CN116262867A - High-heat-hardness water-based polyester modified organic silicon high-temperature-resistant coating and preparation method thereof - Google Patents
High-heat-hardness water-based polyester modified organic silicon high-temperature-resistant coating and preparation method thereof Download PDFInfo
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- CN116262867A CN116262867A CN202211743950.4A CN202211743950A CN116262867A CN 116262867 A CN116262867 A CN 116262867A CN 202211743950 A CN202211743950 A CN 202211743950A CN 116262867 A CN116262867 A CN 116262867A
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- resistant coating
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- 229920000728 polyester Polymers 0.000 title claims abstract description 66
- 238000000576 coating method Methods 0.000 title claims abstract description 61
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052710 silicon Inorganic materials 0.000 title claims description 43
- 239000010703 silicon Substances 0.000 title claims description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims description 43
- 239000011347 resin Substances 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 30
- 150000003608 titanium Chemical class 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000006184 cosolvent Substances 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical group COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 4
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 16
- 230000007062 hydrolysis Effects 0.000 abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 13
- 238000004140 cleaning Methods 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006150 hyperbranched polyester Polymers 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- 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
- C09D5/18—Fireproof paints including high temperature resistant 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention relates to the field of high polymer materials, and discloses a high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant coating and a preparation method thereof. The nano titanium dioxide particles can protect ester bonds from hydrolysis and oxidation, so that the coating cannot be back-adhered and softened under a heating environment, and still has better hardness; in addition, the nano-titania particles also impart self-cleaning ability to the coating.
Description
Technical Field
The invention relates to the field of new materials, in particular to a high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant coating and a preparation method thereof.
Background
The organic silicon resin takes Si-O bond as main chain, and has better heat resistance because Si-O bond energy is higher (363 kJ/mol) and is relatively stable, so the organic silicon resin is commonly used for preparing high-temperature resistant paint. However, pure silicone resin has the disadvantages of higher curing temperature, longer curing time, poorer mechanical property, adhesive force and organic solvent resistance of a paint film and the like, and generally needs to be modified. The polyester resin is a high polymer prepared by the polycondensation reaction of polybasic acid and polyhydric alcohol, and all the chains are connected by ester groups, so that the polyester resin has good physical and mechanical properties, chemical corrosion resistance and the like. The high-temperature resistant coating taking the polyester modified organic silicon resin as a main film forming material has the advantages of excellent heat resistance, low adhesive force, low surface tension and the like, can be contacted with open fire, can be used for a long time at 230-260 ℃, does not change color after being baked for 1h at 280 ℃, and has been widely applied to the coating of the outer surfaces of various cookers and small household appliances. However, the polyester modified organosilicon high-temperature resistant coating can generate phenomena of back adhesion, softening and the like under high temperature conditions, and the hardness is reduced, so that the wear resistance and mechanical properties of the coating are reduced, and the service life of the coating is influenced.
In addition, the polyester modified organosilicon high temperature resistant coating is still mainly solvent type, and has numerous advantages and market share, but organic volatile matters (VOCs) discharged in production and construction pose a threat to the environment and human health. With the increasing environmental awareness and the increasing sustainable development concept of people, low-VOCs paint is a trend to replace traditional solvent paint, and various large paint enterprises are accelerating the development of environmental protection paint. In the field of high temperature resistant coatings, there is an urgent need to develop aqueous coatings to replace the corresponding solvent-borne products. The water-based paint is a paint which uses water as a solvent or a dispersion medium, and the water replaces an organic solvent in the traditional paint, so that the emission of VOCs is obviously reduced in the production and use processes. The main film forming substance of the water-based high temperature resistant coating, namely the water-based polyester modified organic silicon resin, is still in a research and development stage, and does not enter a large-scale industrial production stage at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-temperature resistant coating of high-heat-hardness water-based polyester modified organosilicon and a preparation method thereof. The invention carries out neutralization salification reaction in situ on the polyester modified organic silicon resin with the water-based group carboxyl end in the water system of the modified titanium sol to obtain the titanium-containing water-based polyester modified organic silicon resin with evenly distributed nano titanium dioxide particles, thereby avoiding the problems of adverse effect of externally added emulsifying agent on the heat resistance of the final cured coating, performance reduction, system instability and the like caused by hydrolysis of ester bonds and hydrolysis self-polymerization of the organic silicon intermediate which is not completely reacted in the resin storage process. The nano titanium dioxide particles can protect ester bonds from hydrolysis and oxidation, so that the coating cannot be back-adhered and softened under a heating environment, and still has better hardness; in addition, the nano-titania particles also impart self-cleaning ability to the coating.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant coating, which is prepared from the following raw materials in parts by weight: 50-80 parts of polyester modified organic silicon resin, 2-6 parts of modified titanium sol, 20-60 parts of high temperature resistant pigment and filler, 1-4 parts of auxiliary agent, 2-4 parts of neutralizer and 30-80 parts of water.
The invention carries out in-situ neutralization salification reaction on the polyester modified organic silicon resin with the water-based group carboxyl end in the water system of the modified titanium sol (the main component is nano titanium dioxide particles), thus obtaining the titanium-containing water-based polyester modified organic silicon resin with uniformly distributed nano titanium dioxide particles, and avoiding the problems of bad influence of externally added emulsifying agent on the heat resistance of the final cured coating, performance reduction, system instability and the like caused by hydrolysis of ester bonds and hydrolysis self-polymerization of the organic silicon intermediate which is not completely reacted in the resin storage process. In addition, when the nano titanium dioxide particles are uniformly distributed in the polyester modified organic silicon resin, the hardness, heat resistance and water resistance of the formed coating can be obviously improved, and the ester bond is protected from hydrolysis and oxidation, so that the coating still has better hardness under a heating environment; meanwhile, the nano titanium dioxide also has excellent ultraviolet shielding, visible light transmittance, antibacterial capability and photocatalytic capability, so that the coating has certain self-cleaning capability.
Preferably, the modified titanium sol comprises the following raw materials in parts by weight: 5-10 parts of titanate, 20-40 parts of cosolvent, 10-20 parts of water, 0.1-0.2 part of acid and 0.5-1 part of silane coupling agent.
Preferably, the preparation method of the modified titanium sol comprises the following steps: putting titanate and 50wt% of cosolvent into a reaction kettle, uniformly mixing, heating to 60-80 ℃, dropwise adding a mixture of water, acid and the other 50wt% of cosolvent, reacting for 1-3h, dropwise adding a silane coupling agent, continuously reacting for 1-2h, and distilling under reduced pressure to remove the cosolvent to obtain the modified titanium sol.
The modified titanium sol is prepared by a sol-gel method, titanate is used as a precursor, and the titanium sol is formed by hydrolytic condensation under the catalysis of acid, titanium dioxide particles prepared by the method are nanoscale, and then the nano titanium dioxide particles are organically modified by a silane coupling agent, so that the compatibility of the nano titanium dioxide particles and polyester modified organic silicon resin is enhanced, and the nano titanium dioxide particles have higher dispersion uniformity and dispersion stability in a system.
Preferably, the titanate is selected from tetrabutyl titanate and tetraisopropyl titanate.
Preferably, the cosolvent is selected from ethanol and isopropanol.
Preferably, the acid is selected from hydrochloric acid and acetic acid.
Preferably, the silane coupling agent is selected from gamma-glycidoxypropyl trimethoxysilane and gamma-glycidoxypropyl triethoxysilane.
Preferably, the polyester modified organic silicon resin comprises the following raw materials in parts by weight: 1-5 parts of dihydric alcohol, 10-20 parts of triol, 10-20 parts of dibasic acid, 12-25 parts of organosilicon intermediate, 3-8 parts of anhydride, 0.0005-0.001 part of catalyst and 10-20 parts of solvent.
The molecular structure of the polyester modified organic silicon resin contains terminal carboxyl groups which can be further neutralized into salt, the water-based coating can be realized without adding an emulsifying agent, and the adverse effect of the emulsifying agent on the heat resistance of the final cured coating is avoided. In addition, the polyester modified organic silicon resin is neutralized and salified when the coating is prepared, so that the problems of performance reduction, system instability and the like caused by hydrolysis of ester bonds and hydrolysis self-polymerization of an organic silicon intermediate which is not completely reacted in the resin storage process are avoided, and the problems of poor construction property and stability of the conventional water-based polyester modified organic silicon resin are solved.
Preferably, the diol is selected from neopentyl glycol, 1, 4-cyclohexanedimethanol, 1, 5-pentanediol.
Preferably, the triol is selected from trimethylol propane and trimethylol ethane.
Preferably, the dibasic acid is selected from isophthalic acid, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid.
Preferably, the organosilicon intermediate is phenyl methyl polysiloxane oligomer, the weight average molecular weight is 500-2000, and the organosilicon intermediate contains 15-18% of methoxy; preferably, the silicone intermediate is selected from KR510 from the company Xinyue, IC232 from the company Wake, DC3074 from the company Dow Corning.
Preferably, the anhydride is selected from trimellitic anhydride and pyromellitic anhydride.
Preferably, the catalyst is selected from aluminum triacetylacetonate, tetrabutyl titanate and sodium metaaluminate.
Preferably, the solvent is selected from dipropylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether acetate.
Preferably, the preparation method of the polyester modified organic silicon resin comprises the following steps: adding dihydric alcohol, triol and dibasic acid into a reaction kettle, heating to 170-190 ℃, preserving heat and esterifying for 1-2h, heating to 210-230 ℃, continuing to react for 2-4h until the acid value is reduced to below 10mgKOH/g, stopping the reaction, cooling to 150-170 ℃, adding solvent and anhydride, continuing to react until the acid value is 60-80mgKOH/g, cooling to 100-120 ℃, adding organosilicon intermediate and catalyst, and reacting for 1-2h until the polyester modified organosilicon resin is transparent.
According to the invention, the hyperbranched polyester is synthesized by taking the triol and the dibasic acid as monomers, and because of the gelation tendency of polymerization between the triol and the dibasic acid, the diol is introduced as a central core to regulate and control the hyperbranched reaction, so that the molecular weight and the molecular weight distribution of a final product are better controlled; and then the end of the polyester is blocked by acid anhydride to obtain carboxyl-hydroxyl terminated hyperbranched polyester, and then the hydroxyl on the hyperbranched polyester and the alkoxy on the organosilicon intermediate are utilized to react to obtain the polyester modified organosilicon resin with carboxyl terminated by water-soluble groups.
Preferably, the high temperature resistant pigment and filler is mixed by any ratio of high temperature resistant pigment and high temperature resistant filler, wherein the pigment is common high temperature resistant pigment in the field, and can be inorganic high temperature resistant pigment such as carbon black, iron oxide red and the like, or organic high temperature resistant pigment such as phthalocyanine green and the like. The filler is a high-temperature-resistant filler commonly used in the field, and can be silicon carbide or aluminum oxide.
Preferably, the auxiliary agent comprises one or more of dispersing agent, leveling agent and defoaming agent; the dispersing agent is selected from UNIQ-690W, BYK-190; the leveling agent is selected from UNIQ-495U, TEGO-450; the defoamer is selected from UNIQ-265W, SURFYNOL-440.
Preferably, the neutralizing agent is selected from triethylamine, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol.
In a second aspect, the invention provides a preparation method of the high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant coating, which specifically comprises the following steps:
(1) And uniformly mixing the high temperature resistant pigment and filler, the auxiliary agent and the water, and grinding to obtain the color paste.
(2) And (3) uniformly mixing the polyester modified organic silicon resin, the modified titanium sol and the neutralizer, shearing and stirring, then adding the mixture into the color paste prepared in the step (1), uniformly mixing, and filtering to obtain the high-heat-hardness water-based polyester modified organic silicon high-temperature-resistant coating.
Compared with the prior art, the invention has the following technical effects:
(1) The polyester modified organic silicon resin is neutralized to form salt when the coating is prepared, so that the problems of performance reduction, system instability and the like caused by hydrolysis of ester bonds and hydrolysis self-polymerization of organic silicon intermediates which do not completely react in the resin storage process are avoided.
(2) According to the invention, the silane coupling agent is used for carrying out organic modification on the nano titanium dioxide particles, so that the compatibility of the nano titanium dioxide particles and polyester modified organic silicon resin is enhanced, and the nano titanium dioxide particles are used as a system to carry out in-situ neutralization salification reaction, so that the nano titanium dioxide can be uniformly distributed in the resin, not only can the ester bond be protected from hydrolysis and oxidization, but also the coating can not be back-adhered and softened under a heating environment, and still has better hardness, and can be endowed with self-cleaning capability; the service life of the coating is prolonged, and the energy conservation and the consumption reduction are facilitated.
(3) The invention prepares the water-based high-temperature-resistant coating by taking the polyester modified organic silicon resin as a main film forming substance, greatly reduces the discharge amount of VOCs, and is an environment-friendly coating.
Detailed Description
The invention is further described below with reference to examples.
General examples
The high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant coating is prepared from the following raw materials in parts by weight:
50-80 parts of polyester modified organic silicon resin, 2-6 parts of modified titanium sol, 20-60 parts of high temperature resistant pigment and filler, 1-4 parts of auxiliary agent, 2-4 parts of neutralizer and 30-80 parts of water.
The high temperature resistant pigment and filler is formed by mixing high temperature resistant pigment and high temperature resistant filler in any ratio, wherein the pigment is common high temperature resistant pigment in the field, and can be inorganic high temperature resistant pigment such as carbon black, iron oxide red and the like, or organic high temperature resistant pigment such as phthalocyanine green and the like. The filler is a high-temperature-resistant filler commonly used in the field, and can be silicon carbide or aluminum oxide. The auxiliary agent comprises one or more of dispersing agent, leveling agent and defoaming agent; the dispersing agent is selected from UNIQ-690W, BYK-190; the leveling agent is selected from UNIQ-495U, TEGO-450; the defoamer is selected from UNIQ-265W, SURFYNOL-440. The neutralizing agent is selected from triethylamine, N-dimethylethanolamine and 2-amino-2-methyl-1-propanol.
The preparation method of the polyester modified organic silicon resin comprises the following steps: adding 1-5 parts by weight of dihydric alcohol, 10-20 parts by weight of triol and 10-20 parts by weight of dibasic acid into a reaction kettle, heating to 170-190 ℃, preserving heat and esterifying for 1-2 hours, heating to 210-230 ℃, continuing to react for 2-4 hours until the acid value is reduced to below 10mgKOH/g, cooling to 150-170 ℃, adding 10-20 parts by weight of solvent and 3-8 parts by weight of anhydride, continuing to react until the acid value is 60-80mgKOH/g, cooling to 100-120 ℃, adding 12-25 parts by weight of organosilicon intermediate and 0.0005-0.001 part by weight of catalyst, and reacting for 1-2 hours until the polyester modified organosilicon resin is transparent.
Wherein the dihydric alcohol is selected from neopentyl glycol, 1, 4-cyclohexanedimethanol and 1, 5-pentanediol. The triol is selected from trimethylol propane and trimethylol ethane. The diacid is selected from isophthalic acid, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid. The silicone intermediate is selected from KR510 from the company Siteover, IC232 from the company Wake, DC3074 from the company Dow Corning. The anhydride is selected from trimellitic anhydride and pyromellitic anhydride. The catalyst is selected from aluminum triacetylacetonate, tetrabutyl titanate and sodium metaaluminate. The solvent is selected from dipropylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol methyl ether acetate.
The preparation method of the modified titanium sol comprises the following steps: adding 5-10 parts by weight of titanate and 10-20 parts by weight of cosolvent into a reaction kettle, uniformly mixing, heating to 60-80 ℃, dropwise adding a mixture of 10-20 parts by weight of water, 0.1-0.2 part by weight of acid and 10-20 parts by weight of cosolvent, reacting for 1-3 hours, dropwise adding 0.5-1 part by weight of silane coupling agent, continuing reacting for 1-2 hours, and distilling under reduced pressure to remove the cosolvent to obtain the modified titanium sol.
Wherein the titanate is selected from tetrabutyl titanate and tetraisopropyl titanate. The cosolvent is selected from ethanol and isopropanol. The acid is selected from hydrochloric acid and acetic acid. The silane coupling agent is selected from gamma-glycidyl ether oxypropyl trimethoxy silane and gamma-glycidyl ether oxypropyl triethoxy silane.
The preparation method of the high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant coating comprises the following steps:
(1) And uniformly mixing the high temperature resistant pigment and filler, the auxiliary agent and the water, and grinding until the fineness is less than or equal to 10 mu m to obtain the color paste.
(2) And (3) uniformly mixing the polyester modified organic silicon resin, the modified titanium sol and the neutralizer, stirring at high speed for 1-3h, adding the mixture into the color paste prepared in the step (1), uniformly mixing, and filtering to obtain the high-heat-hardness water-based polyester modified organic silicon high-temperature-resistant coating.
Preparation of polyester-modified organosilicon
Example 1
Adding 1 part by weight of neopentyl glycol, 10 parts by weight of trimethylolpropane and 10 parts by weight of isophthalic acid into a reaction kettle, heating to 170 ℃, preserving heat and esterifying for 2 hours, heating to 210 ℃, continuing to react for 4 hours until the acid value is reduced to 8.6mgKOH/g, stopping the reaction, cooling to 150 ℃, adding 10 parts by weight of ethylene glycol butyl ether and 3 parts by weight of trimellitic anhydride, continuing to react until the acid value is 69.2mgKOH/g, cooling to 100 ℃, adding 12 parts by weight of organosilicon intermediate DC3074 and 0.0005 part by weight of tetrabutyl titanate, and reacting for 2 hours until the polyester modified organosilicon resin is transparent.
Example 2
Adding 5 parts by weight of 1, 4-cyclohexanedimethanol, 20 parts by weight of trimethylolethane and 20 parts by weight of 1, 4-cyclohexanedicarboxylic acid into a reaction kettle, heating to 190 ℃, preserving heat and esterifying for 1h, heating to 230 ℃ again, continuing to react for 2h until the acid value is reduced to 9.4mgKOH/g, stopping the reaction, cooling to 170 ℃, adding 20 parts by weight of propylene glycol methyl ether acetate and 8 parts by weight of pyromellitic anhydride, continuing to react until the acid value is 71.5mgKOH/g, cooling to 120 ℃, adding 25 parts by weight of organosilicon intermediate IC232 and 0.001 part by weight of aluminum triacetate, and reacting for 1h to transparency to obtain the polyester modified organic silicon resin.
Example 3
2 parts by weight of 1, 5-pentanediol, 15 parts by weight of trimethylolpropane and 18 parts by weight of terephthalic acid are put into a reaction kettle, the temperature is raised to 180 ℃ for heat preservation and esterification for 1.5 hours, then the temperature is raised to 220 ℃, the reaction is continued for 3 hours until the acid value is reduced to 9.5mgKOH/g, the reaction is stopped, the temperature is lowered to 160 ℃, 15 parts by weight of dipropylene glycol methyl ether and 5 parts by weight of trimellitic anhydride are added, the reaction is continued until the acid value is 70.8mgKOH/g, the temperature is lowered to 110 ℃, 20 parts by weight of organosilicon intermediate KR510 and 0.0008 part by weight of sodium metaaluminate are added, and the reaction is continued for 1.5 hours until the reaction is transparent, thus obtaining the polyester modified organosilicon resin.
Modified titanium Sol preparation example
Example 4
Adding 5 parts by weight of tetrabutyl titanate and 10 parts by weight of ethanol into a reaction kettle, uniformly mixing, heating to 60 ℃, dropwise adding a mixture of 10 parts by weight of water, 0.1 part by weight of hydrochloric acid and 10 parts by weight of ethanol, reacting for 3 hours, dropwise adding 0.5 part by weight of gamma-glycidol ether oxypropyl trimethoxysilane, continuing reacting for 2 hours, and distilling under reduced pressure to remove a cosolvent to obtain the modified titanium sol.
Example 5
Adding 10 parts by weight of tetraisopropyl titanate and 20 parts by weight of isopropanol into a reaction kettle, uniformly mixing, heating to 80 ℃, dropwise adding a mixture of 20 parts by weight of water, 0.2 part by weight of acetic acid and 20 parts by weight of isopropanol, reacting for 1h, dropwise adding 1 part by weight of gamma-glycidoxypropyl triethoxysilane, continuing reacting for 1h, and distilling under reduced pressure to remove a cosolvent to obtain the modified titanium sol.
Preparation of coating
Example 6
(1) Uniformly mixing 5 parts by weight of carbon black, 15 parts by weight of silicon carbide, 0.7 part by weight of UNIQ-690W, 0.3 part by weight of UNIQ-495U and 30 parts by weight of water, and grinding until the fineness is less than or equal to 10 mu m to obtain black color paste.
(2) Uniformly mixing 50 parts by weight of the polyester modified organic silicon resin prepared in the embodiment 1, 2 parts by weight of the modified titanium sol prepared in the embodiment 4 and 2 parts by weight of N, N-dimethylethanolamine, stirring for 1h at high speed, adding the mixture into the black color paste prepared in the step (1), uniformly mixing, and filtering to obtain the high-heat-hardness water-based polyester modified organic silicon high-temperature-resistant coating.
Example 7
(1) Uniformly mixing 20 parts by weight of iron oxide red, 40 parts by weight of aluminum oxide, 2 parts by weight of BYK-190, 1 part by weight of TEGO-450, 1 part by weight of UNIQ-265W and 80 parts by weight of water, and grinding until the fineness is less than or equal to 10 mu m to obtain red color paste.
(2) And (2) uniformly mixing 80 parts by weight of the polyester modified organic silicon resin prepared in the example 2, 6 parts by weight of the modified titanium sol prepared in the example 5 and 4 parts by weight of triethylamine, shearing and stirring at a high speed for 3 hours, adding the mixture into the red color paste prepared in the step (1), uniformly mixing, and filtering to obtain the high-heat-hardness water-based polyester modified organic silicon high-temperature-resistant coating.
Example 8
(1) Uniformly mixing 15 parts by weight of phthalocyanine green, 25 parts by weight of alumina, 2 parts by weight of UNIQ-690W, 0.7 part by weight of UNIQ-495U, 0.3 part by weight of SURFYNOL-440 auxiliary agent and 60 parts by weight of water, and grinding until the fineness is less than or equal to 10 mu m to obtain green color paste.
(2) And (2) uniformly mixing 60 parts by weight of the polyester modified organic silicon resin prepared in the example 3, 5 parts by weight of the modified titanium sol prepared in the example 4 and 3 parts by weight of 2-amino-2-methyl-1-propanol, stirring for 2 hours at high speed, adding the mixture into the green color paste prepared in the step (1), uniformly mixing, and filtering to obtain the high-heat-hardness water-based polyester modified organic silicon high-temperature-resistant coating.
Comparative example 1
The difference from example 6 is only that no modified titanium sol was added in step (2), and the remaining steps and materials and compositions were the same as those of example 6.
Comparative example 2
The difference from example 6 is only that the modified titanium sol was not added in step (2), the same parts by weight of unmodified titanium sol was used instead, and the remaining steps and materials and compositions were the same as those of example 6.
Comparative example 3
The only difference from example 6 is that the polyester-modified silicone resin in step (2) was first neutralized with N, N-dimethylethanolamine, water and then added, and the remaining steps and materials and compositions were the same as those in example 6.
Performance testing
The high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant paint prepared in examples 6-8 and the paint prepared in comparative examples 1-3 are respectively coated on an aluminum substrate (the thickness of the coating film is controlled to be 15 mu m), and then the performances of hardness, adhesive force, heat resistance, heat hardness, self-cleaning stain resistance and the like are tested, wherein the hardness test is carried out according to the GB/T6739 rule, and the result is evaluated: paint film scratch; the adhesive force test is carried out according to the specification of GB/T9286, and the interval is 1mm; heat resistance was measured according to the standard of GB/T1735, test conditions: 280 ℃ for 30min, evaluation of the results: the chromatic aberration is less than or equal to 1 and is qualified; hot hardness testing, namely placing the coated substrate in a baking oven at 150 ℃, and then measuring hardness according to GB/T6739; the self-cleaning anti-fouling test is carried out by staining oily pen stains on the coating, then scrubbing, repeating 50 times, and completely scrubbing to be qualified. The test results are shown in Table 1.
Table 1 results of product performance tests for examples 6-8 and comparative examples 1-3:
| hardness of | Adhesion force | Heat resistance | Hot hardness | Self-cleaning anti-fouling property | |
| Example 6 | 3H | Level 0 | Qualified product | 2H | Qualified product |
| Example 7 | 3H | Level 0 | Qualified product | 2H | Qualified product |
| Example 8 | 3H | Level 0 | Qualified product | 2H | Qualified product |
| Comparative example 1 | 2H | Level 0 | Qualified product | B | Failure to pass |
| Comparative example 2 | 3H | Level 1 | Qualified product | B | Failure to pass |
| Comparative example 3 | 3H | Level 0 | Qualified product | H | Failure to pass |
From the comparison of the above data, it can be seen that:
in comparative example 1, the hardness of the aqueous polyester modified organosilicon coating is reduced without adding modified titanium sol, and the better hot hardness cannot be maintained, so that the coating is damaged under a heating environment, and the self-cleaning dirt resistance is not qualified.
Comparative example 2 was added with an unmodified titanium sol, which had poor compatibility with the polyester-modified silicone, uneven coating, decreased adhesion, although the initial hardness was improved, the decrease in hot hardness was significant after heating, and the coating did not have good self-cleaning stain resistance.
The polyester modified silicone resin added in comparative example 3 has been subjected to neutralization to form salt and then to waterborne modification, and then to addition, the nano titanium dioxide particles have limited uniform dispersion therein, and the initial hardness and the hot hardness are still acceptable, but the self-cleaning and anti-fouling properties are not acceptable, and in addition, the storage stability of the polyester modified silicone resin subjected to waterborne modification is not good, which leads to performance degradation.
Compared with comparative examples 1-3, the high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant coating of examples 6-8 can uniformly distribute nano titanium dioxide in resin, can protect ester bonds from hydrolysis and oxidation, can prevent the coating from being sticky back and softening in a heating environment, has better heat hardness, and can endow the coating with self-cleaning capability.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A high-heat-hardness water-based polyester modified organosilicon high-temperature-resistant coating is characterized in that: the material is prepared from the following raw materials in parts by weight:
50-80 parts of polyester modified organic silicon resin,
2-6 parts of modified titanium sol,
20-60 parts of high-temperature resistant pigment and filler,
1-4 parts of an auxiliary agent,
2-4 parts of neutralizing agent,
30-80 parts of water.
2. The aqueous polyester modified silicone high temperature resistant coating of claim 1, wherein: the modified titanium sol comprises the following raw materials in parts by weight: 5-10 parts of titanate, 20-40 parts of cosolvent, 10-20 parts of water, 0.1-0.2 part of acid and 0.5-1 part of silane coupling agent.
3. The aqueous polyester modified silicone high temperature resistant coating of claim 2, wherein: the preparation method of the modified titanium sol comprises the following steps: adding 5-10 parts by weight of titanate and 10-20 parts by weight of cosolvent into a reaction kettle, uniformly mixing, heating, dropwise adding a mixture of 10-20 parts by weight of water, 0.1-0.2 part by weight of acid and 10-20 parts by weight of cosolvent, reacting, dropwise adding 0.5-1 part by weight of silane coupling agent, continuing reacting, and distilling under reduced pressure to remove the cosolvent to obtain the modified titanium sol.
4. The aqueous polyester modified silicone high temperature resistant coating of claim 2 or 3, characterized in that:
the titanate is selected from tetrabutyl titanate and tetraisopropyl titanate;
the silane coupling agent is selected from gamma-glycidyl ether oxypropyl trimethoxy silane and gamma-glycidyl ether oxypropyl triethoxy silane;
the cosolvent is selected from ethanol and isopropanol;
the acid is selected from hydrochloric acid and acetic acid.
5. The aqueous polyester-modified silicone high temperature resistant coating of claim 3, wherein:
the first reaction temperature is 60-80 ℃ and the reaction time is 1-3h;
the reaction was continued for 1-2h.
6. The aqueous polyester modified silicone high temperature resistant coating of claim 1, wherein: the polyester modified organic silicon resin comprises the following raw materials in parts by weight: 1-5 parts of dihydric alcohol, 10-20 parts of triol, 10-20 parts of dibasic acid, 12-25 parts of organosilicon intermediate, 3-8 parts of anhydride, 0.0005-0.001 part of catalyst and 10-20 parts of solvent.
7. The aqueous polyester-modified silicone high temperature resistant coating of claim 6, wherein: the preparation method of the polyester modified organic silicon resin comprises the following steps: adding 1-5 parts by weight of dihydric alcohol, 10-20 parts by weight of triol and 10-20 parts by weight of dibasic acid into a reaction kettle, heating to 170-190 ℃, preserving heat for esterification for 1-2 hours, heating to 210-230 ℃, continuing to react for 2-4 hours until the acid value is lower than 10mgKOH/g, stopping the reaction, cooling to 150-170 ℃, adding 10-20 parts by weight of solvent and 3-8 parts by weight of anhydride, continuing to react until the acid value is 60-80mgKOH/g, cooling to 100-120 ℃, adding 12-25 parts by weight of organosilicon intermediate and 0.0005-0.001 part by weight of catalyst, and reacting for 1-2 hours until the polyester modified organosilicon resin is transparent.
8. The aqueous polyester modified silicone high temperature resistant coating according to claim 6 or 7, wherein:
the dihydric alcohol is selected from neopentyl glycol, 1, 4-cyclohexanedimethanol and 1, 5-pentanediol;
the triol is selected from trimethylol propane and trimethylol ethane;
the dibasic acid is selected from isophthalic acid, terephthalic acid and 1, 4-cyclohexanedicarboxylic acid;
the anhydride is selected from trimellitic anhydride and pyromellitic anhydride;
the organosilicon intermediate is phenyl methyl polysiloxane oligomer, has a weight average molecular weight of 500-2000 and contains 15-18% of methoxy;
the catalyst is selected from aluminum triacetylacetonate, tetrabutyl titanate and sodium metaaluminate;
the solvent is selected from dipropylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol methyl ether acetate.
9. The aqueous polyester modified silicone high temperature resistant coating of claim 1, wherein: the auxiliary agent comprises one or more of dispersing agent, leveling agent and defoaming agent.
10. A method for preparing the aqueous polyester modified organosilicon high temperature resistant coating according to any one of claims 1 to 9, comprising the steps of:
(1) Uniformly mixing the high temperature resistant pigment and filler, the auxiliary agent and the water, and grinding to obtain color paste;
(2) And (3) uniformly mixing the polyester modified organic silicon resin, the modified titanium sol and the neutralizer, shearing and stirring, then adding the mixture into the color paste prepared in the step (1), uniformly mixing, and filtering to obtain the high-heat-hardness water-based polyester modified organic silicon high-temperature-resistant coating.
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