CN113845826B - Two-component water-based paint - Google Patents
Two-component water-based paint Download PDFInfo
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- CN113845826B CN113845826B CN202111381566.XA CN202111381566A CN113845826B CN 113845826 B CN113845826 B CN 113845826B CN 202111381566 A CN202111381566 A CN 202111381566A CN 113845826 B CN113845826 B CN 113845826B
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- polyurea
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003973 paint Substances 0.000 title claims abstract description 41
- 150000002148 esters Chemical class 0.000 claims abstract description 33
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 30
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 24
- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl hydroxyethyl carbonate Chemical compound 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 11
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000013530 defoamer Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 claims description 8
- UOQTVEMFXWKBBS-UHFFFAOYSA-N ethyl 2-hydroxyethyl carbonate Chemical group CCOC(=O)OCCO UOQTVEMFXWKBBS-UHFFFAOYSA-N 0.000 claims description 8
- 229920000608 Polyaspartic Polymers 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- RHDGPGHQFICLKH-UHFFFAOYSA-N anisole propane-1,2-diol Chemical compound CC(O)CO.COC1=CC=CC=C1 RHDGPGHQFICLKH-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 1
- 229920002396 Polyurea Polymers 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000004383 yellowing Methods 0.000 abstract description 5
- 238000005034 decoration Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010276 construction Methods 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000001033 ether group Chemical group 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BBRSEFOSZWEMPE-UHFFFAOYSA-N 2-hydroxyethyl hydrogen carbonate Chemical compound OCCOC(O)=O BBRSEFOSZWEMPE-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- JJRXNONHGBNFSK-UHFFFAOYSA-N 2-hydroxyethyl methyl carbonate Chemical compound COC(=O)OCCO JJRXNONHGBNFSK-UHFFFAOYSA-N 0.000 description 2
- ZGSQMVQJVOJLJX-UHFFFAOYSA-N 2-hydroxyethyl propyl carbonate Chemical compound CCCOC(=O)OCCO ZGSQMVQJVOJLJX-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C09D175/02—Polyureas
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a novel environment-friendly two-component water-based paint, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is (4-6): 1; the component A comprises: the adhesive comprises a hydrophilic modified polyaspartic acid ester resin, a water-based fluorocarbon emulsion, a defoaming agent, a flatting agent, a film-forming assistant and deionized water, wherein the component B comprises a water-based isocyanate curing agent and propylene glycol methyl ether acetate in parts by weight; the two-component aqueous polyurea-fluorocarbon paint disclosed by the invention not only keeps the advantages of the oil-soluble polyurea paint and the oil-soluble fluorocarbon paint in performance, but also is strong in water solubility, safe, nontoxic, environment-friendly and low in reaction activity, is friendly to environment and constructors, greatly prolongs the gel time and the application period, is added with the aqueous fluorocarbon emulsion as a film forming material, further improves the water resistance, yellowing resistance, weather resistance, salt spray resistance and durability of a paint film, provides long-term protection and maintenance of decoration life, and greatly prolongs the service life of the paint film.
Description
Technical Field
The invention belongs to the technical field of coating of high polymer composite material coatings, and particularly relates to a bi-component water-based coating.
Background
Polyurea is a compound generated by reacting an isocyanate-based compound and an amino compound, the polyurea material has the characteristics of low VOC content, high corrosion resistance, durability, high-efficiency construction, wide adaptability and the like, and has wide application prospects in the fields of corrosion protection, material protection and the like.
The polyurea material is subjected to three stages of aromatic polyurea, conventional aliphatic polyurea and novel aliphatic-Polyaspartic Acid Ester (PAEs) polyurea, the aromatic polyurea has the problems of easy yellowing, excessively high reaction speed and the like when being used outdoors, although the aliphatic spray polyurea can prolong the gel time to 30-60s and has better coating performance, a certain difference exists from an ideal state, the PAEs are amino acid (aliphatic secondary amine) containing two secondary amines, the structural characteristic is that amino is in an environment surrounded by spatial coronary steric hindrance, and an ester department plays an inducing role, so the reaction with isocyanate groups of polyisocyanate is slowed down, and the effect of 'speed reduction' is shown.
The PAEs polyurea overcomes the defects of the traditional polyurea, has controllable reaction speed, strong weather resistance and environmental erosion resistance, low-temperature curing, high hardness, high gloss and no yellowing, can be thickly coated, and has wide application prospect in the fields of anticorrosion protection, material protection and the like.
In view of the fact that the current legislation on environmental protection is becoming more and more strict, the development of the water-based nature of traditional coatings is becoming a high trend, the "oil to water" trend has become more and more a consensus in the coatings world. The water-based polyurea material is one of water-based coatings, water is used as a solvent and is uniformly dispersed in the water, and the water-based polyurea has the characteristics of no toxicity, no irritation, no combustibility and the like, so the water-based polyurea is a good environment-friendly material. However, the water-based polyurea coating has the general defect of the water-based coating, namely the mechanical property and stability of the coating, and the performance of the coating is poorer than that of an oil-based coating, and the prior art CN111303368A provides a water-dispersible polyaspartate and a synthetic method thereof, which are mainly prepared from the following raw materials: the polyatomic primary amino compound, the maleic acid ester and the alkyl etherified monohydroxy polyether, and the hydrophilic alkyl etherified polyether group replaces the alkyl group on one or more branched chains on the molecular chain of the polyaspartic acid intermediate product, so that the polarity of polyaspartic acid resin molecules is obviously changed, the hydrophilicity of the polyaspartic acid resin molecules is increased, and the water-based polyaspartic acid ester resin product is prepared; the alkyl etherified monohydroxy polyether used in the method comprises polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol monopropyl ether and polypropylene glycol monobutyl ether, and most preferably triethylene glycol monomethyl ether.
However, after esterification reaction of monohydroxy polyether such as triethylene glycol monomethyl ether, the molecular chain only contains linear chain ether group, and although the linear chain ether group has high hydrophilicity, the steric hindrance effect is small, the reaction activity is single, and as a result, the prepared polyaspartic acid ester has high reaction activity, the gelling time and drying time are short when the reaction activity is high, the pot life is also shortened, and the large-scale construction and use of PAEs polyurea are not facilitated.
Fluorocarbon paint, also known as fluorocarbon coating, refers to a coating product whose resin molecular structure contains fluorine atoms and exists in the form of fluorine-carbon bonds (CF). By virtue of excellent adhesive force, solvent resistance, hardness, chemical resistance and other properties, the fluorocarbon paint is widely applied to various fields such as national defense, buildings, bridges, petrochemical industry and the like. The fluorocarbon paint mainly comprises solvent type fluorocarbon paint and water-based fluorocarbon paint. The fluorocarbon paint on the market mainly takes a solvent type fluorocarbon paint as a main material, but the solvent type fluorocarbon paint contains high Volatile Organic Compounds (VOC), and the organic compounds directly volatilize into the air during construction and cannot be recycled, so that resource waste and environmental pollution are caused.
Disclosure of Invention
The invention provides a novel environment-friendly two-component water-based paint aiming at the defects of the prior art, in particular to a novel environment-friendly two-component water-based polyurea-fluorocarbon paint, which not only keeps the advantages of oil-soluble polyurea paint and oil-based fluorocarbon paint in performance, but also has strong water solubility, safety, no toxicity, environmental friendliness and constructor friendliness, and the polyurea resin has low reaction activity, thereby greatly prolonging the gel time and the application period, greatly improving the constructability and the efficiency, adding water-based fluorocarbon emulsion as a film forming material, further improving the water resistance, yellowing resistance, weather resistance, salt mist resistance and durability of a paint film, providing long-term protection and maintaining the decoration life, and greatly prolonging the service life of the paint film.
In order to achieve the purpose, the invention creatively provides an environment-friendly two-component water-based polyurea-fluorocarbon paint, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 4-6: 1;
the component A comprises the following raw materials in parts by weight:
30-60 parts of hydrophilic modified polyaspartic ester resin
10-20 parts of water-based fluorocarbon emulsion
0.1 to 0.3 portion of defoaming agent
0.1 to 0.5 portion of flatting agent
2-5 parts of film-forming additive
15-30 parts of deionized water
The component B comprises the following raw materials in parts by weight:
25-50 parts of water-based isocyanate curing agent
6-12 parts of propylene glycol methyl ether acetate
The hydrophilic modified polyaspartate is represented by the following structural formula:
Wherein X is of the formula II
Or formula III
，
The hydrophilic modified polyaspartic acid ester resin is prepared by the following steps: (1) respectively weighing aliphatic primary diamine, diethyl maleate and hydroxyethyl alkyl carbonate in a molar ratio of 4-9:8-18: 16-36; (2) slowly dripping diethyl maleate into aliphatic primary diamine, heating to 50-80 ℃ and reacting for 24-48 hours to prepare oily polyaspartic acid prepolymer; (3) and (3) adding hydroxyethyl alkyl carbonate into the product obtained in the step (2), heating to 90-110 ℃, vacuumizing to negative pressure, dehydrating for 2-4 hours, adding one of catalysts tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate, heating to 100 ℃ and 140 ℃, reacting for 4-10 hours, vacuumizing to remove byproducts, cooling to 20-80 ℃, adding deionized water, fully stirring, and filtering to obtain the hydrophilic modified polyaspartic acid ester resin.
The molar ratio of the aliphatic primary diamine to the diethyl maleate to the hydroxyethyl alkyl carbonate is 4-9:8-18:16-36, the molar ratio of the aliphatic primary diamine to the diethyl maleate can ensure that active groups in the three can fully react to form the polyaspartic acid ester with a structure shown in formula I, namely 1 mole of the aliphatic primary diamine and 2 moles of the diethyl maleate react through Michael to form an oil-soluble polyaspartic acid ester prepolymer, then 4 moles of the hydroxyethyl alkyl carbonate and the oily polyaspartic acid ester prepolymer undergo esterification reaction, all lipophilic alkyl groups on the side chain of the prepolymer are replaced by hydrophilic hydroxyethyl alkyl carbonate, and the hydrophilic alkyl groups are different from monohydroxy polyethers such as triethylene glycol monomethyl ether adopted in CN111303368A, and hydrophilic groups in the side chain after grafting by the triethylene glycol monomethyl ether have only ether groups, so that the reaction activity is single and the steric hindrance is small, after the hydroxyethyl alkyl carbonate is subjected to grafting reaction, the hydrophilic group in the structure comprises an ether group and an ester group, the steric hindrance of the ester group is larger than that of the ether group although the hydrophilicity of the ester group is smaller than that of the ether group, and the formed polyaspartic ester is optimally balanced between the hydrophilicity and the steric hindrance by controlling the length of a carbon chain and substituting all alkyl groups of side chains.
R1And R2The direct or branched alkyl group with the same or different carbon atoms can be selected, and the inventor obtains R through repeated experiments according to the steric hindrance effect generated by the chain structure and the influence of the carbon chain length on the hydrophilicity1And R2When the modified polyaspartic acid ester is ethyl (in this case, hydroxyethyl alkyl carbonate is hydroxyethyl ethyl carbonate), the obtained modified polyaspartic acid ester can achieve the best performance indexes of water solubility and reaction activity, and the mechanism is as follows: the longer the carbon chain, the greater the steric hindrance of the polyaspartic ester, the more obvious the steric hindrance effect when the isocyanate group is close to the amino group, resulting in a reduction in reaction rate and a reduction in reaction activity, but the longer the alkyl carbon chain, the poorer the hydrophilicity thereof, resulting in poorer water solubility and water dispersion stability of the polyaspartic ester, which is not conducive to the preparation of a water-based polyaspartic ester and a water-based polyurea coating which can be stably stored and efficiently used.
The reduction of the reactivity enables constructors to determine the composition of PAEs according to conditions such as environmental temperature and the like, thereby effectively mastering the construction rhythm and progress, improving the construction efficiency and saving materials and cost. Through research, the PAEs have moderate reactivity and the polyurea coating prepared from the PAEs has longer gel time when X is represented by a formula II and a formula III, the corresponding aliphatic primary diamine is selected from 3,3 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane when X is represented by the formula II, and the corresponding aliphatic primary diamine is selected from 4,4 ' -diaminodicyclohexylmethane when X is represented by the formula III, particularly the aliphatic primary diamine is selected from 3,3 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane, so that the PAEs have larger steric hindrance, slow reaction speed and low reaction activity, and are most preferable.
The defoamer is a mineral oil defoamer or an organic silicon defoamer, the film-forming assistant is alcohol ester dodeca, ethylene glycol monobutyl ether or propylene glycol anisole, the leveling agent is a modified polysiloxane leveling agent, and the water-based isocyanate curing agent is selected from a Bayer XP2655 curing agent.
The invention further provides a preparation method of the bi-component water-based polyurea-fluorocarbon paint, which comprises the following steps: (1) adding the hydrophilic modified polyaspartic acid ester resin, the defoaming agent, the flatting agent and the deionized water into a reaction kettle, and stirring at the rotating speed of 600-1000r/min for 5-10min to uniformly disperse the resin; (2) uniformly stirring, adding the aqueous fluorocarbon emulsion and the film-forming assistant, stirring at the rotating speed of 800r/min for 5-10min to uniformly disperse, uniformly stirring, and filtering to obtain a component A of the bi-component aqueous polyurea-fluorocarbon paint; (3) and mixing the aqueous isocyanate curing agent and propylene glycol monomethyl ether acetate according to a ratio, uniformly stirring and filtering to obtain a component B of the bi-component aqueous polyurea-fluorocarbon paint.
When the paint is used, the component A and the component B are mixed according to the mass ratio of 4-6: 1, uniformly mixing, diluting with deionized water to proper construction viscosity, spraying on the surface of a base material, and drying at room temperature.
Advantageous effects
According to the invention, aliphatic primary diamine and diethyl maleate react through Michael to form an oil-soluble polyaspartic acid ester prepolymer, then the prepolymer and hydroxyethyl alkyl carbonate, especially hydroxyethyl ethyl carbonate, are subjected to grafting reaction to form waterborne Polyaspartic Acid Ester (PAEs) with reduced reactivity and higher hydrophilicity, and the reactivity of the PAEs is reduced by controlling the spatial structure of the PAEs, so that the prepared polyurea coating has longer gel time and longer pot life, and meanwhile, the high corrosion resistance, hardness and durability of the oil-soluble PAEs polyurea coating can be maintained.
The water-based fluorocarbon emulsion and the formed water-based PAEs polyurea are jointly used as film forming substances, and under the synergistic effect, the water resistance, the yellowing resistance, the weather resistance, the salt spray resistance and the durability of a paint film are further improved by virtue of the excellent adhesive force, solvent resistance, hardness, chemical resistance and other properties of fluorocarbon resin, so that long-term protection is provided, the decoration life is kept, and the service life of the paint film is greatly prolonged.
Detailed Description
Example 1
The two-component water-based polyurea-fluorocarbon paint is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 5: 1;
the component A comprises the following raw materials in parts by weight:
50 parts of hydrophilic modified polyaspartic acid ester resin
15 parts of water-based fluorocarbon emulsion
0.2 portion of organic silicon defoamer
0.3 part of modified polysiloxane flatting agent
Twelve (4) parts of alcohol ester
25 parts of deionized water
The component B comprises the following raw materials in parts by weight:
35 parts of Bayer XP2655 isocyanate curing agent
8 parts of propylene glycol methyl ether acetate
The structural formula of the hydrophilic modified polyaspartic ester is as follows:
wherein R is1And R2Are all ethyl, X is of formula II
。
The hydrophilic modified polyaspartic acid ester resin is prepared by the following steps: (1) respectively weighing 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, diethyl maleate and hydroxyethyl carbonate in a molar ratio of 6:12: 24; (2) slowly dripping diethyl maleate into 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, heating to 60 ℃ and reacting for 24 hours to prepare oily polyaspartic acid ester prepolymer; (3) adding hydroxyethyl ethyl carbonate into the product obtained in the step (2), heating to 100 ℃, vacuumizing to negative pressure of-0.10 MPa, dehydrating for 2 hours, adding tetraethyl titanate, heating to 120 ℃, reacting for 5 hours, vacuumizing to remove byproducts, cooling to 40 ℃, adding deionized water, fully stirring, and filtering to obtain hydrophilic modified polyaspartic acid ester resin;
the preparation method of the bi-component water-based polyurea-fluorocarbon paint comprises the following steps: (1) adding the hydrophilic modified polyaspartic acid ester resin, the defoaming agent, the flatting agent and the deionized water into a reaction kettle, and stirring at the rotating speed of 800r/min for 8min to uniformly disperse the resin; (2) uniformly stirring, adding the aqueous fluorocarbon emulsion and the film-forming assistant, stirring at the rotating speed of 600r/min for 10min to uniformly disperse, uniformly stirring, and filtering to obtain a component A of the bi-component aqueous polyurea-fluorocarbon paint; (3) and mixing the aqueous isocyanate curing agent and propylene glycol monomethyl ether acetate according to a ratio, uniformly stirring and filtering to obtain a component B of the bi-component aqueous polyurea-fluorocarbon paint.
When in use, the component A and the component B are mixed according to the mass ratio of 5: 1, uniformly mixing, diluting with deionized water to proper construction viscosity, spraying on the surface of a base material, and drying at room temperature.
Example 2
Example 2 differs from example 1 in that the same amount of material of 4,4 ' -diaminodicyclohexylmethane was used instead of 3,3 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane, all of which were otherwise identical to example 1.
Example 3
The two-component water-based polyurea-fluorocarbon paint is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 4: 1;
the component A comprises the following raw materials in parts by weight:
30 parts of hydrophilic modified polyaspartic acid ester resin
10 parts of water-based fluorocarbon emulsion
0.1 part of organic silicon defoamer
0.1 part of modified polysiloxane flatting agent
Twelve (2) parts of alcohol ester
15 portions of deionized water
The component B comprises the following raw materials in parts by weight:
25 parts of Bayer XP2655 isocyanate curing agent
6 parts of propylene glycol methyl ether acetate
The others were in accordance with example 1.
Example 4
The two-component water-based polyurea-fluorocarbon paint is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 6: 1;
the component A comprises the following raw materials in parts by weight:
60 parts of hydrophilic modified polyaspartic acid ester resin
20 parts of water-based fluorocarbon emulsion
0.3 portion of organic silicon defoamer
0.5 part of modified polysiloxane flatting agent
Twelve (5) parts of alcohol ester
30 portions of deionized water
The component B comprises the following raw materials in parts by weight:
50 parts of Bayer XP2655 isocyanate curing agent
Propylene glycol methyl ether acetate 12 parts
The others were in accordance with example 1.
Comparative example 1
Comparative example 1 differs from example 1 in that the same amount of hydroxyethyl methyl carbonate was used instead of hydroxyethyl ethyl carbonate, all other things remaining the same as in example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that hydroxyethyl propyl carbonate is used in place of hydroxyethyl ethyl carbonate in the same amount of material, all other things remaining in accordance with example 1.
Comparative example 3
Comparative example 3 differs from example 1 in that triethylene glycol monomethyl ether was used in the same amount as the hydroxyethyl carbonate in place of the hydroxyethyl carbonate, all other things remaining in agreement with example 1.
Comparative example 4
Comparative example 4 differs from example 1 in that no aqueous fluorocarbon emulsion was added, and otherwise remains the same as example 1.
Table 1 shows the reactivity of PAEs with Bayer XP2655 and the water solubility of PAEs, which is different from the test performance in Table 1 of the same-day application of the invention, namely 'an environment-friendly antibacterial polyurea coating', so that the data are not comparable.
TABLE 1
As can be seen from table 1, PAEs prepared by using 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane as aliphatic primary diamine and hydrophilic modified PAEs obtained by grafting PAEs with hydroxyethyl ethyl carbonate can reach the best in both the comprehensive performance indexes of reactivity and water solubility (see example 1, gel time is 50min, water solubility is 70 g), the lower the reactivity is, the slower the reaction rate is, the longer the gel time is, the longer the pot life is, the longer the operation time can be ensured, and the construction is facilitated; example 2 PAEs were prepared using 4, 4' -diaminodicyclohexylmethane as the aliphatic primary diamine, with reduced steric hindrance, resulting in shorter gel times than example 1, but with improved water solubility (25 ℃, 75 g); in the comparative example 1, hydroxyethyl methyl carbonate is adopted for grafting reaction, carbon chains in four branched chains in PAEs are all shortened, the steric hindrance is greatly reduced, the cross-linking reaction with isocyanate is accelerated, the gelation time is greatly shortened (20 min), although the water solubility is improved to a certain extent (25 ℃, 78 g), the application period is too short, and the effective construction and use cannot be realized; comparative example 2 adopts hydroxyethyl propyl carbonate for grafting reaction, the length of carbon chain in branched chain in PAEs is increased, steric hindrance is aggravated to a certain extent, and the gelation time is prolonged, but the water solubility is greatly reduced (25 ℃, 40 g), which is not beneficial to the storage stability of PAEs and the water dispersion stability and the service performance of the prepared PAEs polyurea resin; comparative example 3 adopts triethylene glycol monomethyl ether to carry out grafting reaction on PAE, and the hydrophilic group in the grafted PAEs side chain only has an ether group, so that the reaction activity is single, the steric hindrance is small, the gelation time is shortened compared with that of example 1, and although the water solubility is good, the construction requirement cannot be better met. From the above examples and comparative examples, it can be determined that hydroxyethyl ethyl carbonate is the best graft modifier.
The performance properties of the examples and comparative example 4 are shown in table 2, test standards: GB/T22374 and 2018.
TABLE 2
As shown in Table 2, the film coating performance of the two-component aqueous polyurea-fluorocarbon paint prepared by the method maintains the main characteristics of the solvent-based polyurea paint and the solvent-based fluorocarbon paint, and has the performances of room temperature curing, excellent water resistance, alkali resistance, salt mist resistance, artificial weather aging resistance, washing resistance, high mechanical strength and the like. From the test results of the comparative example 4, when the aqueous fluorocarbon emulsion is not added, the water resistance, alkali resistance, salt spray resistance, artificial weather aging resistance and washing resistance of the coating are reduced compared with those of the coating in the example 1, so that the addition of the aqueous fluorocarbon emulsion can provide long-term protection for the coating, maintain the decoration life and greatly prolong the service life of a paint film, and the aqueous fluorocarbon emulsion and the aqueous PAEs polyurea are jointly used as film forming substances, have a synergistic effect and are all indispensable.
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 (9)
1. The two-component water-based paint is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is (4-6): 1;
the component A comprises the following raw materials in parts by weight:
30-60 parts of hydrophilic modified polyaspartic ester resin;
10-20 parts of water-based fluorocarbon emulsion;
0.1-0.3 part of defoaming agent;
0.1-0.5 part of leveling agent;
2-5 parts of a film-forming assistant;
15-30 parts of deionized water;
the component B comprises the following raw materials in parts by weight:
25-50 parts of a water-based isocyanate curing agent;
6-12 parts of propylene glycol methyl ether acetate;
the hydrophilic modified polyaspartate is represented by the following structural formula:
Wherein X is of the formula II
Or formula III
， R1And R2Are all selected from ethyl.
2. The two-component aqueous coating composition of claim 1, wherein X is
。
3. The two-component waterborne coating of claim 1, wherein the hydrophilically modified polyaspartate resin is prepared by the steps of: (1) respectively weighing aliphatic primary diamine, diethyl maleate and hydroxyethyl alkyl carbonate; (2) slowly dripping diethyl maleate into aliphatic primary diamine, heating to 50-80 ℃ and reacting for 24-48 hours to prepare oily polyaspartic acid ester prepolymer; (3) adding hydroxyethyl alkyl carbonate into the product obtained in the step (2), heating to 90-110 ℃, vacuumizing to negative pressure, dehydrating for 2-4 hours, adding a catalyst, heating to 100 ℃ and 140 ℃, reacting for 4-10 hours, vacuumizing to remove byproducts, cooling to 20-80 ℃, adding deionized water, fully stirring, and filtering to obtain the hydrophilic modified polyaspartic acid ester resin.
4. The two-component waterborne coating of claim 3, wherein the alkyl hydroxyethyl carbonate is ethyl hydroxyethyl carbonate.
5. The two-component waterborne coating of claim 3, wherein the molar ratio of the aliphatic primary diamine, diethyl maleate, and alkyl hydroxyethyl carbonate is from 4-9:8 to 18:16 to 36.
6. The two-component waterborne coating of claim 3, wherein the aliphatic primary diamine is selected from the group consisting of 3,3 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane and 4,4 ' -diaminodicyclohexylmethane; the catalyst is one of tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate.
7. The two-component waterborne coating of claim 6, wherein the aliphatic primary diamine is selected from the group consisting of 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane.
8. The two-component water-based paint according to claim 1, wherein the defoamer is a mineral oil defoamer or an organic silicon defoamer, the film-forming assistant is alcohol ester dodeca, ethylene glycol monobutyl ether or propylene glycol anisole, and the leveling agent is a modified polysiloxane leveling agent.
9. The two-component waterborne coating of claim 1, wherein the waterborne isocyanate curing agent is selected from the group consisting of bayer XP2655 curing agents.
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| JP2008231188A (en) * | 2007-03-19 | 2008-10-02 | Dic Corp | One-pack type aqueous coating agent, method for producing the same, and painted product |
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| JP2008231188A (en) * | 2007-03-19 | 2008-10-02 | Dic Corp | One-pack type aqueous coating agent, method for producing the same, and painted product |
| CN101817924A (en) * | 2010-03-19 | 2010-09-01 | 上海市建筑科学研究院(集团)有限公司 | Method for preparing novel polyaspartic ester and application thereof |
| DE102014214130A1 (en) * | 2014-07-21 | 2016-01-21 | Evonik Degussa Gmbh | Highly reactive uretdione-containing polyurethane compositions containing carbonate salts |
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