CN116829615A - Coating composition - Google Patents
Coating composition Download PDFInfo
- Publication number
- CN116829615A CN116829615A CN202180088178.4A CN202180088178A CN116829615A CN 116829615 A CN116829615 A CN 116829615A CN 202180088178 A CN202180088178 A CN 202180088178A CN 116829615 A CN116829615 A CN 116829615A
- Authority
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- China
- Prior art keywords
- weight
- polyurethane prepolymer
- component
- coating
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000008199 coating composition Substances 0.000 title claims abstract description 102
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 112
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 60
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 59
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000010439 graphite Substances 0.000 claims abstract description 46
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 27
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002516 radical scavenger Substances 0.000 claims abstract description 21
- -1 aromatic isocyanate Chemical class 0.000 claims abstract description 18
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005481 NMR spectroscopy Methods 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- FYUZFGQCEXHZQV-UHFFFAOYSA-N triethoxy(hydroxy)silane Chemical compound CCO[Si](O)(OCC)OCC FYUZFGQCEXHZQV-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000007561 laser diffraction method Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 30
- 239000000758 substrate Substances 0.000 description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 11
- 239000003063 flame retardant Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000009970 fire resistant effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 1
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to coating compositions and uses thereof, and articles comprising coatings formed from the coating compositions. The coating composition comprises: a polyurethane prepolymer comprising 60 to 100 wt% of an aromatic isocyanate-based polyurethane prepolymer and 0 to 40 wt% of an aliphatic and/or cycloaliphatic isocyanate-based polyurethane prepolymer, relative to the total weight of the polyurethane prepolymers; expandable graphite; surface untreated ammonium polyphosphate; and a water scavenger; the isocyanate group content of the polyurethane prepolymer is 2.5 to 14 wt% relative to the total weight of the solid components of the polyurethane prepolymer; the amount of the water scavenger is 0.1 wt% to 5 wt%, relative to the total weight of the composition; the weight ratio of the polyurethane prepolymer to the sum of the weight of the expandable graphite and the surface untreated ammonium polyphosphate is 1/2 to 2/1, and the weight ratio of the expandable graphite to the surface untreated ammonium polyphosphate is 1/10 to 4/1.
Description
Technical Field
The present invention relates to a coating composition and its use, and articles comprising a coating formed from the coating composition.
Background
In recent years, new energy automobiles, particularly pure electric automobiles, are actively promoted. The battery of the electric automobile, particularly the battery core positive electrode explosion-proof valve position of the lithium battery, has the risk of internal combustion and thermal runaway, and the situation of thermal runaway of the battery of the electric automobile occurs. In order to improve the safety of the electric automobile, the industrial information department establishes three mandatory national standards of GB18384-2020 electric automobile safety requirements, GB38031-2020 electric bus safety requirements and GB38032-2020 electric automobile power storage battery safety requirements, and higher requirements are provided for the fire resistance and the temperature resistance of an electric automobile battery box. For example, a new thermal diffusion test item in the safety requirement of a power storage battery for an electric automobile is to require that a battery box does not fire or explode within 5 minutes after thermal runaway of a battery of the electric automobile occurs, so that sufficient escape time is provided for passengers in the automobile.
In order to improve the fire resistance and the temperature resistance of the battery box, the preferred scheme is to replace the battery box body material with a flame-retardant material, but the flame-retardant effect is relatively limited. The inner side of the battery box can be riveted with a layer of mica sheet, but the relative density of the mica sheet is larger, so that the vehicle body is not beneficial to light weight, and if the design of the battery box has a certain special-shaped structure, the mica sheet is difficult to be completely attached to the battery box.
It is a very suitable and economical option to make a flame retardant coating on the inside or outside of the battery box. The systems of the flame retardant coating may be solvent-based, aqueous and solvent-free. Solvent-based systems have excellent adhesion to battery case substrates, but conventional solvent-based systems have severe corrosion to plastic battery case substrates due to the presence of large amounts of solvents, particularly esters, ketones, and the like. Flame retardant coatings for aqueous systems are an environmentally friendly solution, but aqueous systems suffer from slow evaporation of water, especially aqueous thick coating systems, often requiring the provision of drying equipment. The volume of the automobile battery box body is large, a production and installation workshop often does not have a pre-arranged drying tunnel, and if an aqueous system is used, a large amount of time is consumed for drying the system, so that the production efficiency of the automobile battery box is greatly affected. The solvent-free system can not corrode the base material of the battery box body, the problem of slow volatilization of water in the system is solved, and the solvent-free system is a better choice than a solvent-based system and an aqueous system. However, the two-component solvent-free system requires special equipment investment for on-site compounding, and the two-component solvent-free system must be used within a certain use time after mixing, so that the construction is inconvenient.
Therefore, it is desirable to develop a new fire-resistant and temperature-resistant coating composition which can be conveniently coated on a battery box of an electric automobile and forms a coating layer, wherein the coating layer has good fire resistance and high temperature resistance, and when a battery in the battery box is on fire or explodes, the battery box can not be on fire or explode for more than 5 minutes, so that escape time is provided for passengers in the automobile.
Disclosure of Invention
The invention aims to provide a coating composition and application thereof, a coating method of the coating composition and an article comprising a coating formed by the coating composition.
The coating composition according to the invention comprises the following components:
a. a polyurethane prepolymer comprising 60 to 100 wt% of an aromatic isocyanate-based polyurethane prepolymer and 0 to 40 wt% of an aliphatic and/or cycloaliphatic isocyanate-based polyurethane prepolymer, relative to the total weight of the polyurethane prepolymers;
b. expandable graphite;
c. surface untreated ammonium polyphosphate;
d. a water scavenger; and
e. optionally not more than 35% by weight of solvent, relative to the total weight of the composition;
the isocyanate group content of the polyurethane prepolymer of component a) is 2.5% to 14% by weight, relative to the total weight of the solid components of the polyurethane prepolymer of component a); the amount of the component d) water scavenger is 0.1-5 wt%, relative to the total weight of the composition; the weight ratio of the polyurethane prepolymer of the component a) to the sum of the weight of the expandable graphite of the component b) and the weight of the ammonium polyphosphate untreated on the surface of the component c) is 1/2 to 2/1, and the weight ratio of the expandable graphite of the component b) to the ammonium polyphosphate untreated on the surface of the component c) is 1/10 to 4/1.
The invention relates in particular to a coating composition comprising the following components:
a. a polyurethane prepolymer comprising 60% to 100% by weight of a polyurethane prepolymer based on aromatic isocyanate and 0 to 40% by weight of a polyurethane prepolymer based on aliphatic and/or cycloaliphatic isocyanate, in each case based on 100% by weight relative to the total weight of the polyurethane prepolymer;
b. expandable graphite;
c. surface untreated ammonium polyphosphate;
d. a water scavenger; and
e. optionally not more than 35% by weight of solvent, in each case calculated as 100% by weight relative to the total weight of the composition; the isocyanate group content of the polyurethane prepolymer of component a) is 2.5% to 14% by weight, relative to the total weight of the solid components of the polyurethane prepolymer of component a); the amount of the polyurethane prepolymer a) is from 20 to 50% by weight, in each case based on 100% by weight of the total weight of the composition; the expandable graphite b) is present in an amount of from 10 to 25% by weight, in each case based on 100% by weight, relative to the total weight of the composition; the amount of surface-untreated ammonium polyphosphate c) is from 15 to 45% by weight, based in each case on 100% by weight, based on the total 100 parts by weight of the composition; component d) the amount of water scavenger is 0.1% to 5% by weight, in each case relative to 100% by weight of the total weight of the composition; the weight ratio of the polyurethane prepolymer of the component a) to the sum of the weight of the expandable graphite of the component b) and the weight of the ammonium polyphosphate untreated on the surface of the component c) is 1/2 to 2/1, and the weight ratio of the expandable graphite of the component b) to the ammonium polyphosphate untreated on the surface of the component c) is 1/10 to 4/1.
According to one aspect of the present invention there is provided the use of a coating composition according to the present invention for slowing or preventing the spread of flame or heat generated by an object.
According to a further aspect of the present invention there is provided the use of a coating composition according to the present invention for slowing or preventing the spread of heat generated by flammable objects.
According to a further aspect of the present invention, there is provided a coating method comprising the steps of: the coating composition provided according to the present invention is applied to an object and/or the storage bin surface of the object and subsequently cured.
According to a further aspect of the present invention there is provided an article comprising an object and a coating layer formed by curing a coating composition provided according to the present invention applied to said object and/or to a storage bin of said object.
According to a further aspect of the present invention, there is provided a method of preparing a coating composition provided according to the present invention, comprising the steps of: the component a) polyurethane prepolymer, component b) expandable graphite, component c) surface untreated ammonium polyphosphate, component d) water scavenger and optionally component e) solvent are mixed in any way.
The coating composition of the present invention is simple and safe to use.
The coating composition, in particular to a single-component solvent-free coating composition, is an environment-friendly solvent-free coating and does not pollute the environment.
The coating composition disclosed by the invention is a fireproof and high-temperature-resistant coating composition, and a formed coating has good fireproof and high-temperature resistance. When a flammable object coated with the coating composition of the present invention explodes on fire, the storage case for the flammable object can withstand high temperatures for more than 5 minutes without burning through.
When the coating composition is coated on the inner side and/or the outer side of the battery box of the automobile, the battery box can be kept from being burnt out for more than 5 minutes when the battery in the battery box is ignited and exploded, and the escape time is provided for passengers in the automobile.
The coating composition of the present invention has good extrusion rate, good sag resistance, fast open time and good storage stability, is easy to apply and does not damage the substrate. The coating formed by the coating composition has good adhesive force and flame retardance, and the coating is not easy to fall off when being heated.
Detailed Description
The invention provides a coating composition, in particular a fire-resistant and high-temperature-resistant coating composition, which comprises the following components: a. a polyurethane prepolymer comprising 60 to 100 wt% of an aromatic isocyanate-based polyurethane prepolymer and 0 to 40 wt% of an aliphatic and/or cycloaliphatic isocyanate-based polyurethane prepolymer, relative to the total weight of the polyurethane prepolymers; b. expandable graphite; c. surface untreated ammonium polyphosphate; d. a water scavenger; optionally not more than 35% by weight of solvent, relative to the total weight of the composition; the isocyanate group content of the polyurethane prepolymer of component a) is 2.5% to 14% by weight, relative to the total weight of the solid components of the polyurethane prepolymer of component a); the amount of the component d) water scavenger is 0.1-5 wt%, relative to the total weight of the composition; the weight ratio of the polyurethane prepolymer of the component a) to the sum of the weight of the expandable graphite of the component b) and the weight of the ammonium polyphosphate untreated on the surface of the component c) is 1/2 to 2/1, and the weight ratio of the expandable graphite of the component b) to the ammonium polyphosphate untreated on the surface of the component c) is 1/10 to 4/1. The invention also provides a coating method and application of the coating composition, and an article comprising a coating formed by the coating composition.
The term "solvent-free" as used herein means that no solvent is actively added to the coating composition and the VOC content of the coating is less than 60g/L.
The term "coating" as used herein refers to a chemical substance that can be applied to the surface of an article using different application processes to form a solid, continuous coating that adheres well, has a certain strength.
The term "cure" as used herein refers to the process of coating from a liquid to a cured state.
The term "surface untreated ammonium polyphosphate" as used herein refers to ammonium polyphosphate that has not been surface treated with a chemical or ammonium polyphosphate that has not been physically coated on the surface.
The term "aromatic isocyanate-based polyurethane prepolymer" as used herein refers to polyurethane prepolymers obtained from the reaction of components comprising aromatic isocyanates.
The term "aliphatic isocyanate-based polyurethane prepolymer" as used herein refers to a polyurethane prepolymer obtained by reacting components comprising aliphatic isocyanates.
The term "cycloaliphatic isocyanate-based polyurethane prepolymer" as used herein refers to a polyurethane prepolymer obtained from the reaction of components comprising a cycloaliphatic isocyanate.
The solid component of the polyurethane prepolymer herein refers to the non-volatile content of the polyurethane prepolymer, and does not contain water or other solvents.
Coating composition
The coating composition is preferably a one-component coating.
The weight ratio of the expandable graphite of component b) to the surface untreated ammonium polyphosphate of component c) is preferably 1/7 to 2/1, most preferably 1/7 to 1/2.
The amount of the polyurethane prepolymer of component a) is preferably from 35% to 60% by weight, relative to the total weight of the composition.
The sum of the amounts of expandable graphite of component b) and surface untreated ammonium polyphosphate of component c) is preferably 39.5% to 64.5% by weight, relative to the total weight of the composition.
The ratio of the weight of the polyurethane prepolymer of component a) to the sum of the weight of the expandable graphite of component b) and the weight of the surface-untreated ammonium polyphosphate of component c) is preferably 7/13 to 3/2.
Component a) polyurethane prepolymers
The isocyanate group content of the polyurethane prepolymer is preferably 3% to 11% by weight, relative to the total weight of the solid components of the polyurethane prepolymer of component a).
The viscosity of the polyurethane prepolymers is preferably 2000 mPas-10000 mPas, the viscosity being in accordance with DIN EN ISO 3219:1994-10 at 23℃and 10s -1 Is determined by selecting a MV-DIN rotor at the shear rate of (2).
The isocyanate functionality of the polyurethane prepolymer is preferably from 2 to 3, the isocyanate functionality being determined according to GPC.
The molecular weight of the polyurethane prepolymers is preferably from 800g/mol to 4200g/mol, the molecular weight being in accordance with gel permeation chromatography and DIN 55672-1:2016-03, polystyrene as a standard and tetrahydrofuran as an eluent.
The amount of the polyurethane prepolymer based on aliphatic and/or cycloaliphatic isocyanates is preferably not more than 35% by weight, relative to the total weight of the polyurethane prepolymer of component a).
The isocyanate group content of the aromatic isocyanate-based polyurethane prepolymer is preferably 2.5% to 14% by weight, most preferably 3.1% to 10.5% by weight, relative to the total weight of the solid components of the aromatic isocyanate-based polyurethane prepolymer.
The aromatic isocyanate-based polyurethane prepolymer is preferably one or more of the following: polyurethane prepolymers based on diphenylmethane diisocyanate and polyurethane prepolymers based on toluene diisocyanate.
The aliphatic and/or cycloaliphatic isocyanate-based polyurethane prepolymers are one or more of the following: polyurethane prepolymers based on isophorone diisocyanate and polyurethane prepolymers based on hexamethylene diisocyanate.
The polyurethane prepolymer is further preferably a combination of a toluene diisocyanate-based polyurethane prepolymer and a hexamethylene diisocyanate-based polyurethane prepolymer, or a combination of a toluene diisocyanate-based polyurethane prepolymer and an isophorone diisocyanate-based polyurethane prepolymer; most preferred is a combination of a toluene diisocyanate based polyurethane prepolymer having a free monomer content of less than 0.5% by weight and a hexamethylene diisocyanate based polyurethane prepolymer having a free monomer content of less than 0.5% by weight, or a combination of a toluene diisocyanate based polyurethane prepolymer having a free monomer content of less than 0.5% by weight and an isophorone diisocyanate based polyurethane prepolymer having a free monomer content of less than 2.0% by weight.
Component b) expandable graphite
The expandable graphite preferably has a particle size of 10 mesh to 100 mesh, the particle size being measured according to GB 10698-89.
The expansion ratio of the expandable graphite is preferably 200ml/g to 400ml/g, and the expansion ratio is tested according to GB 10698-89.
The expandable graphite is preferably crystalline flake graphite.
The expandable graphite is preferably present in an amount of 5% to 43% by weight, relative to the total weight of the composition.
Component c) surface untreated ammonium polyphosphate
The phosphorus content of the surface untreated ammonium polyphosphate is preferably not less than 25 wt%, most preferably 25 wt% to 40 wt%, relative to the total weight of the surface untreated ammonium polyphosphate.
The surface untreated ammonium polyphosphate preferably has a particle size of 1 μm to 100 μm, as measured by laser diffraction.
The decomposition temperature of the surface untreated ammonium polyphosphate is preferably greater than 275℃and the decomposition temperature is measured according to GB/T13464-92.
The surface untreated ammonium polyphosphate preferably has a degree of polymerization greater than 1000, as measured by nuclear magnetic resonance.
The surface untreated ammonium polyphosphate preferably comprises one or more of the following: ammonium polyphosphate with an untreated surface and ammonium polyphosphate with an untreated surface.
The amount of surface untreated ammonium polyphosphate is preferably from 13% to 57% by weight, relative to the total weight of the composition,
component d) water scavenger
The amount of the water scavenger is preferably 0.1 wt% to 5 wt% relative to the total weight of the composition.
The water scavenger is preferably one having one or more of the following structural formulas:
the water scavenger most preferably is one or more of the following: vinyl trimethoxy silane, phenyl isocyanate and triethyl orthosilicate.
Component e) solvent
The solvent is preferably an active hydrogen-free solvent, and more preferably one or more of the following: esters, ketones and ether esters, also preferably ether esters having a boiling point in the range of 100 ℃ to 180 ℃, most preferably one or more of the following: propylene glycol methyl ether acetate (PMA) and propylene glycol methyl ether propionate (PMP).
The solvent in the coating composition may be added separately or may be present in the components of the system, for example in the polyurethane prepolymer.
When the coating composition comprises component e) a solvent, the coating composition is applied in a manner known to the person skilled in the art, most preferably by spraying.
The coating composition is most preferably a one-part solvent-free coating composition, which is well suited for applications requiring low VOC emissions. When the coating composition is solvent-free, the coating composition is most preferably applied by knife coating.
Additive agent
The composition may further comprise an additive.
The additive is preferably one or more of the following: aluminum silicate fiber, titanium dioxide, fumed silica, an adhesion promoter and a catalyst.
The additives are added according to methods and amounts known to those skilled in the art.
Article of manufacture
The object is preferably a flammable object, further preferably from a battery, train chassis, car chassis and doors and windows, most preferably a car battery.
The storage bin for the object is preferably a storage bin for flammable objects, further preferably a battery bin, further preferably an automotive battery bin, most preferably one or more of the following: the upper cover of the automobile battery box, the lower cover of the automobile battery box and the bonding parts of all parts of the automobile battery box.
Examples
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that the definitions of terms in this specification are inconsistent with the ordinary understanding of those skilled in the art to which this invention pertains, the definitions described herein control.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties to be obtained.
As used herein, "and/or" means one or all of the elements mentioned.
The use of "including" and "comprising" herein encompasses both the situation in which only the elements are mentioned and the situation in which other elements not mentioned are present in addition to the elements mentioned.
All percentages in the present invention are by weight unless otherwise indicated.
Analytical measurements according to the invention were carried out at 23.+ -. 2 ℃ unless otherwise indicated.
Raw materials and reagents
Desmodur E22: polyurethane prepolymers based on diphenylmethane diisocyanate having a solids content of 100% by weight and an isocyanate group content of 8.6.+ -. 0.3% by weight (relative to the total weight of the solid components of the polyurethane prepolymer), an isocyanate functionality of 2.0, a molecular weight of 950g/mol and a viscosity of 2800.+ -. 400 mPas are available from Kogynecan polymers (China).
Desmodur SBU Isocyanate 0620: polyurethane prepolymers based on diphenylmethane diisocyanate having a solids content of 100% by weight and an isocyanate group content of 10.+ -. 0.5% by weight (relative to the total weight of the solid components of the polyurethane prepolymers), an isocyanate functionality of 2.0, a molecular weight of 860g/mol and a viscosity of 2700.+ -. 500mPa.s are available from Kogynecan polymers (China).
Desmodur E21: polyurethane prepolymers based on diphenylmethane diisocyanate having a solids content of 100% by weight and an isocyanate group content of 16.+ -. 0.7% by weight (relative to the total weight of the solid components of the polyurethane prepolymer), an isocyanate functionality of 2.8, a molecular weight of 720g/mol and a viscosity of 5400.+ -. 1300mpa.s are commercially available from the company Kogyo Polymer (China).
Desmodur E23: polyurethane prepolymers based on diphenylmethane diisocyanate having a solids content of 100% by weight and an isocyanate group content of 15.4.+ -. 0.4% by weight (relative to the total weight of the solid components of the polyurethane prepolymers), an isocyanate functionality of 2.1, a molecular weight of 560g/mol and a viscosity of 1800.+ -. 250mPa.s are available from Kogynecan Polymer (China).
Desmoseal M280: based on the polyurethane prepolymer of diphenylmethane diisocyanate, the solid content is 80% by weight, the isocyanate group content is 1.7.+ -. 0.3% by weight (relative to the total weight of the solid components of the polyurethane prepolymer), the isocyanate functionality is 2.5, the molecular weight is 5000g/mol, the viscosity is 33000.+ -. 700 mPas, which is available from Kogynecan Polymer (China).
Desmodur E14: polyurethane prepolymers based on toluene diisocyanate having a solids content of 100% by weight and an isocyanate group content of 3.3.+ -. 0.2% by weight (relative to the total weight of the solid components of the polyurethane prepolymer), an isocyanate functionality of 2.5, a molecular weight of 3100g/mol, a viscosity of 6800.+ -. 1200 mPa.s and a free monomer content of less than 0.5% by weight are available from Kogyo Polymer Co., ltd.
Desmodur E30600: based on the polyurethane prepolymer of hexamethylene diisocyanate, the solid content is 100% by weight, the isocyanate group content is 6.+ -. 0.5% by weight (relative to the total weight of the solid components of the polyurethane prepolymer), the isocyanate functionality is 4.0, the molecular weight is 2800g/mol, the viscosity is 2500.+ -. 500mPa.s, the free monomer content is less than 0.5% by weight, and the polyurethane prepolymer is available from Korschc polymer (China).
Desmodur VP LS 2371: polyurethane prepolymers based on isophorone diisocyanate, having a solids content of 100% by weight, an isocyanate group content of 3.4 to 4.0% by weight (relative to the total weight of the solid components of the polyurethane prepolymer), an isocyanate functionality of 2.0, a molecular weight of 2200g/mol, a viscosity of 7300 mPas to 12300 mPas, and a free monomer content of less than 2.0% by weight, are available from Kogyo Polymer (China).
PUREGP-95: the expandable graphite has a particle size of 50-80 meshes and an expansion ratio of 250-300 ml/g, and can be purchased from WiHaiyaka technology Co.
EXOLIT AP 428: surface untreated ammonium polyphosphate, having a phosphorus content of 31-32% by weight, an average particle diameter (D50) of 20 μm, a decomposition temperature of > 275℃and a degree of polymerization of > 1000, is commercially available from Craien.
EXOLIT AP 422: surface untreated ammonium polyphosphate, having a phosphorus content of 31-32% by weight, an average particle diameter (D50) of 17 μm, a decomposition temperature of > 275℃and a degree of polymerization of > 1000, is commercially available from Craien.
EXOLIT AP 423: surface untreated ammonium polyphosphate, having a phosphorus content of 31-32% by weight, an average particle diameter (D50) of 8 μm, a decomposition temperature of > 275℃and a degree of polymerization of > 1000, is commercially available from Craien.
EXOLIT AP 435: the ammonium polyphosphate with the surface treated by the flame retardant synergist has the phosphorus content of 31-32 wt%, the average particle diameter (D50) of 17 mu m, the decomposition temperature of more than 275 ℃, the polymerization degree of more than 1000 and is available from Craien.
EXOLIT AP 462: the ammonium polyphosphate with the surface treated by the flame retardant synergist has the phosphorus content of 29-31 wt%, the average particle diameter (D50) of 20 mu m, the decomposition temperature of more than 275 ℃, the polymerization degree of more than 1000 and is available from Craien.
Dynasylan VTMO: vinyl trimethoxy silane, water scavenger, is available from winning chemistry.
Additive TI: phenyl isocyanate, a water scavenger, is available from oanthraji.
CAB-O-SIL LM150: gas silicon, commercially available from cabot.
Pentaerythritol: the char-forming agent is available from Hubei adapted group.
Desmodur RFE: solvent-based curing agents are available from kestosis polymer (chinese) limited.
Propylene glycol methyl ether acetate (PMA): solvents, available from Shanghai Michlin Biochemical technologies Co.
Commercial solvent-based neoprene: the solvent was toluene, and the resin component was a mixture of neoprene and a terpene phenol resin, with a solids content of 34.5 wt%.
Commercial solvent polyurethane 1: the solvent is butanone, the resin component is hydroxyl polyester polyurethane, and the solid content is 14.5 weight percent.
Commercial solvent polyurethane 2: the solvent is a mixture of butanone and ethyl acetate, the resin component is hydroxyl polyester polyurethane, and the solid content is 14.5 weight percent.
Table 1 shows the compositions of the coating compositions of examples 1 to 7 and comparative examples 1 to 11 and the results of evaluating the properties of the coatings formed from the coating compositions. Table 2 shows the compositions of the coating compositions of examples 1, 8 to 9 and comparative examples 12 to 13 and the results of evaluating the properties of the coatings formed from the coating compositions. Table 3 shows the compositions of the coating compositions of examples 1, 10 to 11 and comparative examples 14 to 15 and the results of evaluating the properties of the coatings formed from the coating compositions. Table 4 shows the compositions of the coating compositions of examples 1, 12 to 15 and comparative example 16 and the results of evaluating the properties of the coatings formed from the coating compositions.
Preparation of coating compositions
According to the components and contents of the coating compositions shown in tables 1-4, polyurethane prepolymer resin, ammonium polyphosphate, expandable graphite, a water scavenger and optional other additives are uniformly mixed in a double-planetary stirring kettle, and are discharged after being stirred and dispersed for 30 minutes by opening vacuum to increase the rotating speed, so that the coating compositions of the examples 1-6, 8-15 and the comparative examples 1-3 and 5-16 are obtained, and are filled and stored for later use, and the coating compositions of the examples are uniform in appearance and thick in texture.
Propylene glycol methyl ether acetate (PMA) was further added according to the components and contents shown in example 7 of table 1, and stirred to obtain the coating composition of example 7 of the present invention, which was filled and stored for use.
Comparative example 4 is a two-component coating system requiring that commercial solvent borne polyurethane 2 and Desmodur RFE be mixed well before use and used over a period of hours.
Preparation of refractory coatings
Refractory coatings of examples 1-6, 8-15 and comparative examples
The coating composition or the two-component coating system is uniformly coated on the surface of a flame-retardant Polycarbonate (PC) plate by scraping, the thickness of the coating on the surface of the plate is controlled to be about 0.25mm, and the flame-retardant coating is obtained after curing for 1 day at room temperature.
Example 7 refractory coating
The coating composition of example 7 was gently stirred and uniformly sprayed on the surface of a flame retardant Polycarbonate (PC) plate using a rock Tian Penqiang W-71 having a caliber of 2mm, and dried in an oven at 80℃for 10 minutes at a dry film thickness of 0.1 mm. And cooling, spraying for the second time, drying the dry film with the thickness of 0.15mm in an oven at 80 ℃ for 10 minutes, taking out, standing and solidifying at room temperature to obtain the fireproof coating with the thickness of 0.25mm.
Evaluation of Performance
Storage stability: and (3) sealing and storing the prepared coating composition or system in a rubber tube, placing in a 50 ℃ oven for 4 weeks, taking out, cooling, checking whether the coating composition or system is solidified, and if not, testing the extrusion rate according to the method of the invention, wherein the extrusion rate is required to be greater than or equal to 80ml/min, and the storage stability is qualified.
Extrusion rate: according to GB/T13477.3-2017, the coating composition or coating system in sealed package is placed into a pneumatic gun, 200KPa air pressure is connected and kept stable, the gun nozzle is opened for 1cm, the composition is extruded for 2-3cm before testing, a sample of the coating composition is extruded by compressed air at one time during testing, and the extrusion rate is calculated according to the volume and extrusion time of the extruded sample, and is accurate to 1ml/min. The extrusion rate of the sample is required to be more than or equal to 80ml/min and is qualified.
Sag resistance: according to GB/T13477.6-2002, sagging molds for testing are washed with acetone solvent and dried, polyethylene strips are lined at the bottom of the mold so as to cover the upper edge of the mold and to be fixed at the outside, and a sample of the coating composition or coating system is filled into the mold with a doctor blade to avoid the formation of bubbles, compaction, and horizontal sagging and vertical sagging of the coating composition or system, respectively, are tested. Horizontal vertical flow: horizontally placing the die in a 50 ℃ oven for 24 hours, and taking out and cooling the die; the distance the coating composition or system extends in the horizontal direction, measured with a steel ruler, is noted as horizontal sag. Vertical flow: vertically hanging the die in an oven with the temperature of 50 ℃ for 24 hours, and taking out and cooling the die; the distance the coating composition or system extends downward, measured with a steel ruler, is noted as vertical sag. It is required that both the horizontal and vertical drafts are not more than 3mm as acceptable.
Surface drying time: according to the B method of GB/T13477.5-2002, a coating composition sample or a system sample is placed in a standard state (23 ℃ and 50% RH) for 10 minutes, the end of a finger is wiped by absolute ethyl alcohol, three different parts on a test piece are lightly contacted, the operation is repeated until no test piece is stuck to the finger, the time from coating to non-sticking is recorded as the surface dry time, and the surface dry time is required to be less than 4 hours to be qualified.
Adhesion force: after the refractory coating was left at room temperature for 7 days, it was tested by drawing a 10mm x 10mm grid on the surface of the coating with a knife, requiring deep drawing onto the substrate surface, and checking whether the coating could fall off or be torn off. It is desirable that the coating be fully adhered to the substrate and that the substrate bottom be acceptable without revealing. When the adhesion of the coating formed by the coating composition or system is unacceptable, the flame retardancy and whether the coating falls off during combustion are no longer tested.
Flame retardancy: the prepared fire-resistant coating is tested after being placed for 7 days at room temperature according to the combustion standard of UL94, and the blue flame is aligned to the lower part of the fire-resistant coating to be continuously combusted for 5 minutes by using methane gas with the flow of 500W, and if the base material is not burnt, the fire resistance of the coating is qualified. The flame retardancy of the coating is considered unacceptable when the substrate burns through. And observing whether the coating falls off or not in the combustion process, and more preferably if the coating does not fall off.
Whether or not it is easy to apply: examples 1-6, 8-15 and comparative examples a film sheet having a thickness of 0.25mm was attached to both sides of a substrate, and a doctor blade was used to blade-coat a coating composition or system. The coating composition of example 7 was spray-applied to a coating thickness of 0.25.+ -. 0.01mm. The coating composition or system is required to be continuous, not break or spread hard during the blade coating or spraying process. If the coating composition or system is difficult to spread and broken, the coating composition or system is difficult to coat or spray. When the coating composition or system is not easily applied or sprayed, it is no longer tested for adhesion, flame retardancy and whether the coating falls off during combustion.
Whether the paint damages the substrate or not: after the coating is finished for 7 days, the existence of deformation, discoloration and cracking and undercut phenomena of the base material are observed visually, if one of the phenomena is generated, the base material is judged to be damaged by the coating composition or the system, and if the phenomenon is not generated, the base material is judged to be not damaged by the coating composition or the system.
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The coating compositions of examples 1-7 have good extrusion rates, good sag resistance, fast open time and good storage stability, the coating compositions are easy to apply or spray, and do not damage the substrate; the coating formed by the coating composition has good adhesive force, flame retardance and no falling off after preheating.
Comparative example 1 is a commercially available flame retardant polycarbonate substrate, the surface of which is uncoated and the substrate is burned through in less than 3 minutes of continuous combustion.
Comparative example 2 is a commercially available one-component solvent-based neoprene resin, the coating is not easily applied, the solvent therein erodes the substrate surface, causing cracking and bending deformation of the substrate surface, and the coating is damaging to the substrate.
Comparative example 3 is a commercially available one-component solvent polyurethane resin, the solvent in the coating erodes the substrate surface, causing cracking and bending deformation of the substrate surface, and the coating damages the substrate.
Comparative example 4 is a commercially available two-component solvent-based polyurethane resin system in which the solvent erodes the substrate surface, causing cracking and bending deformation of the substrate surface, and the coating system damages the substrate.
The polyurethane prepolymers of comparative examples 5-6 have an isocyanate group content greater than 14% and the coating compositions form coatings that fail adhesion to the substrate. The polyurethane prepolymer of comparative example 7 has an isocyanate group content of less than 2.5% by weight, and the coating composition is difficult to continuously coat on the substrate surface.
The coating compositions of comparative examples 8-9 contained only the aliphatic isocyanate-based polyurethane prepolymer, and the substrate containing the coating formed from the comparative coating composition was burned through, failing the flame retardancy. The polyurethane prepolymer of the coating composition of comparative example 10 comprised 50% by weight of an aromatic isocyanate-based polyurethane prepolymer and 50% by weight of an aliphatic isocyanate-based polyurethane prepolymer, and the substrate comprised of the coating formed from the comparative coating composition was burned through, failing the flame retardancy.
The coating composition of comparative example 11 included a polyurethane prepolymer, pentaerythritol, ammonium polyphosphate, and a water scavenger, and the coating composition failed to meet storage stability requirements. The storage stability of the expandable graphite of example 1 in combination with polyurethane prepolymer, ammonium polyphosphate and water scavenger is significantly better than the combination of comparative example 11.
TABLE 2 compositions and coating Properties of the coating compositions of examples 1, 8-9 and comparative examples 12-13
Remarks: the weight ratio refers to the ratio of the weight of the polyurethane prepolymer to the sum of the weights of the expandable graphite and ammonium polyphosphate; the weight ratio of 2 refers to the weight ratio of expandable graphite and ammonium polyphosphate.
Comparative examples 12 to 13 used ammonium polyphosphate with physically coated or chemically treated surface, and examples 1 and 8 to 9 used ammonium polyphosphate with untreated surface. The coating compositions of comparative examples 12-13 failed to have satisfactory storage stability, and the coating compositions of example 1 and examples 8-9 were significantly better evaluated for various properties than those of comparative examples 12-13.
TABLE 3 composition and coating Properties of the coating compositions of examples 1, 10-11 and comparative examples 14-15
Remarks: weight ratio 1 refers to the ratio of the weight of polyurethane prepolymer to the sum of the weight of expandable graphite and ammonium polyphosphate; weight ratio 2 refers to the weight ratio of expandable graphite to ammonium polyphosphate; "/" indicates no test.
The ratio of the weight of the polyurethane prepolymer to the sum of the weights of the expandable graphite and the ammonium polyphosphate of comparative example 14 was 3/7, and the coating composition was difficult to apply and was not easy to uniformly continue. The ratio of the weight of the polyurethane prepolymer to the sum of the weights of the expandable graphite and ammonium polyphosphate of comparative example 15 was 7/3, and the flame retardancy of the coating composition was poor. Each performance evaluation of the coating compositions of example 1 and examples 10-11 was satisfactory.
TABLE 4 composition and coating Properties of the coating compositions of examples 1, 12-15 and comparative example 16
Remarks: weight ratio 1 refers to the ratio of the weight of polyurethane prepolymer to the sum of the weight of expandable graphite and ammonium polyphosphate; weight ratio 2 refers to the weight ratio of expandable graphite to ammonium polyphosphate; "/" indicates no test.
The coating composition of comparative example 16 had a weight ratio of expandable graphite to ammonium polyphosphate of 33/558 and was not uniformly and continuously applied. The coating compositions of example 1 and examples 12-15 had a weight ratio of expandable graphite to ammonium polyphosphate of between 1/10 and 4/1, and the coating composition had significantly better coating properties than comparative example 16. Also, according to examples 1 and 15, when the weight ratio of the expandable graphite of the coating composition to the ammonium polyphosphate is between 1/7 and 1/2, the coating layer formed by the coating composition does not fall off upon heat.
It will be evident to those skilled in the art that the invention is not limited to the precise details set forth, and that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (15)
1. A coating composition comprising the following components:
a. a polyurethane prepolymer comprising 60% to 100% by weight of a polyurethane prepolymer based on aromatic isocyanate and 0 to 40% by weight of a polyurethane prepolymer based on aliphatic and/or cycloaliphatic isocyanate, in each case based on 100% by weight relative to the total weight of the polyurethane prepolymer;
b. expandable graphite;
c. surface untreated ammonium polyphosphate;
d. a water scavenger; and
e. optionally not more than 35% by weight of solvent, in each case calculated as 100% by weight relative to the total weight of the composition;
the isocyanate group content of the polyurethane prepolymer of component a) is 2.5% to 14% by weight, relative to the total weight of the solid components of the polyurethane prepolymer of component a); the amount of the polyurethane prepolymer a) is from 20 to 50% by weight, in each case based on 100% by weight of the total weight of the composition; the expandable graphite b) is present in an amount of from 10 to 25% by weight, in each case based on 100% by weight, relative to the total weight of the composition; the amount of surface-untreated ammonium polyphosphate c) is from 15 to 45% by weight, based in each case on 100% by weight, based on the total 100 parts by weight of the composition; the amount of the component d) water scavenger is 0.1% to 5% by weight, in each case relative to 100% by weight of the total weight of the composition; the weight ratio of the polyurethane prepolymer of the component a) to the sum of the weight of the expandable graphite of the component b) and the weight of the ammonium polyphosphate untreated on the surface of the component c) is 1/2 to 2/1, and the weight ratio of the expandable graphite of the component b) to the ammonium polyphosphate untreated on the surface of the component c) is 1/10 to 4/1.
2. The composition of claim 1 wherein the ratio of the weight of the polyurethane prepolymer of component a) to the sum of the weight of the expandable graphite of component b) and the surface untreated ammonium polyphosphate of component c) is 7/13 to 3/2.
3. The composition according to claim 1 or 2, characterized in that the aromatic isocyanate-based polyurethane prepolymer is one or more of the following: polyurethane prepolymers based on diphenylmethane diisocyanate and polyurethane prepolymers based on toluene diisocyanate.
4. A composition according to any one of claims 1 to 3, characterized in that the aliphatic and/or cycloaliphatic isocyanate-based polyurethane prepolymer is one or more of the following: polyurethane prepolymers based on isophorone diisocyanate and polyurethane prepolymers based on hexamethylene diisocyanate.
5. The composition of any one of claims 1-4, wherein the expandable graphite is at least one of the following:
i. the particle size is 10-100 meshes, and the particle size is tested according to GB 10698-89; and
ii expansion ratio of 200ml/g-400ml/g, expansion ratio according to GB 10698-89 test.
6. The composition of any one of claims 1-5, wherein the expandable graphite is flake graphite.
7. The composition of any one of claims 1-6, wherein the surface untreated ammonium polyphosphate meets at least one of the following characteristics:
A. a phosphorus content of not less than 25% by weight relative to the total weight of the ammonium polyphosphate;
B. particle size of 1 μm-100 μm, and the particle size is measured by laser diffraction method;
C. decomposition temperature not lower than 275 ℃, and according to GB/T13464-92 test; and
D. the degree of polymerization is greater than 1000, and the degree of polymerization is measured according to nuclear magnetic resonance.
8. Composition according to any one of claims 1 to 7, characterized in that the weight ratio of expandable graphite to surface untreated ammonium polyphosphate is 1/7-2/1, most preferably 1/7-1/2.
9. The composition according to any one of claims 1 to 8, wherein the water scavenger is one or more of the following: vinyl trimethoxy silane, phenyl isocyanate and triethyl orthosilicate.
10. The composition according to any one of claims 1 to 9, wherein the solvent is an active hydrogen free solvent, most preferably an ether ester having a boiling point in the range of 100 ℃ to 180 ℃.
11. Use of a coating composition according to any one of claims 1-10 for slowing or preventing the spread of flame or heat generated by an object.
12. A coating method comprising the steps of: application of a coating composition according to any of claims 1-10 to an object and/or to the surface of a storage bin of an object, followed by curing.
13. An article comprising an object and a coating layer formed by curing the coating composition according to any one of claims 1-10 applied to the object and/or the storage bin of the object.
14. The article according to claim 13, wherein the object is a flammable object, further preferably from a battery, a train chassis, an automobile chassis and doors and windows, most preferably an automobile battery.
15. Article according to claim 13, characterized in that the storage bin of objects is a storage bin of inflammable objects, further preferably a battery bin, further preferably an automotive battery bin, most preferably one or more of the following: the upper cover of the automobile battery box, the lower cover of the automobile battery box and the bonding parts of all parts of the automobile battery box.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011610724.XA CN114686083A (en) | 2020-12-29 | 2020-12-29 | Coating composition |
| CN202011610724X | 2020-12-29 | ||
| EP21160165.3A EP4053184A1 (en) | 2021-03-02 | 2021-03-02 | Coating composition |
| EP21160165.3 | 2021-03-02 | ||
| PCT/EP2021/087516 WO2022144305A1 (en) | 2020-12-29 | 2021-12-23 | Coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116829615A true CN116829615A (en) | 2023-09-29 |
Family
ID=79730321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180088178.4A Pending CN116829615A (en) | 2020-12-29 | 2021-12-23 | Coating composition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN116829615A (en) |
| WO (1) | WO2022144305A1 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3095809A1 (en) * | 2015-05-21 | 2016-11-23 | HILTI Aktiengesellschaft | Foamable, multi-component composition forming an insulating layer and its use |
-
2021
- 2021-12-23 CN CN202180088178.4A patent/CN116829615A/en active Pending
- 2021-12-23 WO PCT/EP2021/087516 patent/WO2022144305A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022144305A1 (en) | 2022-07-07 |
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