CN114989707A - Polyurea coating - Google Patents
Polyurea coating Download PDFInfo
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- CN114989707A CN114989707A CN202210199483.7A CN202210199483A CN114989707A CN 114989707 A CN114989707 A CN 114989707A CN 202210199483 A CN202210199483 A CN 202210199483A CN 114989707 A CN114989707 A CN 114989707A
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- component
- coating
- silicone oil
- polyurea coating
- polyurea
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- 238000000576 coating method Methods 0.000 title claims abstract description 211
- 239000011248 coating agent Substances 0.000 title claims abstract description 170
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 144
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 47
- 239000000049 pigment Substances 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 24
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 20
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013638 trimer Substances 0.000 claims abstract description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 41
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 33
- 229920002545 silicone oil Polymers 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- -1 silicon oxide tricarbamate Chemical compound 0.000 claims description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 claims description 10
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000001052 yellow pigment Substances 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- JLATXDOZXBEBJX-UHFFFAOYSA-N cadmium(2+);selenium(2-);sulfide Chemical compound [S-2].[Se-2].[Cd+2].[Cd+2] JLATXDOZXBEBJX-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920013822 aminosilicone Polymers 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 125000005504 styryl group Chemical group 0.000 claims description 6
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 229940057995 liquid paraffin Drugs 0.000 claims description 5
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 4
- KOVAQMSVARJMPH-UHFFFAOYSA-N 4-methoxybutan-1-ol Chemical compound COCCCCO KOVAQMSVARJMPH-UHFFFAOYSA-N 0.000 claims description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- SRKRSWKCLVMJRZ-UHFFFAOYSA-N [S-2].S.[SeH2].[Cd+2] Chemical compound [S-2].S.[SeH2].[Cd+2] SRKRSWKCLVMJRZ-UHFFFAOYSA-N 0.000 claims 2
- 230000007797 corrosion Effects 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 18
- 238000009472 formulation Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 15
- 239000003973 paint Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 235000010215 titanium dioxide Nutrition 0.000 description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 239000004970 Chain extender Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000001066 destructive effect Effects 0.000 description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910021487 silica fume Inorganic materials 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 102100035474 DNA polymerase kappa Human genes 0.000 description 2
- 101710108091 DNA polymerase kappa Proteins 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920000608 Polyaspartic Polymers 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920000162 poly(ureaurethane) Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
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
- 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
-
- 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
Abstract
The present invention provides a polyurea coating comprising: diisocyanate trimer, 12-14 wt%; component A solvent 2-4 wt%; 8-14 wt% of polyaspartic acid ester; 1-3% by weight of an HDI trimer type urethane component; a silica-based inorganic powder having a fineness of 200 mesh or more, more than 45% by weight; 15-25 wt% of pigment; 2-8 wt% of a plasticizer; component B solvent 2-8 wt%. The present invention also provides another polyurea coating comprising: diisocyanate trimer, 12-14 wt%; 10-30 wt% of component A solvent; 8-14 wt% of polyaspartic acid ester; 1-3 wt% of HDI trimeric urethane component; 0 to 55% by weight of a silica-based inorganic powder having a fineness of 200 mesh or more; 0-55% of pigment; 0-8 wt% of a plasticizer; component B solvent 10-40 wt%.
Description
Technical Field
The invention belongs to the field of polyurea coatings. In particular, the present invention relates to a polyurea coating, more particularly, the present invention relates to a slow polyurea coating.
Background
Polyurea coatings have been widely used in many fields such as the automotive industry, the marine industry, the construction industry, etc. due to the advantages of fast curing, high solid content, moisture resistance, excellent physical and chemical properties, etc. However, with the expansion of application scenes, the popularization and application of polyurea coatings are gradually influenced by the fast curing reaction.
In the case of a conventional polyurea coating, such as spray polyurea elastomer (SPUA), the gel time is about 5 seconds, so that the wetting property to a substrate is poor due to factors such as concentrated heat release, and the like, thereby causing the problems of adhesion reduction, poor interlayer bonding, appearance problems such as "orange peel" and "pinholes". In addition, spray polyurea elastomers (SPUA) are typically coated with polyurea coatings using high temperature, high pressure, impingement mixing equipment, which is expensive, bulky and not suitable for small area repairs.
Polyurea coatings having a gel time greater than 1 hour are now commonly referred to in the industry as slow-reacting polyurea coatings (also referred to simply as slow polyureas). Reducing the reaction rate of polyurea systems is currently a major concern in roughly two ways: on one hand, a novel chain extender is adopted, and on the other hand, a novel prepolymer is adopted. However, despite attempts to use improved prepolymers, the gel time of the polyureas did not exceed 30 minutes. The presence of polyaspartic esters for the chain extender extends the gel time of the polyurea to tens of minutes.
With many years of development and research, the gel time of polyurea coatings can be prolonged to one hour by adopting polyaspartic acid ester as a chain extender, and a low-solid content polyurea coating can reach 2 hours by some reports. However, there has been no report on the use of polyaspartic acid esters to increase the gel time of polyurea coatings to more than one hour for polyurea coatings having a high solids content.
Although the gel time of polyurea coatings with higher solid content is close to one hour, compared with the traditional coating process, the problems of complicated equipment (special equipment is needed), complex operation and insufficient operation time exist during the anticorrosion coating process.
Therefore, the invention provides a novel polyurea coating and a preparation method thereof, and further solves some key technical problems existing in the field.
Disclosure of Invention
In a first aspect of the invention, there is provided a polyurea coating comprising or consisting of:
wherein the polyaspartic acid ester has a structure represented by the following formula 1:
in the general formula 1, R is C 1-4 Straight or branched chain alkyl, X is C 1-15 An alkylene group;
the HDI trimer type carbamate component is carbamate generated by HDI trimer and monohydroxy compounds, and is selected from one or more of methyl octadecyl triurea tricarbamate, diethylene glycol ethyl ester octadecyl triurea tricarbamate, dipropylene glycol monomethyl ether octadecyl triurea tricarbamate, 1, 4-butanediol methyl ether octadecyl triurea tricarbamate, siloxane ester octadecyl triurea tricarbamate and combinations thereof;
the diisocyanate trimer has a structure represented by the following general formula 2:
in the general formula 2, R is C 3-10 A straight-chain alkylene group having a linear alkylene group,
the component A solvent is selected from acetone, ethyl acetate, dipropylene glycol dimethyl ether, and combinations thereof,
the ethyl component solvent is selected from ethanol, methylal, ethyl acetate, dipropylene glycol dimethyl ether, N-methyl pyrrolidone and components thereof,
wherein the weight% is based on the weight of the polyurea coating.
In one embodiment, the pigment is selected from the group consisting of titanium dioxide based pigments, carbon based pigments, iron oxide based pigments, cadmium selenide sulfide based red yellow pigments, lead chromate based yellow pigments, ultramarine pigments. In another embodiment, the pigment is selected from the group consisting of titanium dioxide, carbon black, iron oxide red, cadmium selenide sulfide, lead chromate, ultramarine.
In one embodiment, in formula 1, R is ethyl and X is a structure represented by the following formula 3:
in one embodiment, in formula 2, R is hexylene.
In one embodiment, the component a solvent is acetone, dipropylene glycol dimethyl ether, ethyl acetate, or combinations thereof, 3.23 wt%. In another embodiment, the ethyl component solvent is 3.23 wt% ethanol, 2.77 wt% methylal, or 2-4 wt% of a mixture of one or more selected from ethyl acetate, dipropylene glycol dibenzoate, and N-methylpyrrolidone in any proportion. In still another embodiment, the component B solvent is one or more selected from the group consisting of ethyl acetate, dipropylene glycol dimethyl ether and N-methylpyrrolidone in an arbitrary proportion, 2 to 4% by weight.
In one embodiment, the HDI trimer type urethane component is octadecyltribusiumyl isocyanurate. In another embodiment, the silica-based inorganic powder is a silica-based inorganic powder having a fineness of 200-2000 mesh, a nano-sized silica-based inorganic powder, or a combination thereof. In yet another embodiment, the silica-based inorganic powder is selected from the group consisting of silica fume, glass beads, glass powder, silica white, silica sand, and combinations thereof. In another embodiment, the inorganic powder is present in an amount of at least 45.20 wt.%.
In one embodiment, the plasticizer is a silicone resin, liquid paraffin, dipropylene glycol dibenzoate, or a combination thereof. In another embodiment, the silicone resin comprises: one or more of methyl silicone oil, hydroxyl silicone oil, amino silicone oil, alkyl modified silicone oil, styryl modified silicone oil, polyether modified silicone oil, polyester modified silicone oil or the combination thereof.
In a second aspect of the invention, there is provided another polyurea coating comprising or consisting of the following components:
wherein the polyaspartic acid ester has a structure represented by the following formula 1:
in the general formula 1, R is C 1-4 Straight or branched chain alkyl, X is C 1-15 An alkylene group;
the HDI trimer type carbamate component is carbamate generated by HDI trimer and monohydroxy compounds, and is selected from one or more of methyl octadecyl triurea tricarbamate, diethylene glycol ethyl ester octadecyl triurea tricarbamate, dipropylene glycol monomethyl ether octadecyl triurea tricarbamate, 1, 4-butanediol methyl ether octadecyl triurea tricarbamate, siloxane ester octadecyl triurea tricarbamate and combinations thereof;
the diisocyanate trimer has a structure represented by the following general formula 2:
in the general formula 2, R is C 3-10 A linear alkylene group,
the component A solvent is selected from acetone, ethyl acetate, dipropylene glycol dimethyl ether, and combinations thereof,
the component B solvent is selected from ethanol, methylal, ethyl acetate, dipropylene glycol dimethyl ether, N-methylpyrrolidone and components thereof,
wherein the weight% is based on the weight of the polyurea coating and the total weight of the inorganic powder and the pigment is not less than 55 weight%.
In one embodiment, the pigment is selected from the group consisting of titanium dioxide based pigments, carbon based pigments, iron oxide based pigments, cadmium selenide sulfide based red yellow pigments, lead chromate based yellow pigments, ultramarine pigments. In another embodiment, the pigment is selected from the group consisting of titanium dioxide, carbon black, iron oxide red, cadmium selenide sulfide, lead chromate, ultramarine.
In one embodiment, in formula 1, R is ethyl and X is a structure represented by the following formula 3:
in one embodiment, in formula 2, R is hexylene.
In one embodiment, the ethyl component solvent is ethanol, methylal, or a mixture of one or more selected from ethyl acetate, dipropylene glycol dimethyl ether and N-methylpyrrolidone in any proportion. In another embodiment, the ethyl component solvent is a mixture of ethanol, methylal, and one or more selected from ethyl acetate, dipropylene glycol dimethyl ether, and N-methylpyrrolidone in any proportion.
In one embodiment, the HDI trimer type urethane component is octadecyltrimethylurea trisiloxanecarbamate. In another embodiment, the silica-based inorganic powder is a silica-based inorganic powder having a fineness of 200-2000 mesh, a nano-sized silica-based inorganic powder, or a combination thereof. In yet another embodiment, the silica-based inorganic powder is selected from the group consisting of silica fume, glass beads, glass powder, silica white, silica sand, and combinations thereof.
In one embodiment, the plasticizer is a silicone, liquid paraffin, dipropylene glycol dibenzoate, or a combination thereof. In another embodiment, the silicone resin comprises: methyl silicone oil, hydroxyl silicone oil, amino silicone oil, alkyl modified silicone oil, styryl modified silicone oil, polyether modified silicone oil, polyester modified silicone oil or any combination of one or more of the methyl silicone oil, the hydroxyl silicone oil, the amino silicone oil, the alkyl modified silicone oil, the styryl modified silicone oil, the polyether modified silicone oil and the polyester modified silicone oil.
Drawings
The accompanying drawings are provided below to further describe embodiments of the present invention and effects thereof, but are only for the purpose of better understanding the disclosure of the present invention by those skilled in the art, and are not intended to limit the scope of the present invention.
FIG. 1 is a graph of the resistance moduli of four different coatings against simulated seawater time, wherein (a) of FIG. 1 is a graph of the four coatings and (b) of FIG. 1 is an enlarged illustration of the curve marked by a circle in (a) of FIG. 1; and
fig. 2 is a photograph of corrosion conditions of the surface of a working electrode coated with four different paints, wherein (a) of fig. 2 is the corrosion conditions of a working electrode coated with an epoxy paint, (b) of fig. 2 is the corrosion conditions of a working electrode coated with acrylic urethane, (c) of fig. 2 is the corrosion conditions of a working electrode coated with polyester, and (d) of fig. 2 is the corrosion conditions of a working electrode coated with polyurea according to the present invention.
Detailed Description
Hereinafter, the present invention will be further illustrated according to specific embodiments. However, the specific embodiments are set forth for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those of skill in the art that a particular feature presented in any of the embodiments below may be used in any other embodiment or may be combined with other particular features in other embodiments without departing from the spirit of the invention.
General definitions
The technical terms given herein may be interpreted using the definitions set out below, and, if not explicitly stated, may also be interpreted using the ordinary meaning in the art. The definitions given herein control when the definitions set forth below are contrary to the ordinary meaning in the art.
As used herein, polyurea coating refers to a coating having a polyamine content greater than 80% of the main chain of the film-forming resin of the coating, wherein the main chain of the resin is a urea group-containing compound.
In this context, a slow polyurea coating is a coating which has a gel time of longer than 1 hour at ambient temperature (25. + -. 0.2 ℃). Herein, the curing of the polyurea coating is mainly achieved by a crosslinking reaction of the curing agent with the chain extender.
As used herein, a high solids coating is defined as: a coating having a film-forming solids content of greater than 75% by weight in the coating.
As used herein, a low viscosity coating is defined as: the viscosity of the coating is measured at a temperature of 25. + -. 0.2 ℃ using a paint-4 viscometer according to the measurement method specified in GB1723-79, and when the viscosity reaches 20-30 seconds, the coating can be regarded as a low-viscosity coating. In short, the viscosity of the coating can be measured by the following method: during measurement, the viscometer is adjusted to be in a horizontal state at the temperature of 25 +/-0.2 ℃, a 150ml beaker is placed under the viscometer, a ball valve is used for blocking a leakage nozzle hole, the viscometer is filled with coating, then the coating flows out, a stopwatch is started to time at the same time until the flowing wire of the coating is interrupted, the time is stopped immediately, the time is the conditional viscosity of the glue solution, the measurement is repeated three times, and the error is not more than 3 percent of the average value.
As used herein, alkyl refers to a monovalent group of a saturated aliphatic hydrocarbon that is straight, branched, or cyclic, or a combination thereof, while alkylene refers to a divalent group of a saturated aliphatic hydrocarbon that is straight, branched, or cyclic, or a combination thereof. C number as used in the description of alkyl or alkylene 1-15 It is to be construed that the group contains 1 to 15 carbon atoms, or any number in the range of 1 to 15 carbon atoms, for example 3, 5, 10 carbon atoms. Other carbon number (e.g. C) 1-4 ) And may be interpreted identically. Examples of alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl and the like.
In this context, the temperature is not particularly limited, and all means that the operation is carried out at ambient temperature (25. + -. 0.2 ℃ C.).
Polyurea coating
In one embodiment, the polyurea coating comprises or consists of the following components:
in one embodiment, the polyaspartic acid ester has a structure represented by the following formula 1:
in the general formula 1, R is C 1-4 Straight or branched chain alkyl, X is C 1-15 An alkylene group. In another embodiment, R can be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and the like. In yet another embodiment, X is a linear alkylene group having a total carbon number of 15 or less, a branched alkylene group, a cyclic alkylene group, or a combination thereof, such as a methyl group or an ethyl group substituted with an alkanyl group or a cycloalkyl group. In further embodiments, the polyaspartic acid urethane is present in an amount of 8, 10, 12, or 14 weight percent, wherein weight percent is based on the weight of the polyurea coating. In one embodiment, in formula 1, X is a structure represented by the following formula 3:
in one embodiment, the HDI trimeric urethane component can be selected from one or more of methyl octadecamethylene triurea tricarbamate, diethylene glycol ethyl octadecamethylene triurea tricarbamate, dipropylene glycol monomethyl ether octadecamethylene triurea tricarbamate, 1, 4-butanediol methyl ether octadecamethylene triurea tricarbamate, silicone octadecamethylene triurea tricarbamate, and combinations thereof. In another embodiment, the HDI trimeric urethane component can be present in an amount of 1 to 3 percent by weight, such as 1 percent by weight, 2 percent by weight, or 3 percent by weight, with each percent by weight being based on the weight of the polyurea coating. In one embodiment, the HDI trimer type urethane component is octadecyltrimethylarbamide siloxane tricarbamate. The adoption of the octadecyl triurea tricarbamate siloxane ester can effectively improve the compatibility of all components of the coating and prevent the surface shrinkage of the coating.
The molecular formula and the synthetic process of the octadecamethylene triurea tricarbamate are shown as follows:
the molecular formula and the synthetic process of the octadecyl triurea triscarbamic acid siloxane ester are shown as follows:
wherein n is 1 to 5
The molecular formula and the synthetic process of the octadecamethylene triurea tricarbamic acid diethylene glycol ethyl ether ester are as follows:
the molecular formula and the synthetic process of the octadecamethylene triurea tricarbamic acid dipropylene glycol monomethyl ether ester are shown as follows:
the molecular formula and the synthetic process of the octadecamethylene triurea tricarbamate 1, 4-butanediol methyl ether ester are shown as follows:
in one embodiment, the diisocyanate trimer has a structure represented by the following formula 2:
in the general formula 2, R is C 3-10 Straight chain alkylene groups such as propylene, butylene, hexylene, and the like.
In yet another embodiment, in formula 2, R is hexylene. In another embodiment, the diisocyanate trimer is present in an amount of 12 wt.%, 13 wt.%, or 14 wt.%, wherein the wt.% are based on the weight of the polyurea coating.
The inventor of the present application finds that the reaction kinetics of the polyaspartic acid polyurea is greatly influenced by the concentration through the chemical reaction kinetics analysis of the polyaspartic acid polyurea. According to the characteristics, the slow polyurea coating with the gel time of more than three hours is obtained by selecting the concentrations of the polyaspartic acid ester chain extender and the isocyanate component and the specific proportion of the polyaspartic acid ester chain extender and the isocyanate component to other components, and meanwhile, the slow polyurea coating can keep higher solid content and lower viscosity.
As shown in the following examples, such formulations were found to provide gel times of at least 3-5 hours for polyurea coatings during specific operations, and if diluents are added, coating operations longer than 24 hours can be achieved while maintaining the coating results. At present, in the field experiment process, the coating operation time can exceed 3 days without influencing the coating effect obviously.
In one embodiment, the component A solvent may be selected from the group consisting of acetone, ethyl acetate, dipropylene glycol dimethyl ether, and combinations thereof. In another embodiment, the component (B) solvent may be selected from the group consisting of ethanol, methylal, ethyl acetate, dipropylene glycol dimethyl ether, N-methylpyrrolidone, and components thereof. In one embodiment, the ethyl component solvent is 3.23 wt% ethanol and 2.77 wt% methylal. In another embodiment, the ethyl component solvent is 3.23% by weight ethanol, 2.77% by weight methylal, and 2-4% by weight mixture of one or more selected from ethyl acetate, dipropylene glycol dimethyl ether, and N-methylpyrrolidone in any proportion.
In one embodiment, the pigment is selected from the group consisting of titanium dioxide based pigments, carbon based pigments, iron oxide based pigments, cadmium selenide sulfide based red yellow pigments, lead chromate based yellow pigments, ultramarine blue based pigments. In another embodiment, the pigment is selected from the group consisting of titanium dioxide, carbon black, iron oxide red, cadmium selenide sulfide, lead chromate, ultramarine. In one embodiment, the pigment may be present in an amount of 15 to 25 weight percent, such as 18 weight percent, 20 weight percent, 22 weight percent, and the like.
In another embodiment, the silica-based inorganic powder is a silica-based inorganic powder having a fineness of 200-2000 mesh, a nano-sized silica-based inorganic powder, or a combination thereof. In yet another embodiment, the silica-based inorganic powder is selected from the group consisting of silica fume, glass beads, glass powder, white carbon, quartz sand, and combinations thereof. In another embodiment, the inorganic powder is present in an amount of at least 45.20 wt.%. The polyurea coating of the invention can contain higher solid content, and simultaneously, the polyurea coating can keep lower viscosity and longer gel time.
The inventors of the present invention have found that silica-based inorganic powder can provide a good effect in prolonging the gel time, however, it should be noted that the water content of the inorganic powder is less than 0.5%, otherwise the inorganic powder is not uniformly dispersed, and small particle-like defects may be generated on the surface of the coating, which may affect the gloss of the coating surface. With the polyurea coating according to the invention, the above inorganic powder can be used to a solids content of more than 70% by weight, even more than 90% by weight, for example up to 90.77% by weight in the polyurea coating of the above formulation. The polyurea coating of the above formulation is an environment-friendly high-solid coating which contains little solvent component, has little volatile matter during actual operation, and can also meet the requirement for high solid content.
In one embodiment, the plasticizer is a silicone resin, liquid paraffin, dipropylene glycol dibenzoate, or a combination thereof. In another embodiment, the silicone resin comprises: one or more of methyl silicone oil, hydroxyl silicone oil, amino silicone oil, alkyl modified silicone oil, styryl modified silicone oil, polyether modified silicone oil, polyester modified silicone oil or the combination thereof. Through the matching of the plasticizer and the solvent, the viscosity of the polyurea coating can be effectively reduced, so that the polyurea coating can be coated by adopting conventional equipment and a conventional coating process, the complex special equipment is avoided, the operation cost can be greatly reduced, and the polyurea coating can be applied to more scenes, particularly small-area coating sites.
In the above polyurea coatings, other solvents disclosed herein may also be selected depending on the actual application of the polyurea coating. For example, when the temperature of the use environment is higher than 60 ℃, dipropylene glycol dimethyl ether (component A) and diethylene glycol monoethyl ether (component B) can be selected; if the odor purification requirement is met, diethylene glycol dimethyl ether (a component A and a component B) can be selected and used, but the superficial drying speed and the solid drying speed are slow; when the concrete base surface is used as a base coat, dipropylene glycol dimethyl ether (component B), chlorinated paraffin (component B), N-methylpyrrolidone (component B) or tetrachloroethylene (component A) can be selected and used. Further, if raw materials such as acetone and methylal are not easily available, ethyl acetate (component A and component B) may be used as an alternative, but it is desirable to avoid use in an environment where a clear taste is required because of its strong taste.
In the polyurea coatings described above, the polyamine content in the main chain of the coating film-forming resin is close to 100%, thus meeting the relevant specifications for polyurea coatings, for example, the classification and definition by the american polyurea development society for polyurea and polyurethane coatings: when the polyamine content in the system is more than 80%, the material is called polyurea coating; when the content of the polyol in the system is more than 80 percent, the material is called polyurethane coating; and when the content of polyamine and polyalcohol in the system is between the two, the materials are collectively called polyurea/polyurethane hybrid or mixture.
The polyurea coatings provided herein can still achieve a viscosity of 20-30 seconds (measured as described above using a coat-4 viscometer) at high solids content. In practice, the polyurea coatings provided herein have a gel time of greater than 3 hours and a paint application time of greater than 1 hour (typically 1-3 hours, i.e., during which time conventional paint equipment and conventional paint process operations may be employed), such as if diluted with a diluent (e.g., ethanol) (e.g., diluted at a rate of plus one-fifteenth of the diluent per hour), the paint application time may be greater than 5 hours while the paint effect remains unchanged. According to current field experience, the coating operation time can be extended beyond 24 hours if 15 to 20% by weight of ethanol is added in one portion or in portions. Because the paint can be diluted by non-benzene solvents such as ethanol and the like, the paint also has remarkable advantages in the aspects of protection of constructors, environmental protection and the like.
Based on the properties, the polyurea coating provided by the invention can be coated by adopting conventional coating equipment according to the requirements of a conventional coating process, and because the polyurea coating provided by the invention has relatively long gel time and low viscosity, the polyurea coating can fully wet a base surface, no destructive stress exists in an interface and the coating, and the phenomena of bubbling, pinholes, shrinkage cracking and the like can be avoided. Furthermore, the polyurea coatings provided herein can produce thin coatings with dry film thicknesses of only 15-20 microns, whereas typical high solids coatings typically have dry film thicknesses of greater than 100 microns, with only a few being able to achieve dry film thicknesses on the order of 80 microns.
In addition, in the case of the conventional polyurea coating, since isocyanate group (-NCO) and liquid amine are toxic, odorous and strongly irritating substances, it is necessary for a worker to wear a gas mask, protective glasses, rubber gloves, protective clothing, protective shoes, etc., and to stand at an air inlet for work. Only when the coating is fully reacted and completely polymerized to form macromolecular polyurea elastomer, and the polyurea coating completely meets the environmental protection requirement under the condition of not containing free monomers. The polyurea coating provided by the invention belongs to an odor-free slow polyurea coating due to specific formula selection and proportion, basically has no odor, and has no harmful influence on environment and people during construction, namely, the coating product is environment-friendly and the product construction is also environment-friendly.
In one embodiment, the polyurea coating comprises or consists of the following components:
wherein the polyaspartic acid ester has a structure represented by the following formula 1:
in the general formula 1, R is C 1-4 Straight or branched chain alkyl, X is C 1-15 An alkylene group;
the HDI trimeric carbamate component is selected from one or more of octadecamethylene triurea methyl tricarbamate, octadecamethylene triurea diethylene glycol ethyl tricarbamate, octadecamethylene triurea dipropylene glycol monomethyl tricarbamate, octadecamethylene triurea 1, 4-butanediol methyl tricarbamate, octadecamethylene triurea silicone tricarbamate and the combination thereof;
the diisocyanate trimer has a structure represented by the following general formula 2:
in the general formula 2, R is C 3-10 A linear alkylene group,
the component A solvent is selected from acetone, ethyl acetate, dipropylene glycol dimethyl ether, and combinations thereof,
the ethyl component solvent is selected from ethanol, methylal, ethyl acetate, dipropylene glycol dimethyl ether, N-methyl pyrrolidone and components thereof,
wherein the weight% is based on the weight of the polyurea coating and the total weight of the inorganic powder and the pigment is not less than 55 weight%, and typically not more than 75 weight%.
The above descriptions about the pigment, the solvent of formula 1, the solvent of formula 2, the solvent of component A, the solvent of component B, the HDI trimer type urethane component, the silica-based inorganic powder and the plasticizer can be used herein, and thus, they will not be described in detail. The polyurea resin contains a higher solvent component and is therefore easier to implement and operate. Although the polyurea coatings generally have solids contents of not more than 75% by weight, they are slow polyurea coatings with long gel times and long coating operation times.
Process for preparing polyurea coatings
In one embodiment, a method of preparing a polyurea coating includes: uniformly mixing diisocyanate trimer represented by a general formula 2 with a component A solvent (namely, the mixed system is clear after standing, and the same applies below), thereby obtaining a component A; uniformly mixing an HDI trimer type urethane component, polyurethane polyaspartate and a plasticizer, uniformly mixing the obtained mixture with a silica-based inorganic powder having a fineness of 200 mesh or more, and then uniformly mixing the obtained mixture with a component B solvent, thereby obtaining a component B; mixing the component A with the component B, thereby obtaining the polyurea coating.
In this embodiment, in the preparation of the component B, the inorganic powder is added after the liquid components are thoroughly mixed. If various liquid components which are not mixed are added into the inorganic powder, the prepared component B is easy to generate the phenomenon of precipitation. In addition, the prepared component B may be layered after being left for more than 5 days, and needs to be stirred again for use without being re-prepared. In contrast, the storage life of the component A and the component B is half a year, and the components are only required to be respectively stirred uniformly before being mixed, so that the final performance is not influenced.
In one embodiment, the water content of the inorganic powder is less than 0.5% prior to addition of the inorganic powder, for benefits see above and not described further herein. In addition, after methylal was added and mixed, the amount of methylal lost was measured, and the lost methylal was replenished. The reason is that the methylal is extremely volatile, loss is generated during the stirring of the prepared ethyl component, the loss amount needs to be measured, and the loss amount is complemented in the later stage of preparing the ethyl component, so that the concentration of each component of the coating is not influenced. In addition, ethanol cannot be used as a solvent for the A component because it reacts with hexamethylene diisocyanate trimer (HDI trimer for short).
In a further embodiment, a method of preparing a polyurea coating includes: mixing hexamethylene diisocyanate trimer and hydroxyl polyester (such as molecular weight 2000) according to a certain proportion uniformly for addition reaction, thereby obtaining diisocyanate represented by a general formula 2 as a chain extender, adding one or a mixture of three of acetone, ethyl acetate or dipropylene glycol dimethyl ether in any proportion, and mixing uniformly to obtain a component A; uniformly mixing an HDI trimer type urethane component, polyurethane polyaspartate and a plasticizer, uniformly mixing the obtained mixture with a silica-based inorganic powder having a fineness of 200 mesh or more, and then uniformly mixing the obtained mixture with a component B solvent, thereby obtaining a component B; mixing the component A with the component B, thereby obtaining the polyurea coating.
In one embodiment, a method of preparing a polyurea coating includes: the HDI trimer type urethane component, the polyaspartic acid ester and the plasticizer were uniformly mixed, the resultant mixture was uniformly mixed with the silica-based inorganic powder having a fineness of 200 mesh or more and the pigment, and then the resultant mixture was uniformly mixed with the component b solvent, thereby obtaining the component b. Mixing the B component with the B component, thereby obtaining the polyurea coating.
Use and use of polyurea coatings
The polyurea coating provided by the invention has long gel time and low viscosity, can be coated without special polyurea coating equipment, and effectively avoids destructive stress caused by quick curing of the polyurea coating. For example, the components A and B can be mixed in proportion and uniformly stirred at room temperature (stirring for 5-8 minutes by a stirrer with the rotating speed of 300-500 rpm is recommended), and then the spraying and coating can be carried out by using conventional air spraying equipment under the condition of the gas pressure of 3-8 kg/square centimeter; and (3) carrying out spraying and coating by using general airless spraying equipment under the condition of gas pressure of 5-12 kg/square centimeter.
As an example, the polyurea coatings provided herein have passed detection and validation by the us KTA laboratory in 2018 and are allowed to be used for container protection. In the same year, the polyurea coating provided by the invention has been subjected to a plurality of spraying experiments in a centralized production field in the south, and can completely meet the process use requirements of a container coating spraying production line. In field tests, the polyurea coatings provided herein can be matched to conventional coating processes due to low viscosity and long gel times, thereby achieving polyurea coating conventions.
The polyurea coating provided by the invention has good environmental protection performance, simple and convenient construction and far better physical and chemical properties than the prior water-based coating, and can be used in the building industry, the metal protection industry and the furniture industry.
Examples
Hereinafter, the present invention is described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto. The reagents used in the examples are commercially available, in particular:
the polyaspartic ester is F-520 of New Material Ltd of Zhuhai Feiyang, and has a relative molecular weight of 580 and an NH equivalent of 290 g/mol; the preparation method of the octadecyl triurea tricarbamate is as a self-made product; the inorganic pigment is R930 titanium dioxide produced by Japan stone original type Co; the inorganic powder is domestic quartz sand with the fineness of 800 meshes; the plasticizer is domestic BD-3310 polyester modified polydimethylsiloxane; the HDI tripolymer is produced by China Wanhua company, and has the model of HT-100; the rest solvents are industrial grade solvents.
Hereinafter, "parts" means parts by weight unless otherwise specified.
Preparation of HDI trimer type urethane component:
HDI trimer was added as 1: adding the molar equivalent ratio of 3 into a solvent containing hydroxyl silicone oil, uniformly stirring, standing for seven days to obtain the octadecyl triurea tricarbamic acid siloxane ester, wherein the specific reaction is as follows, wherein n is 1-5:
similarly, methyl octadecylidene triurea tricarbamate is formed from the reaction of HDI trimer with methanol, for example, by reacting the HDI trimer in the ratio of 1: 3, adding the mixture into a solvent containing methanol, uniformly stirring, and standing for seven days; the octadecamethylene triurea tricarbamic acid diethylene glycol ethyl ester is generated by reacting HDI tripolymer and diethylene glycol ethyl ether, for example, the HDI tripolymer is added into a solvent containing the diethylene glycol ethyl ether according to a certain equivalent ratio, the mixture is uniformly stirred and stands for seven days; the octadecyl triurea tricarbamic acid dipropylene glycol monomethyl ether ester is generated by the reaction of HDI tripolymer and dipropylene glycol monomethyl ether, for example, the HDI tripolymer is added into a solvent containing the dipropylene glycol monomethyl ether according to a certain equivalent ratio, the mixture is uniformly stirred and stands for seven days; the octadecyl methylene triurea tricarbamate 1, 4-butanediol methyl ether ester is generated by the reaction of HDI tripolymer and 1, 4-butanediol methyl ether, for example, the HDI tripolymer is added into a solvent containing 1, 4-butanediol methyl ether according to a certain equivalent ratio, the mixture is uniformly stirred, and the mixture is kept stand for seven days.
Example 1
At room temperature, 137 parts of HDI trimer and 35 parts of acetone are mixed together, and fully and uniformly stirred by a dispersion stirrer (at the moment, the mixed system is clear after standing), so that the component A of the polyurea coating is obtained and is stored in a sealed manner.
26 parts of octadecyl triurea triscarbamate siloxane ester, 141 parts of polyaspartic acid ester F-520 and 70 parts of plasticizer BD-3310 are mixed uniformly, 490 parts of 800-mesh quartz sand and 120 parts of R930 titanium dioxide are added, the mixture is fully and uniformly ground by a three-roll machine to prepare 847 parts of color paste of the polyurea coating, 35 parts of ethanol and 30 parts of methylal are added, and the mixture is fully and uniformly stirred by a dispersion mixer, so that the component B of the slow polyurea coating is obtained and is sealed and stored.
Before coating, the coating comprises the following components: the component B is 1: 5.3, and stirring uniformly to obtain the coating. The formulation of the polyurea coating of example 1 is shown in table 1 below.
Table 1: formulation of the polyurea coating of example 1
Example 2
At room temperature, 137 parts of HDI trimer and 35 parts of dipropylene glycol dimethyl ether are mixed together and sufficiently and uniformly stirred by a dispersion stirrer (at this time, the mixed system is clear after standing), so that the component A of the polyurea coating is obtained and is stored in a sealed manner.
26 parts of octadecyl triurea tricarbamate siloxane ester, 35 parts of dipropylene glycol dimethyl ether, 141 parts of polyaspartic acid ester F-520 and 10 parts of plasticizer BD-3310 are uniformly mixed, 650 parts of 800-mesh quartz sand and 150 parts of R930 titanium dioxide are added, a three-roller machine is used for fully and uniformly grinding to prepare 1012 parts of color paste of the polyurea coating, 35 parts of ethanol and 35 parts of dipropylene glycol dimethyl ether are added, a dispersion mixer is used for fully and uniformly stirring, and therefore the component B of the slow polyurea coating is obtained and is sealed and stored.
Before coating, the coating comprises the following components: the component B is 1: 5.22, and stirring uniformly to obtain the coating. The formulation of the polyurea coating of example 2 is shown in table 2 below, and this coating is a matte type coating.
Table 2: formulation of polyurea coating of example 2
Example 3
At room temperature, 137 parts of HDI trimer and 35 parts of dipropylene glycol dimethyl ether are mixed together and sufficiently and uniformly stirred by a dispersion stirrer (at this time, the mixed system is clear after standing), so that the component A of the polyurea coating is obtained and is stored in a sealed manner.
26 parts of octadecyl triurea tricarbamate siloxane, 35 parts of dipropylene glycol dimethyl ether, 141 parts of polyaspartic acid ester F-520 and 10 parts of plasticizer BD-3310 are uniformly mixed, 650 parts of 1250-mesh glass powder and 150 parts of R930 titanium dioxide are added, the mixture is fully and uniformly ground by a three-roll machine to prepare 1012 parts of color paste of the polyurea coating, 35 parts of ethanol and 35 parts of dipropylene glycol dimethyl ether are added, the mixture is fully and uniformly stirred by a dispersion mixer, and the component B of the slow polyurea coating is obtained and is sealed and stored.
Before coating, the coating comprises the following components: the component B is 1: 5.22, and stirring uniformly to obtain the coating. The formulation of the polyurea coating of example 3 is shown in Table 3 below, and this coating is a surface slip type coating.
Table 3: formulation of polyurea coating of example 3
Example 4
At room temperature, 137 parts of HDI trimer and 35 parts of dipropylene glycol dimethyl ether are mixed together and sufficiently and uniformly stirred by a dispersion stirrer (at this time, the mixed system is clear after standing), so that the component A of the polyurea coating is obtained and is stored in a sealed manner.
26 parts of octadecyl triurea tricarbamate siloxane, 35 parts of dipropylene glycol dimethyl ether, 141 parts of polyaspartic acid ester F-520 and 10 parts of plasticizer BD-3310 are uniformly mixed, 650 parts of 3-150 micron glass beads and 150 parts of R930 titanium dioxide are added, the mixture is fully and uniformly stirred by a dispersion stirrer to prepare 1012 parts of color paste of the polyurea coating, 35 parts of ethanol and 35 parts of dipropylene glycol dimethyl ether are added, the mixture is fully and uniformly stirred by the dispersion stirrer to obtain the component B of the slow polyurea coating, and the component B is sealed and stored.
Before coating, the coating comprises the following components: the component B is 1: 5.22, and stirring uniformly to obtain the coating. The formulation of the polyurea coating of example 4 is shown in table 4 below, and this coating can be used as a heat insulating type coating.
Table 4: formulation of polyurea coating of example 4
Example 5
217 parts of HDI trimer and 160 parts of ethyl acetate are mixed together at room temperature, and the mixture is fully and uniformly stirred by a dispersion stirrer (at the moment, the mixed system is clear after standing), so that the component A of the polyurea coating is obtained and is stored in a sealed manner.
26 parts of octadecyl triurea tricarbamate siloxane ester, 243 parts of polyaspartic acid ester F-520 and 70 parts of plasticizer BD-3310 are mixed uniformly, 350R930 titanium dioxide is added, a three-roll mill is used for fully and uniformly grinding to prepare 689 parts of color paste of the polyurea coating, 450 parts of ethanol and 350 parts of dipropylene glycol dimethyl ether are added, a dispersion mixer is used for fully and uniformly stirring, and therefore the component B of the slow polyurea coating is obtained and is sealed for storage.
Before coating, the coating comprises the following components: the component B is 1: 3.95, and stirring uniformly to obtain the coating. The formulation of the other type of polyurea coating, example 5, is shown in Table 5 below, and this coating is a thin, medium gloss type coating.
Table 5: formulation of other types of polyurea coatings
Comparative example 1
Polyurea coatings were prepared in the same manner as in example 1, except that 800 mesh quartz sand was not used, and 800 mesh kaolin was used instead. The formulation of the polyurea coating of comparative example 1 is shown in Table 6 below, but after obtaining the A component and the B component separately, before application, as the A component: the component B is 1: 5.3, and stirring uniformly, wherein the viscosity of the coating is extremely high at the moment, so that the coating cannot be coated by a conventional method.
Table 6: formulation of the polyurea coating of comparative example 1
Comparative example 2
A polyurea coating was prepared in the same manner as in example 1, except that instead of using octadecyltributyl triscarbamate silicone oxide, and plasticizer BD-3310, the other plasticizer (diisononyl phthalate DINP) was used. The formulation of the polyurea coating of comparative example 2 is shown in Table 7 below, but after obtaining the A component and the B component separately, before application, as the A component: the component B is 1: 5.3, and stirring uniformly, wherein when the coating is sprayed on the surface of a base material, the phenomenon of shrinkage holes generated in the coating can occur, and the quality of the coating is greatly influenced.
Table 7: formulation of the polyurea coating of comparative example 2
| Numbering | Composition of | Number of parts | Weight content (%) |
| 1 | F-520 | 141 | 13.01 |
| 2 | R930 titanium white powder | 120 | 11.07 |
| 3 | 800 mesh quartz sand | 490 | 45.20 |
| 4 | Ethanol | 35 | 3.23 |
| 5 | DINP | 96 | 8.86 |
| 6 | Acetone (II) | 35 | 3.23 |
| 7 | HT-100 | 137 | 12.64 |
| 8 | |
30 | 2.77 |
| 9 | Total up to | 1084 | 100 |
Experimental example 1
Table 8 shows the test results of the polyurea coatings obtained in example 1.
Table 8: parameters of polyurea coating
As can be seen from the above, after studying the chemical reaction kinetics of polyaspartic acid, the inventors of the present application realized excellent polyurea coating properties and ensured the relative balance among various properties through specific component ratios.
Experimental example 2
Impedance experiments were performed on the polyurea coatings of the present invention at the electrochemical laboratory of Wuhan university, and the test results are shown in FIG. 1. Briefly, the working electrode surface was coated with four paints and the soaking time was plotted as the impedance film value at the lowest frequency (10 mhz) in a simulated seawater corrosion experiment. Coatings No. 01 to 03 are commercially available epoxy coating, acrylic urethane coating and polyester coating, respectively, and coating No. 04 is the polyurea coating of the present invention (example 1). In the whole experiment, the parameters are the same except that the coating material is different.
In this experiment, the lowest frequency (10 mhz) mode value of the impedance can be considered as the resistance of the coating, and the resistance of the three other coatings is gradually reduced except that the No. 01 epoxy coating is too quickly soaked by the saline water. This is related to the coating's ability to resist water penetration, and as salt water penetrates and swells, the coating's resistance decreases. As can be seen from fig. 1, of the four coatings, polyurea No. 04 has the best resistance and corrosion protection, followed by polyester No. 03.
In addition, FIG. 2 is a photograph showing the surface corrosion condition of the working electrode coated with four different paints (the scribed region is the working electrode area, and the area is 1.56 cm) 2 ) Wherein (a) of fig. 2 is a corrosion condition of the working electrode coated with epoxy intercoat, (b) of fig. 2 is a corrosion condition of the working electrode coated with acrylic urethane, (c) of fig. 2 is a corrosion condition of the working electrode coated with polyester, and (d) of fig. 2 is a corrosion condition of the working electrode coated with polyurea of the present invention. As can be seen from fig. 2 (d), the working electrode coated with the polyurea of the present invention showed no corrosion spots, whereas fig. 2 (a) showed almost total corrosion, fig. 2 (b) showed large-area edge corrosion and severe center corrosion, and fig. 2 (c) showed many corrosion spots.
Experimental example 3
The polyurea coatings of the present invention (example 1) were subjected to salt spray aging testing at the Guangdong province paint inspection center according to GB/T1771-2007 determination of neutral salt spray resistance of paints and varnishes using a L3022SST-9NL salt spray test chamber, and the results are shown in Table 3 below.
Table 3: salt spray test results for polyurea coatings of the invention
Therefore, the technical indexes of the polyurea of the invention reach or exceed the indexes of the existing general anticorrosive paint. In contrast, the slow polyurea of the present invention has a relatively long gel time, can sufficiently wet a base surface, has no destructive stress at the interface or inside the coating, and has a very high corrosion resistance.
While specific embodiments of the present invention have been described above with reference to specific examples, it will be appreciated by those skilled in the art that various modifications and changes may be made thereto without departing from the scope and spirit of the invention.
Claims (10)
1. A polyurea coating, comprising:
wherein the polyaspartic acid ester has a structure represented by formula 1 below:
in the general formula 1, R is C 1-4 Straight or branched chain alkyl, X is C 1-15 An alkylene group;
the HDI trimeric carbamate component is one or more selected from the group consisting of octadecamethylene triurea methyl tricarbamate, octadecamethylene triurea diethylene glycol ethyl ether tricarbamate, octadecamethylene triurea dipropylene glycol monomethyl ether tricarbamate, octadecamethylene triurea 1, 4-butanediol methyl ether tricarbamate, octadecamethylene triurea silicon oxide tricarbamate and the combination thereof;
the diisocyanate trimer has a structure represented by the following general formula 2:
in the general formula 2, R is C 3-10 A linear alkylene group,
the component A solvent is selected from acetone, ethyl acetate, dipropylene glycol dimethyl ether, and combinations thereof,
the ethyl component solvent is selected from ethanol, methylal, ethyl acetate, dipropylene glycol dimethyl ether, N-methyl pyrrolidone and components thereof,
wherein the weight% is based on the weight of the polyurea coating.
2. The polyurea coating of claim 1, wherein the pigment is selected from the group consisting of titanium dioxide based pigments, carbon based pigments, iron oxide based pigments, cadmium selenide sulfide based red yellow pigments, lead chromate based yellow pigments, ultramarine pigments, e.g. the pigment is selected from titanium dioxide, carbon black, iron oxide red, cadmium selenide sulfide, lead chromate, ultramarine.
3. The polyurea coating of claim 1, wherein in formula 1, R is ethyl and X is a structure represented by the following formula 3:
optionally, in formula 2, R is hexylene.
4. The polyurea coating of claim 1, wherein the component a solvent is acetone, dipropylene glycol dimethyl ether, ethyl acetate, or a combination thereof, 3.23 wt%; and/or the presence of a gas in the gas,
the component B solvent is 3.23 wt% of ethanol, 2.77 wt% of methylal and/or one or more of ethyl acetate, dipropylene glycol dimethyl ether and N-methyl pyrrolidone in any proportion.
5. The polyurea coating of claim 1 wherein the HDI trimeric urethane component is octadecyltribusium tricarbamate siloxane ester; and/or
The silica-based inorganic powder is silica-based inorganic powder having a fineness of 200-2000 mesh, nano-scale silica-based inorganic powder, or a combination thereof, and is selected from the group consisting of fine silica powder, glass beads, glass powder, white carbon, silica sand and a combination thereof, and the content of the inorganic powder is at least 45.20 wt%; and/or
The plasticizer is a silicone, liquid paraffin, dipropylene glycol dibenzoate, or a combination thereof, optionally, the silicone comprises: one or more of methyl silicone oil, hydroxyl silicone oil, amino silicone oil, alkyl modified silicone oil, styryl modified silicone oil, polyether modified silicone oil, polyester modified silicone oil or the combination thereof.
6. A polyurea coating, comprising:
wherein the polyaspartic acid ester has a structure represented by the following formula 1:
in the general formula 1, R is C 1-4 Straight or branched chain alkyl, X is C 1-15 An alkylene group;
the HDI trimeric carbamate component is selected from one or more of octadecamethylene triurea methyl tricarbamate, octadecamethylene triurea diethylene glycol ethyl tricarbamate, octadecamethylene triurea dipropylene glycol monomethyl tricarbamate, octadecamethylene triurea 1, 4-butanediol methyl tricarbamate, octadecamethylene triurea silicone tricarbamate and the combination thereof;
the diisocyanate trimer has a structure represented by the following general formula 2:
in the general formula 2, R is C 3-10 A linear alkylene group,
the component A solvent is selected from acetone, ethyl acetate, dipropylene glycol dimethyl ether, and combinations thereof,
the component B solvent is selected from ethanol, methylal, ethyl acetate, dipropylene glycol dimethyl ether, N-methylpyrrolidone and components thereof,
wherein the weight% is based on the weight of the polyurea coating and the total weight of the inorganic powder and the pigment is not less than 55 weight%.
7. The polyurea coating according to claim 6, wherein the pigment is selected from the group consisting of titanium dioxide based pigments, carbon based pigments, iron oxide based pigments, red yellow pigments based on selenium cadmium sulfide, yellow pigments based on lead chromate, ultramarine pigments, for example the pigment is selected from the group consisting of titanium dioxide, carbon black, iron oxide red, selenium cadmium sulfide, lead chromate, ultramarine.
8. The polyurea coating of claim 6, wherein in formula 1, R is ethyl and X is a structure represented by the following formula 3:
optionally, in formula 2, R is hexylene.
9. The polyurea coating of claim 6, wherein the ethyl component solvent is ethanol, methylal, and/or a mixture of one or more selected from ethyl acetate, dipropylene glycol dimethyl ether, and N-methylpyrrolidone in any proportion.
10. The polyurea coating of claim 6, wherein the HDI trimer type urethane component is octadecyltrimethylurea trisiloxanecarbamate; and/or
The silica-based inorganic powder is silica-based inorganic powder having a fineness of 200-2000 mesh, nano-scale silica-based inorganic powder, or a combination thereof, and is selected from the group consisting of silica micropowder, glass beads, glass powder, white carbon, silica sand, and a combination thereof; and/or
The plasticizer is a silicone, liquid paraffin, dipropylene glycol dibenzoate, or a combination thereof, optionally, the silicone comprises: one or more of methyl silicone oil, hydroxyl silicone oil, amino silicone oil, alkyl modified silicone oil, styryl modified silicone oil, polyether modified silicone oil, polyester modified silicone oil or the combination thereof.
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| CN113045972A (en) * | 2019-12-27 | 2021-06-29 | 深圳市精彩科技有限公司 | Polyurea coating |
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| CN113045973A (en) * | 2019-12-27 | 2021-06-29 | 深圳市精彩科技有限公司 | Odor-free polyurea coating and preparation method thereof |
| CN113045971A (en) * | 2019-12-27 | 2021-06-29 | 深圳市精彩科技有限公司 | Polyurea coating and preparation method thereof |
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