the organosilicon chain segment synthesized in example 1, 0.75 part by mass of N, N-dimethylcyclohexylamine and 19.7 parts by mass of diethyl malonate are added into a reaction kettle, the temperature is raised to 100 ℃ after the addition, and the stirring reaction is continued for 8 hours under the condition of heat preservation and nitrogen atmosphere. After cooling to room temperature, the resulting 70% solids hydrophilically-modified polyisocyanate was a pale yellow, nearly colorless, transparent viscous liquid having an NCO value of 7.7% and a viscosity (25 ℃ C.) of 500 cps.
Example 6
Silicone resins containing primary amino groups X2 according to the literature (Silicone Synthesis Process and productsApplication, Beijing: chemical industry publishers, 2000.9, happy pine, royal monolite) were synthesized: 10mL of n-butyllithium were added under argon to a charge of 7.4g of (Me)2SiO)4After stirring for 30min in the reaction flask of (2), 120g of (Me) was added2SiO)3and 200g of dried tetrahydrofuran, stirring at room temperature for 18H, and adding 3.4g of H2NC3H6Me2SiF blocking agent (consisting of (H)2NC3H6Me2Si)2O and NH4F) is prepared, the viscosity of the reaction mass is rapidly reduced, after stirring and reacting for 2h, the solvent is removed under reduced pressure, lithium fluoride is filtered off by cooling, 125g of transparent colorless organic silicon resin X2 (n-BuMe) containing primary amino group is obtained2SiO(Me2SiO)nSiMe2C3H6NH2) And has a theoretical molecular weight of 5000.
Synthesis of sulfamic acid Y2 containing organosilicon segments: 500.0 parts by mass of the synthesized organic silicon resin X2 (with the molecular weight of 5000) containing primary amino, 12.21 parts by mass of 1, 3-propane sultone and 500 parts by mass of methanol are put into a reaction kettle, nitrogen is introduced for protection, the reaction kettle is heated to 60 ℃, a large amount of white solid is separated out after 4 hours of reaction, the white solid is cooled to room temperature, and after suction filtration, the white solid Y2 of 503g is obtained after washing with methanol for three times and drying, and the theoretical molecular weight is 5122.
74.06 parts by mass of Desmodur N3900 (Corsikon solvent-free HDI tripolymer, the NCO content of which is 23.5 +/-0.3%), 25.41 parts by mass of the synthesized sulfamic acid Y2 (the theoretical molecular weight of 5122) containing the organic silicon chain segment and 0.53 part by mass of triethylamine are added into a reaction kettle, and after the addition is finished, the temperature is raised to 90 ℃, and the stirring reaction is continued for 8 hours under the condition of heat preservation and nitrogen atmosphere. After cooling to room temperature, the resulting 100% solids hydrophilically-modified polyisocyanate was a nearly colorless transparent viscous liquid having an NCO value of 17.2% and a viscosity (25 ℃ C.) of 1100 cps.
Example 7
The primary amino group-containing silicone resin X3 was synthesized according to the method described in the literature (silicone synthesis process and product application, Beijing: chemical industry Press, 2000.9, Happy Sonmin, Wangyijilu): 10mL of n-butyllithium (nBu-Li) were added to the reaction mixture under an argon gas atmosphereContaining 7.4g of (Me)2SiO)4after stirring for 30min, 24g of (Me) was added to the reaction flask2SiO)3，20g(Ph2SiO)3And 200g of dried tetrahydrofuran, stirring at room temperature for 18H, and adding 3.4g of H2NC3H6Me2SiF blocking agent (consisting of (H)2NC3H6Me2Si)2O and NH4F) and the viscosity of the reaction mass rapidly decreased, after stirring for 2 hours, the solvent was removed under reduced pressure, and lithium fluoride was filtered off by cooling to give 50g of a transparent, colorless silicone resin X3 (n-BuMe) containing primary amino groups2SiO(Me2SiO)m(Ph2SiO)nSiMe2C3H6NH2) Having a theoretical molecular weight of 2000.
Synthesis of sulfamic acid Y3 containing organosilicon segments: 200.0 parts by mass of the synthesized organic silicon resin X3 (molecular weight is 2000) containing primary amino, 12.21 parts by mass of 1, 3-propane sultone and 500 parts by mass of methanol are put into a reaction kettle, nitrogen is introduced for protection, the reaction kettle is heated to 60 ℃, a large amount of white solid is separated out after 4 hours of reaction, the white solid is cooled to room temperature, and after suction filtration, methanol is used for washing for three times and drying, 205g of white solid Y3 with theoretical molecular weight of 2122 is obtained.
84.37 parts by mass of Desmodur N3900 (Corsikon solvent-free HDI trimer with NCO content of 23.5 +/-0.3%), 14.89 parts by mass of the synthesized sulfamic acid Y3 (with the theoretical molecular weight of 2122) containing the organic silicon chain segment and 0.75 part by mass of triethylamine are added into a reaction kettle, and after the addition is finished, the temperature is raised to 90 ℃, and the stirring reaction is continued for 8 hours under the condition of heat preservation and nitrogen atmosphere. After cooling to room temperature, the resulting 100% solids hydrophilically-modified polyisocyanate was a nearly colorless transparent viscous liquid having an NCO value of 19.5% and a viscosity (25 ℃ C.) of 1400 cps.
performance testing
The isocyanate curing agent composition prepared in the above example was compared with a commercial isocyanate curing agent CoSi-Bayhydur 2655(NCO value of 21.2%). Wherein, commercial hydroxy acrylic acid secondary dispersion resin is selected: PA-4845 (New Guanzhi material, hydroxyl content 2.0%, solid content 42%), and the isocyanate curing agent are prepared into the aqueous two-component polyurethane coating according to the following formula.
TABLE 1 formulation of the hydroxyl component
| Specific reagent | Mass percent | Components | Manufacturer of the product |
| PA-4845 | 80 | Aqueous hydroxy resin | New material for Guanzhi |
| Tego-902W | 0.2 | Defoaming agent | Digao (high) |
| BYK-333 | 0.4 | Leveling agent | chemistry of Pico |
| BYK-024 | 0.3 | Defoaming agent | Air chemistry |
| Hydropalat-140 | 0.4 | Wetting agent | Kening medicine |
| DPnB | 2 | Film forming aid | Chemistry of Dow |
| DPM | 3 | Film forming aid | Chemistry of Dow |
| OS-8W | 0.3 | Thickening agent | Guanzhi (crown word) |
| OS-2020 | 0.4 | Thickening agent | Guanzhi (crown word) |
| pure water | 13 |
An isocyanate component: the curative in the above examples and Bayhydur2655 as a comparative curative were each diluted to 70% solids with PMA for use.
Wherein the ratio of the hydroxyl component to the isocyanate component is calculated as NCO/OH 1.5. And mixing the hydroxyl component and the isocyanate component, and then adjusting the mixture to proper viscosity by using water for construction. The construction conditions are as follows: at 25 ℃ and 60% humidity, the wet film thickness is 80 μm. And testing the hardness after the coating is dried for 7 days at normal temperature, wherein the pencil hardness test standard is GB/T6739-2006. The initial water resistance test is that the water is soaked in normal temperature water after being air-dried for 3 days at normal temperature, and whether the water turns white and foams or not is observed; the final water resistance test is that the mixture is baked for 1h at 80 ℃ and then placed for three days at normal temperature, and then normal temperature water is soaked to observe whether the mixture turns white and foams. The test results are shown in table 2 below:
TABLE 2 polyurethane coating Performance parameters
| Initial water resistance | Final water resistance | Hardness of pencil | |
| Example 1 | 7 days | 14 days | H |
| Example 2 | 5 days | 12 days | H |
| Example 3 | 14 days | 18 days | 2H |
| Example 4 | 7 days | 14 days | H |
| Example 6 | 12 days | 18 days | 2H |
| Example 7 | 12 days | 18 days | 2H |
| Bayhydur2655 | 2 days | 5 days | H |
The results above show that the coating prepared from the curing agent composition prepared according to the present invention all exhibit significantly improved water resistance properties, while exhibiting comparable or superior pencil hardness, relative to the standard commercial water-dispersible isocyanate curing agent Bayhydur 2655. The hydrophobic organic silicon chain segment introduced by the composition structure of the invention is grafted with sulfonic acid, so that the hydrophilicity of sulfonic acid groups is greatly reduced, and the water resistance of a paint film is greatly improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A water dispersible isocyanate curing agent composition with high water resistance is characterized in that the water dispersible isocyanate curing agent composition is obtained by heating and reacting 40-99 parts by weight of aliphatic polyisocyanate, 5-40 parts by weight of sulfamic acid containing organosilicon chain segments and 0.1-5 parts by weight of tertiary amine;
The molecular structure of the sulfamic acid containing the organosilicon chain segment is as follows:
Wherein R is1、R2、R3、R4Identical or different, respectively, monovalent, unsubstituted or substituted aryl radicals or C1-C20 alkanyl radicals; r5Is a divalent, unsubstituted or substituted alkylene radical of C1-C20; n is more than 5; and m is 0-2.
2. The water dispersible isocyanate curing agent composition having high water resistance according to claim 1, characterized in that: r1、R2、R3、R4Identical or different are each methyl or phenyl; r5is alkylene of C2-C5.
3. The water dispersible isocyanate curing agent composition having high water resistance according to claim 1, characterized in that: the sulfamic acid containing the organic silicon chain segment is obtained by the reaction of organic silicon resin containing primary amino and sultone;
The structural formula of the organic silicon resin containing primary amino groups is shown as follows:
the structural formula of the sultone is shown as follows:
4. The water dispersible isocyanate curing agent composition having high water resistance according to claim 3, characterized in that: the using amount molar ratio of the organosilicon resin containing primary amino groups to sultone is 1:0.9-1: 1.1; the reaction condition is that the reaction is carried out for 4 to 10 hours at the temperature of between 40 and 80 ℃.
5. The water dispersible isocyanate curing agent composition having high water resistance according to claim 1, characterized in that: the NCO functionality of the aliphatic polyisocyanate is more than 2.5; the tertiary amine is trialkylamine without hydroxyl or amino groups.
6. The water dispersible isocyanate curing agent composition having high water resistance according to claim 1, characterized in that: the aliphatic polyisocyanate comprises at least one of HDI (hexamethylene diisocyanate) and IPDI (isophorone diisocyanate) trimer type polyisocyanates; the tertiary amine comprises at least one of triethylamine, triisopropylamine, tributylamine, diisopropylethylamine and N, N-dimethylcyclohexylamine.
7. The water dispersible isocyanate curing agent composition having high water resistance according to claim 1, characterized in that: the mol ratio of the sulfamic acid containing the organic silicon chain segment to the tertiary amine is 1:0.8-1: 1.5.
8. The water dispersible isocyanate curing agent composition having high water resistance according to claim 1, characterized in that: the temperature of the heating reaction is 50-120 ℃; the heating reaction time is 3-10 h.
9. The water dispersible isocyanate curing agent composition having high water resistance according to claim 1, characterized in that: the heating reaction is carried out in a solvent system; the amount of the solvent is 0 to 40 parts by weight.
10. A method for producing a water dispersible isocyanate curing agent composition having high water resistance according to any one of claims 1 to 9, characterized in that: the organic silicon-containing aliphatic polyisocyanate is prepared by mixing 40-99 parts by weight of aliphatic polyisocyanate, 5-40 parts by weight of sulfamic acid containing organic silicon chain segments and 0.1-5 parts by weight of tertiary amine, and heating and reacting at 50-120 ℃ for 3-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910899193.1A CN110563923A (en) | 2019-09-23 | 2019-09-23 | Water-dispersible isocyanate curing agent composition with high water resistance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910899193.1A CN110563923A (en) | 2019-09-23 | 2019-09-23 | Water-dispersible isocyanate curing agent composition with high water resistance and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110563923A true CN110563923A (en) | 2019-12-13 |
Family
ID=68781848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910899193.1A Withdrawn CN110563923A (en) | 2019-09-23 | 2019-09-23 | Water-dispersible isocyanate curing agent composition with high water resistance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110563923A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116865A (en) * | 2020-01-06 | 2020-05-08 | 万华化学集团股份有限公司 | High-water-resistance and hydrophilic polyisocyanate curing agent and preparation method and application thereof |
| CN114605606A (en) * | 2022-03-31 | 2022-06-10 | 安徽省金盾涂料有限责任公司 | Preparation method and application of multi-curing anionic organosilicon modified polyisocyanate aqueous curing agent |
| CN114605606B (en) * | 2022-03-31 | 2024-06-07 | 安徽省金盾涂料有限责任公司 | Preparation method and application of multi-curing anionic organosilicon modified polyisocyanate water-based curing agent |
-
2019
- 2019-09-23 CN CN201910899193.1A patent/CN110563923A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116865A (en) * | 2020-01-06 | 2020-05-08 | 万华化学集团股份有限公司 | High-water-resistance and hydrophilic polyisocyanate curing agent and preparation method and application thereof |
| CN114605606A (en) * | 2022-03-31 | 2022-06-10 | 安徽省金盾涂料有限责任公司 | Preparation method and application of multi-curing anionic organosilicon modified polyisocyanate aqueous curing agent |
| CN114605606B (en) * | 2022-03-31 | 2024-06-07 | 安徽省金盾涂料有限责任公司 | Preparation method and application of multi-curing anionic organosilicon modified polyisocyanate water-based curing agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107325262B (en) | Blocked isocyanate, coating composition, adhesive composition, and article | |
| JP6165419B2 (en) | Aqueous two-component coating composition, ink composition, adhesive composition, and method of using the same | |
| CN109844041B (en) | Rheology modifying urethane compounds | |
| JPWO2018056408A1 (en) | Polyisocyanate composition, block polyisocyanate composition, coating composition, aqueous coating composition, and coating substrate | |
| TWI655244B (en) | Radiation-curable aqueous composition having controlled polymer flow and preparation method thereof | |
| US20100168297A1 (en) | High-gloss polyurethane coatings prepared from allophanate/polyisocyanate hardener compositions | |
| JP2008045072A (en) | Blocked isocyanate-containing emulsion composition, process for producing the same, and composition for baking-type coating or for adhesive | |
| WO2019065890A1 (en) | Blocked polyisocyanate composition and use thereof | |
| CN109957091B (en) | Polyurethane polymer suitable for adjusting viscosity of aqueous high-solvent system and composition containing polyurethane polymer | |
| JPWO2019078241A1 (en) | Polyisocyanate composition, coating composition and coating film | |
| JP5446077B2 (en) | Aqueous resin composition comprising a blocked isocyanate-containing aqueous emulsion composition as a curing agent, and an aqueous baking type paint or adhesive composition using the same | |
| CN111423775A (en) | Single-component water-based finishing varnish and preparation method thereof | |
| EP2556097A1 (en) | Aqueous anionic polyurethane dispersions | |
| CN109535372B (en) | Waterborne polyurethane and preparation method thereof | |
| CN107636096B (en) | Polyurethane coating composition | |
| JPH07232052A (en) | Hardenable oil-in-water type emulsion, method for production thereof and use thereof | |
| CN110563923A (en) | Water-dispersible isocyanate curing agent composition with high water resistance and preparation method thereof | |
| CN111848923B (en) | Preparation method of water-based polyisocyanate curing agent | |
| US9353285B2 (en) | Water-based two-component coating compositions | |
| CN104592469A (en) | Anionic polyurethane aqueous dispersion, prepolymer monomer and preparation process thereof | |
| CN112225878A (en) | High-alkali-resistance aqueous bi-component isocyanate curing agent and preparation method thereof | |
| CN111574921A (en) | Easily-cured waterproof polyurethane wood paint and preparation method thereof | |
| KR100446672B1 (en) | New Polyamines and Their Use in Coating Compositions | |
| JP2020023664A (en) | Polyisocyanate composition, coating composition and coating film | |
| CN109627424B (en) | Preparation method and application of perfluoroalkyl side chain modified ketimine curing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20191213 |
|
| WW01 | Invention patent application withdrawn after publication |