CN111116865B - High-water-resistance and hydrophilic polyisocyanate curing agent and preparation method and application thereof - Google Patents
High-water-resistance and hydrophilic polyisocyanate curing agent and preparation method and application thereof Download PDFInfo
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- CN111116865B CN111116865B CN202010010505.1A CN202010010505A CN111116865B CN 111116865 B CN111116865 B CN 111116865B CN 202010010505 A CN202010010505 A CN 202010010505A CN 111116865 B CN111116865 B CN 111116865B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 79
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 49
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 239000003973 paint Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 11
- 239000011324 bead Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 239000002612 dispersion medium Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical group O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940116423 propylene glycol diacetate Drugs 0.000 claims description 3
- 239000011253 protective coating Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical group CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical group CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 12
- 238000005536 corrosion prevention Methods 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- 239000010962 carbon steel Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
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- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- -1 acetylene glycol Chemical compound 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
-
- 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
- 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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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polyisocyanate curing agent with high water resistance and hydrophilicity, and a preparation method and application thereof. The polyisocyanate curing agent has the structural formula shown below:the polyisocyanate curing agent has higher NCO content, lower viscosity and excellent water resistance; the paint is prepared by matching with acrylic acid dispersoids with different hydroxyl values, and the tests on the appearance, the water resistance and other properties of a paint film show that the polyisocyanate curing agent not only keeps the appearance characteristic of high light and high transparency of a water-based curing agent, but also has the water resistance and other properties which are comparable to those of a solvent-based curing agent, and is particularly suitable for the field of metal corrosion prevention.
Description
Technical Field
The invention belongs to the field of macromolecules, and particularly relates to a high-water-resistance and hydrophilic polyisocyanate curing agent, and a preparation method and application thereof.
Background
In recent years, with the stricter environmental regulations, the water-based paint is favored by the market because of effectively degrading the emission of VOC, and the superiority thereof is highlighted. However, the water-based paint has certain differences from the solvent-based paint in workability, appearance effect, particularly water resistance, so that the oil-based paint still occupies a main market in many fields, and the oil-based two-component polyurethane system occupies more than 60 percent of the whole paint market. The two-component polyurethane water paint is the best scheme for replacing an oily two-component polyurethane system, and can reach most of performance indexes at present, even some performance indexes exceed those of oily paint. The double-component polyurethane water-based paint is crosslinked and cured by means of the reaction of-NCO group and-OH group to obtain a compact paint film, thereby obtaining excellent anticorrosion and appearance effects.
In the field of metal corrosion prevention, two obstacles of appearance and resistance (particularly water resistance) exist in the process of comprehensively replacing solvent-based coatings in the water-based two-component coating, and the obstacle is brought to the oil-to-water process of the coating industry. The invention relates to a water-based isocyanate curing agent, which is invented by the earliest Bayer company (Cordsura). The trimer such as HDI, IPDI, TDI or PDI is subjected to sulfonate or polyether hydrophilic modification, so that the trimer has certain hydrophilicity and thus has certain water dispersibility. The sulfonate modification has higher appearance effect, can achieve better luster and fullness, and is generally accepted in the field of metal bi-component corrosion prevention. Although the hydrophilic modified tripolymer can keep better stability and gloss in a water system, the water resistance and other properties of a final paint film are greatly reduced due to the existence of hydrophilic groups, and the performance of the final paint film is greatly different from that of a solvent system. In order to ensure the hydrophilicity and water resistance of the curing agent, patent document CN107880270A discloses the incorporation of a silicone resin or segment into a trimer through reaction with NCO groups on the trimer. Although the method can give consideration to both water resistance and gloss, the NCO group on the tripolymer is consumed by hydrophilic modification and introduction of the organic silicon, so that the NCO content of the curing agent is lower. Under the same formula system, the curing agent with lower NCO content is selected, which means that more curing agents are used, and consequently, more curing agents such as diluent solvent are used, so that the VOC content of the whole formula system is increased, and more environmental pollution and other problems are caused; meanwhile, the organic silicon or other chain segments connected by the method can obviously increase the viscosity of the curing agent, and bring obvious inconvenience to the use and construction of the curing agent.
In addition, many attempts have been made to silicon-modify aqueous isocyanate curing agents, for example, patent document CN107619465A discloses the use of γ -glycidoxypropyltrimethoxysilane to directly modify HDI trimer. Because the gloss fullness is an important performance index in the field of metal corrosion prevention, although the silicon modified water-based isocyanate curing agent can improve the hardness and the adhesive force of a final paint film, the modified tripolymer has insufficient hydrophilic capability, the hydrophilicity caused by siloxane hydrolysis is far insufficient to maintain the requirement of a high-gloss and high-fullness system, the dispersibility of the whole system is poor, and the gloss fullness of the paint film can be greatly influenced.
Therefore, a polyisocyanate curing agent which is highly water-resistant, hydrophilic and has a gloss fullness meeting the requirements of the metal corrosion prevention field is urgently needed.
Disclosure of Invention
Therefore, the invention aims to provide a polyisocyanate curing agent which is high in water resistance, hydrophilic and has luster fullness meeting the requirements of the metal anticorrosion field, and further provides a preparation method and application thereof, and further provides a water-based double-component metal anticorrosion coating prepared by the polyisocyanate curing agent.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides a highly water-resistant and hydrophilic polyisocyanate curing agent having the structural formula shown below:
Preferably, the reaction equation is as follows:
in a second aspect, the present invention provides a method for preparing the above polyisocyanate curing agent with high water resistance and hydrophilicity, comprising the steps of: under the condition that nitrogen is selected as an inert atmosphere, butane sultone is added into a reaction container, silane coupling agent is slowly added under the stirring of 55-70 ℃, then the stirring is continued for reaction for 10-30 min, HDI trimer is added, the temperature is raised to 90-120 ℃, neutralizer is slowly dropped under the stirring for neutralization, the reaction is continued under the condition of keeping 90-120 ℃ until the NCO content is 21-22 wt%, and the polyisocyanate curing agent with high water resistance and hydrophilicity is obtained.
Preferably, in the above preparation method of the highly water-resistant and hydrophilic polyisocyanate curing agent according to the present invention, the silane coupling agent is selected from γ -aminopropyltrimethoxysilane KH540 and/or γ -aminopropyltriethoxysilane KH 550.
Preferably, in the preparation method of the polyisocyanate curing agent with high water resistance and hydrophilicity, the mass ratio of the butane sultone to the silane coupling agent is 0.8-1.2: 1, and preferably 1: 1.
Preferably, in the preparation method of the highly water-resistant and hydrophilic polyisocyanate curing agent, the mass ratio of the HDI trimer, the butane sultone and the silane coupling agent is 98-95: 1-2.5: 1 to 2.5.
Preferably, in the preparation method of the polyisocyanate curing agent with high water resistance and hydrophilicity, the neutralizing agent is an amine neutralizing agent, preferably a tertiary amine, and more preferably N, N-dimethylcyclohexylamine; and/or, adding a neutralizing agent dropwise for neutralization until the neutralization degree is 100%.
In a third aspect, the invention provides the application of the polyisocyanate curing agent with high water resistance and hydrophilicity in the field of metal anticorrosive coatings; preferably, the application is in the field of aqueous two-component metal anticorrosive coatings.
In a fourth aspect, the invention provides a water-based two-component metal anticorrosive paint, which comprises a component A and a component B,
the component A comprises: 40-90 parts by weight, preferably 55-65 parts by weight, of an aqueous hydroxyacrylic dispersion; 20-50 parts of color paste, preferably 30-35 parts; 0.5 to 15 parts by weight of a solvent, preferably 2 to 8 parts by weight; the water is selected from 0 to 20 parts by weight of deionized water, preferably 1 to 10 parts by weight; 0.5-5 parts by weight of water-based auxiliary agent, preferably 1-2 parts by weight;
the component B comprises: 5 to 40 parts by weight, preferably 10 to 25 parts by weight of the high-water-resistant and hydrophilic polyisocyanate curing agent prepared by the above-mentioned high-water-resistant and hydrophilic polyisocyanate curing agent of the invention or the above-mentioned preparation method of the invention; 0 to 10 parts by weight of a solvent, preferably 2 to 8 parts by weight.
Preferably, in the aqueous two-component metal anticorrosive paint of the present invention, in the component a, the solvent is selected from diethylene glycol butyl ether DBG and/or ethylene glycol butyl ether BCS; and/or, in component B, the solvent is selected from propylene glycol diacetate PGDA and/or propylene glycol methyl ether acetate PMA, preferably from propylene glycol methyl ether acetate PMA; and/or the color paste comprises the following components: the titanium dioxide is preferably 15.0 to 37.5 parts by weight of R706 titanium dioxide, preferably 25 parts by weight; 0.6 to 1.5 parts by weight of a dispersant, preferably 1.0 part by weight; the water is preferably deionized water 5.0-9.0 parts by weight, preferably 7.0 parts by weight; 0.1 to 0.3 part by weight of a defoaming agent, preferably 0.2 part by weight; and/or in the component A, the aqueous auxiliary agent is selected from at least one of the following components: 0 to 0.5 part by weight of a pH regulator, preferably 0.1 to 0.2 part by weight; 0.1 to 1 part by weight of a wetting agent, preferably 0.1 to 0.5 part by weight; 0.1 to 1 part by weight of leveling agent, preferably 0.2 to 0.5 part by weight; 0.1 to 1 part by weight of a thickener, preferably 0.2 to 0.4 part by weight.
In the color paste, the defoaming agent is selected from at least one of mineral oil type, organic silicon type and acetylene glycol type, and is preferably selected from Tego 904W.
In the aqueous auxiliary agent, the pH regulator is an amine pH regulator, preferably N, N-dimethylethanolamine DMEA. The wetting agent is selected from polyether organic silicon and/or nonionic surfactant, the polyether organic silicon is selected from Tego-4100, BYK-345, BYK-346, BYK-348 and BYK-349, and the nonionic surfactant is selected from Tego-4100. The leveling agent is selected from modified silicone type, preferably from Tego Glide 100. The thickener is selected from polyurethane associative type, preferably from Haimines 299 and/or BYK-425.
In a fourth aspect, the invention provides a preparation method of the aqueous two-component metal anticorrosive paint, which comprises the following steps:
the preparation of the component A comprises the following steps: firstly, preparing color paste, grinding the color paste, then sequentially adding the selected parts by weight of aqueous hydroxyl acrylic acid dispersoid, solvent, water and aqueous auxiliary agent into the ground color paste under stirring, and stirring until the components are uniformly mixed to obtain a component A;
the preparation of component A preferably comprises the following steps: adding a dispersing agent, titanium dioxide, water, a defoaming agent and a dispersion medium into a container, dispersing to prepare color paste, grinding the color paste until the fineness is lower than 10 mu m, then sequentially adding a selected weight part of aqueous hydroxyl acrylic acid dispersoid, a solvent, water and an aqueous auxiliary agent into the ground color paste under stirring, stirring until the components are uniformly mixed, and filtering the dispersion medium to obtain a component A; wherein the dispersion medium is preferably zirconium beads or glass beads, more preferably zirconium beads;
the preparation of component a more preferably comprises the following steps: adding a dispersing agent, titanium dioxide, water, a defoaming agent and zirconium beads into a grinding tank, dispersing at a high speed of 3000r/min for 30-60min to prepare color paste, grinding the color paste until the fineness is lower than 10 mu m, then sequentially adding an aqueous hydroxy acrylic acid dispersoid, a solvent, water and an aqueous auxiliary agent into the ground color paste under the stirring of 600r/min, stirring at 600r/min for 15-20min until the mixture is uniform, and filtering the zirconium beads by using a 300-mesh filter screen to obtain a component A;
the preparation of component B comprises the following steps: and (2) mixing the solvent with the high-water-resistance and hydrophilic polyisocyanate curing agent or the high-water-resistance and hydrophilic polyisocyanate curing agent prepared by the preparation method in parts by weight, and uniformly stirring to obtain the component B.
When the dispersion agent is used, the component A and the component B are mixed and dispersed for 10-15min at the rotating speed of 600-800 r/min.
The technical scheme provided by the invention has the following beneficial effects:
(1) according to the invention, the butane sultone and the HDI tripolymer modified by the silane coupling agent containing primary amine are used for preparing the polyisocyanate curing agent containing the organic silicon sulfonate, and the prepared polyisocyanate curing agent has higher NCO content, lower viscosity and excellent water resistance;
(2) the polyisocyanate curing agent is matched with acrylic dispersions with different hydroxyl values to prepare the coating, and tests on the appearance, water resistance and other properties of a paint film show that the polyisocyanate curing agent not only keeps the appearance characteristics of high gloss and high transparency of a water-based curing agent, but also has the water resistance and other properties comparable to those of a solvent-based curing agent, and is particularly suitable for the field of metal corrosion prevention.
Drawings
FIG. 1 is an IR spectrum of an HDI trimer in example 1 of the present invention;
FIG. 2 is an IR spectrum of a polyisocyanate curing agent of high water resistance and hydrophilicity prepared by the present invention.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The raw materials and sources of this example are as follows:
BYK-190, dispersant, birk;
ti-pure R-706, titanium dioxide, DuPont;
tego 904W, defoamer, Digao;
zirconium beads, a dispersion medium and digao;
DMEA, pH adjuster, hamming;
tego 4100, wetting agent, digao;
tego 100, leveling agent, Digao;
diethylene glycol monobutyl ether DBG, solvent and Chinese medicines;
ethylene glycol monobutyl ether BCS, solvent and Chinese medicine;
propylene glycol diacetate PGDA, solvent and Chinese medicaments;
propylene glycol methyl ether acetate PMA, a solvent and Chinese medicaments;
rheelate 299/BCS/water (5/3/2), thickener, hamming;
HDI trimer, wanhua.
In the following examples of the present invention, NCO group content was measured by the di-n-butylamine method.
Example 1
The structural formula of the polyisocyanate curing agent with high water resistance and hydrophilicity in the embodiment is shown as follows:
The preparation method comprises the following steps: under the protection of nitrogen, 1kg of butane sultone is added into a reaction vessel, 1kg of silane coupling agent KH540 is slowly added under stirring at 60 ℃, then the mixture is stirred and continuously reacted for 10min, 98kg of HDI tripolymer is added, the temperature is raised to 100 ℃, N-dimethyl cyclohexylamine is slowly added dropwise under stirring to carry out 100% neutralization, the temperature is kept at 100 ℃, the reaction is continuously carried out until the NCO content is 21-22 wt%, and the high-water-resistance and hydrophilic polyisocyanate curing agent is obtained.
The IR spectrum of HDI trimer is shown in FIG. 1, and the IR spectrum of the polyisocyanate curing agent having high water resistance and hydrophilicity prepared in this example is shown in FIG. 2.
As can be seen from comparison between FIG. 1 and FIG. 2, the IR spectrum of the highly water-resistant and hydrophilic polyisocyanate curing agent of this example not only retained the characteristic absorption peak of HDI trimer structure, but also ranged from-2258 cm-1Obvious characteristic absorption peak of isocyanic acid radical is simultaneously in 1180cm-1、~1060cm-1、~610cm-1、~580cm-1Has obvious sulfonate characteristic peak at 1080cm-1、830cm-1Has obvious characteristic peak of silicon-oxygen bond. NCO group content test node by combining di-n-butylamine methodAs a result, example 1 was shown to produce a modified HDI trimer with siloxane bonds and sulfonate groups replacing the monoisocyanate groups.
Example 2
The structural formula of the polyisocyanate curing agent with high water resistance and hydrophilicity in the embodiment is shown as follows:
The preparation method of this example differs from example 1 only in that: the silane coupling agent KH540 was replaced with KH550, and the remaining raw materials and reaction conditions were the same as in example 1.
Examples 3 to 11
The preparation methods of the highly water-resistant and hydrophilic polyisocyanate curing agents of examples 3 to 11 are shown in Table 1, as differences from example 1.
TABLE 1 differences between the preparation of examples 3 to 11 and example 1
Example 12
The formulation of the waterborne two-component metal anticorrosive coating of the present example is shown in table 2:
TABLE 2 coating formulation of example 12 (unit: kg)
The preparation of the component A comprises the following steps: respectively adding dispersant BYK-1901 g, titanium pigment Ti-pure R-70625 g, deionized water 7.1g, defoaming agent Tego 904W 0.2g and zirconium beads 25g into a 300mL iron tank at the rotating speed of 600R/min, then dispersing at 3000R/min to prepare color paste, grinding the color paste until the fineness is lower than 10 μm, adding 58.8g of Antkote2035 hydroxyacrylic acid dispersoid, 5g of solvent DBG, 1.5g of deionized water, 0.1g of pH regulator DMEA, 41000.3 g of wetting agent Tego, 1000.3 g of flatting agent and 0.4g of thickener RHELATE 299/BCS/water (5/3/2) at 600R/min, dispersing for 15-20min to be uniformly mixed, and then filtering the zirconium beads by using a 300-mesh filter screen to obtain a component A;
the preparation of component B comprises the following steps: 14.4g of the highly water-resistant and hydrophilic polyisocyanate curing agent of example 1 and 3.6g of the solvent PMA were mixed and stirred uniformly to obtain component B.
Example 13
The formulation of the aqueous two-component metal anticorrosive coating of this example differs from that of example 12 only in that: the highly water-resistant and hydrophilic polyisocyanate curing agent of example 1 was replaced with the highly water-resistant and hydrophilic polyisocyanate curing agent of example 2, and the remaining raw materials and experimental conditions were the same as those of example 12.
Examples 14 to 15
The formulation of the aqueous two-component metal corrosion protective coating of examples 14-15 differs from that of example 12 as shown in table 3.
TABLE 3 coating formulations of examples 14-15 (unit: kg)
Experimental example 1Early water resistance test at 40 ℃
The component A and the component B of the example 12 are mixed and dispersed for 10-15min at the rotating speed of 600r/min, and the water-based two-component white paint prepared by the coating of the example 12 is prepared. An aqueous two-component white paint prepared from the coating of example 13 was prepared in a similar manner. The aqueous two-component white paints of examples 12 and 13 were then respectively drawn on degreased and sanded carbon steel panels using a 150 μm wire bar, and after overnight the gloss was measured using a BGD gloss meter and the early water resistance at 40 ℃ was measured by immersion in water at 40 ℃ with the experimental results shown in Table 4.
Table 440 ℃ early water resistance test results
Curing agent viscosity (LV,63#12r) | Self-drying 40 ℃ early water resistance | Gloss of paint film | |
Example 12 | 1580 | Foaming for 4 days | 85%/93% |
Example 13 | 2006 | Foaming for 4 days | 83%/91% |
As can be seen from Table 4, the water resistance at 40 ℃ early stage of the aqueous two-component white paints of examples 12 and 13 was both acceptable; the coating of example 12 is superior in view of excellent workability and slightly high gloss due to low viscosity.
Experimental example 2
The highly water-resistant and hydrophilic polyisocyanate curing agent of example 1, the curing agent prepared in example 1 of patent document CN107619465A, a commercially available aqueous product Aquolin270, and a commercially available solvent-based product HT600 were used to measure the viscosity using LV viscometer with rotor number 63 and rotation speed 12. The test results are shown in Table 5.
The curing agent prepared in example 1 of patent document CN107619465A, the commercially available aqueous product Aquolin270 and the commercially available solvent-based product HT600 were prepared into coatings in a similar manner to example 12, and the coatings of example 12 were taken, and the coatings were respectively knife-coated on different substrates with a thickness of 150 μm, adhesion was measured by the Baige method, and the coatings were respectively knife-coated on carbon steel plates with a thickness of 150 μm, and after leaving overnight, the carbon steel plates were respectively placed in water at a temperature of 25 ℃ and a temperature of 40 ℃ to be tested for early water resistance by air drying at 25 ℃ and 40 ℃ and at the same time, the coatings were respectively knife-coated on the carbon steel plates with a thickness of 150 μm, and the coatings were baked at a temperature of 80 ℃ for 30 min. After cooling, the gloss is tested by using a BGD gloss instrument, and then the test sample is placed in water at the temperature of 25 ℃ and 40 ℃ and is tested and baked at the temperature of 25 ℃ and early stage water resistance at the temperature of 40 ℃. The test results are shown in Table 5.
TABLE 5 test results of Experimental example 2
As can be seen from Table 5, the highly water-resistant and hydrophilic polyisocyanate curing agent of example 1 achieves the water-resistant performance of the solvent-based curing agent while ensuring the high appearance of the aqueous system.
Experimental example 3Compatibility testing
Coatings were prepared in a similar manner to example 12, except that the aqueous hydroxyacrylic dispersion Antkote2035 in example 12 was replaced with Antkote2025, Antkote2701 and Antkote2042, respectively, having different hydroxyl numbers (from low to high), respectively, in accordance with the same NCO/OH molar ratio, and then the experiments were carried out in accordance with the method of Experimental example 2, the results of which are shown in Table 6.
TABLE 6 test results of Experimental example 2
As can be seen from Table 6, the highly water-resistant and hydrophilic polyisocyanate curing agent of example 1 has better compatibility in aqueous hydroxyacrylic dispersions of different hydroxyl values, and the final paint film resistance is continuously improved with the continuous increase of the hydroxyl value of the hydroxyacrylic dispersion.
Experimental example 4Effect of Synthesis conditions on Synthesis product Properties
Polyisocyanate curing agents were prepared according to the synthesis conditions in Table 7, then coatings were prepared according to the method of example 12, and the properties of the coatings were tested by the test method in Experimental example 1, and the results are shown in Table 7.
Table 7 experimental example 4 test results
As can be seen from table 7, when the reaction temperature of the butane sultone and the silane coupling agent is 60 ℃ and the reaction time is 10min, and the temperature is maintained at 100 ℃ after the HDI trimer is added, the improvement of the reaction temperature or the extension of the reaction time does not significantly improve the performance of the finally obtained curing agent product, so the preferable scheme is that the reaction temperature of the butane sultone and the silane coupling agent is 60 ℃, the reaction time is 10min, and the reaction and heat preservation temperature after the HDI trimer is added is 100 ℃.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (12)
1. The preparation method of the polyisocyanate curing agent with high water resistance and hydrophilicity is characterized by comprising the following steps: under an inert atmosphere, adding butane sultone into a reaction container, slowly adding a silane coupling agent under stirring at 55-70 ℃, then stirring to continue reacting for 10-30 min, adding an HDI trimer, heating to 90-120 ℃, slowly dropwise adding a neutralizer under stirring to neutralize, keeping the temperature of 90-120 ℃, and continuing reacting until the NCO content is 21-22 wt%, thereby obtaining a high-water-resistant and hydrophilic polyisocyanate curing agent;
the mass ratio of the HDI tripolymer to the butane sultone to the silane coupling agent is 98-95: 1-2.5: 1 to 2.5; the silane coupling agent is selected from gamma-aminopropyl trimethoxy silane KH540 and/or gamma-aminopropyl triethoxy silane KH 550; the neutralizer is N, N-dimethylcyclohexylamine.
2. The highly water-resistant hydrophilic polyisocyanate curing agent according to claim 1, wherein the mass ratio of the butane sultone to the silane coupling agent is 0.8 to 1.2: 1.
3. The highly water-resistant and hydrophilic polyisocyanate curing agent according to claim 2, wherein the mass ratio of the butane sultone to the silane coupling agent is 1: 1.
4. The highly water-resistant and hydrophilic polyisocyanate curing agent according to any one of claims 1 to 3, wherein the neutralization is carried out by dropping a neutralizing agent to a degree of neutralization of 100%.
5. Use of the highly water-resistant and hydrophilic polyisocyanate curing agent according to any one of claims 1 to 4 in the field of metal anticorrosive coatings.
6. Use according to claim 5, in the field of aqueous two-component metal corrosion protection coatings.
7. The water-based double-component metal anticorrosive paint is characterized by comprising a component A and a component B,
the component A comprises: 40-90 parts by weight of aqueous hydroxy acrylic acid dispersoid; 20-50 parts of color paste; 0.5-15 parts by weight of a solvent; 0-20 parts of water; 0.5-5 parts of water-based auxiliary agent;
the component B comprises: 5 to 40 parts by weight of the highly water-resistant and hydrophilic polyisocyanate curing agent according to any one of claims 1 to 4; 0-10 parts of solvent.
8. The aqueous two-component metal corrosion protective coating of claim 7,
the component A comprises: 55-65 parts of aqueous hydroxy acrylic acid dispersoid; 30-35 parts of color paste; 2-8 parts of a solvent; 1-10 parts of water; 1-2 parts of water-based auxiliary agent;
the component B comprises: 10 to 25 parts by weight of the highly water-resistant and hydrophilic polyisocyanate curing agent according to any one of claims 1 to 4; 2-8 parts of solvent.
9. The aqueous two-component metal anticorrosive coating according to claim 7 or 8,
in the component A, the solvent is selected from diethylene glycol butyl ether and/or ethylene glycol butyl ether; and/or the presence of a gas in the gas,
in the component B, the solvent is selected from propylene glycol diacetate and/or propylene glycol methyl ether acetate; and/or the presence of a gas in the gas,
the color paste comprises the following components: 15.0-37.5 parts of titanium dioxide; 0.6 to 1.5 parts by weight of a dispersant; 5.0 to 9.0 weight portions of water; 0.1-0.3 part by weight of defoaming agent; and/or the presence of a gas in the gas,
in the component A, the aqueous auxiliary agent is selected from at least one of the following components: 0-0.5 part of pH regulator; 0.1-1 part by weight of wetting agent; 0.1-1 part by weight of a leveling agent; 0.1 to 1 weight portion of thickening agent.
10. The aqueous two-component metal corrosion protective coating of claim 9,
in the component B, the solvent is selected from propylene glycol methyl ether acetate; and/or the presence of a gas in the gas,
the color paste comprises the following components: 25 parts of titanium dioxide; 1.0 part by weight of a dispersant; 7.0 parts by weight of water; 0.2 part by weight of defoaming agent; and/or the presence of a gas in the gas,
in the component A, the aqueous auxiliary agent is selected from at least one of the following components: 0.1-0.2 weight part of pH regulator; 0.1-0.5 part by weight of wetting agent; 0.2 to 0.5 weight part of flatting agent; 0.2 to 0.4 weight portion of thickening agent.
11. A method for preparing the aqueous two-component metal anticorrosive coating according to any one of claims 7 to 10, characterized by comprising the steps of:
the preparation of the component A comprises the following steps: firstly, preparing color paste, then sequentially adding the selected parts by weight of aqueous hydroxyl acrylic acid dispersoid, solvent, water and aqueous auxiliary agent into the ground color paste under stirring, and stirring until the mixture is uniformly mixed to obtain a component A;
the preparation of component B comprises the following steps: mixing the selected weight parts of solvent and the highly water-resistant and hydrophilic polyisocyanate curing agent according to any one of claims 1 to 4, and uniformly stirring to obtain component B.
12. The production method according to claim 11,
the preparation of the component A comprises the following steps: adding a dispersing agent, titanium dioxide, water, a defoaming agent and a dispersion medium into a container, dispersing to prepare color paste, grinding until the fineness is lower than 10 mu m, then sequentially adding a selected weight part of aqueous hydroxyl acrylic acid dispersoid, a solvent, water and an aqueous auxiliary agent into the ground color paste under stirring, stirring until the mixture is uniformly mixed, and filtering out the dispersion medium to obtain a component A; wherein the dispersion medium is zirconium beads or glass beads.
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