CN111777887A - Flame-retardant heat-resistant waterborne polyurethane coating and preparation method thereof - Google Patents
Flame-retardant heat-resistant waterborne polyurethane coating and preparation method thereof Download PDFInfo
- Publication number
- CN111777887A CN111777887A CN202010724224.2A CN202010724224A CN111777887A CN 111777887 A CN111777887 A CN 111777887A CN 202010724224 A CN202010724224 A CN 202010724224A CN 111777887 A CN111777887 A CN 111777887A
- Authority
- CN
- China
- Prior art keywords
- parts
- weight
- flame
- retardant
- polyurethane coating
- 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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- 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 title claims abstract description 80
- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 49
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004970 Chain extender Substances 0.000 claims abstract description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 ether polyol Chemical class 0.000 claims abstract description 27
- 229920000728 polyester Polymers 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- 229940070527 tourmaline Drugs 0.000 claims abstract description 14
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 14
- 239000011032 tourmaline Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011324 bead Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 11
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 10
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010451 perlite Substances 0.000 claims abstract description 10
- 235000019362 perlite Nutrition 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 229920002545 silicone oil Polymers 0.000 claims abstract description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229920005906 polyester polyol Polymers 0.000 claims description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 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 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 4
- 229940083037 simethicone Drugs 0.000 claims description 4
- 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 3
- RATPJCIXMZJVFK-UHFFFAOYSA-N 3-amino-1-(N-[2-(hydrazinecarbonylhydrazinylidene)hydrazinyl]anilino)-1-phenylurea Chemical compound C1(=CC=CC=C1)N(N(N=NNNC(=O)NN)C1=CC=CC=C1)C(=O)NN RATPJCIXMZJVFK-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000004321 preservation Methods 0.000 description 4
- 238000010074 rubber mixing Methods 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000417 polynaphthalene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/5078—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a flame-retardant heat-resistant waterborne polyurethane coating which is prepared from a prepolymer and a dispersing agent, wherein the mass ratio of the prepolymer to the dispersing agent is (3-5): 1-2; the prepolymer is prepared from the following raw materials; polytetrahydrofuran ether glycol, flame-retardant polyester ether polyol, diisocyanate, dimethyl silicone oil, a micromolecule chain extender, acetone, hollow glass beads and a filler; the dispersing agent comprises a hydrophilic chain extender, a defoaming agent, deionized water and ethylenediamine. The invention also discloses a preparation method of the waterborne polyurethane coating, wherein the flame-retardant polyester ether polyol and the filler are added into the raw materials, the flame-retardant polyester ether polyol contains benzene ring groups and phosphorus flame-retardant elements, so that the coating is endowed with excellent flame-retardant performance, the filler comprises tourmaline powder, talcum powder, kaolin and expanded perlite, and the filler has a strong specific surface area and a surface multi-medium open pore structure, so that the heat conductivity coefficient of the waterborne polyurethane coating is reduced, and the flame-retardant capability of the waterborne polyurethane coating is further improved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a flame-retardant heat-resistant waterborne polyurethane coating and a preparation method thereof.
Background
Polyurethane coatings are the common coatings at present and can be divided into two-component polyurethane coatings and one-component polyurethane coatings. The paint has a plurality of varieties and wide application range, generally has good mechanical property, higher solid content and better performances in all aspects, is a paint variety with development prospect at present, and has main application directions of wood paints, automobile repair paints, anticorrosive paints, floor paints, electronic paints, special paints, polyurethane waterproof paints and the like. The disadvantages are that the construction process is complex, the requirement on the construction environment is high, and the paint film is easy to generate defects. The single-component polyurethane coating mainly comprises urethane oil coating, moisture-cured polyurethane coating, closed polyurethane coating and the like. The coating has a wider application range than a two-component coating, is mainly used for floor coatings, anticorrosive coatings, pre-roll coatings and the like, and has less overall performance than the two-component coating.
The waterborne polyurethane coating is the most ideal waterborne coating at present, but the comprehensive performances such as chemical resistance, water resistance, wear resistance, high temperature resistance and the like of the waterborne polyurethane coating are poorer in domestic research. In the prior art, the first three performances are mostly researched, and the research on the high temperature resistance is less. With the development of science and technology in recent years, people have increasingly increased demands for heat-resistant and flame-retardant water-based paint, and how to prepare flame-retardant and heat-resistant water-based paint becomes a technical problem to be solved at present.
Disclosure of Invention
The invention aims to provide a flame-retardant heat-resistant waterborne polyurethane coating and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
in the prior art, the water-based polyurethane coating has poor heat resistance, potential safety hazards exist when the water-based polyurethane coating is applied to the fields of building materials, textiles, leather and the like, the flame retardant property of the existing flame-retardant polyurethane coating is improved by introducing halogen groups, toxic and harmful substances are easy to generate, and the water-based flame-retardant polyurethane coating is single in property, poor in toughness and poor in wear resistance.
The purpose of the invention can be realized by the following technical scheme:
the flame-retardant heat-resistant waterborne polyurethane coating is prepared from a prepolymer and a dispersing agent, wherein the mass ratio of the prepolymer to the dispersing agent is (3-5): 1-2;
the prepolymer is prepared from the following raw materials: 20-25 parts of polytetrahydrofuran ether glycol, 25-30 parts of flame-retardant polyester ether polyol, 10-20 parts of diisocyanate, 2-5 parts of dimethyl silicone oil, 1-2 parts of small molecular chain extender, 60-80 parts of acetone, 2-4 parts of hollow glass beads and 3-8 parts of filler;
the dispersing agent is prepared from the following raw materials: 2-6 parts of hydrophilic chain extender, 0.1-0.8 part of defoaming agent, 25-35 parts of deionized water and 0.1-1.5 parts of ethylenediamine;
the preparation method of the flame-retardant heat-resistant waterborne polyurethane coating comprises the following steps:
firstly, putting 20-25 parts by weight of polytetrahydrofuran ether glycol and 25-30 parts by weight of flame-retardant polyester ether polyol into a reaction kettle, uniformly stirring, heating to 100-115 ℃, dehydrating in vacuum under the condition of-0.1 MPa until the water content is below 0.04%, putting 10-20 parts by weight of diisocyanate, heating to 85-95 ℃, carrying out heat preservation reaction for 1-3h, and cooling to 40 ℃ to obtain a mixture A;
secondly, adding 2-5 parts by weight of dimethyl silicone oil, 1-2 parts by weight of micromolecule chain extender and 60-80 parts by weight of acetone into the mixture A, heating to 50-55 ℃, uniformly stirring and mixing, then adding 2-4 parts by weight of hollow glass beads and 3-8 parts by weight of filler, and stirring for 3-5 hours to obtain a prepolymer;
thirdly, transferring the prepolymer into an emulsifier, adding 25-35 parts by weight of deionized water and 0.1-1.5 parts by weight of ethylenediamine into the prepolymer under the high-speed stirring of 1000-1500r/min, continuing to stir for 5min, then adjusting the rotating speed to 400-600r/min, adding 2-6 parts by weight of hydrophilic chain extender, and continuing to stir for 3-5h to obtain a mixture B;
and fourthly, removing acetone from the mixture B at the temperature of 40-45 ℃ and under the pressure of-0.09 MPa, adding 0.1-0.8 part by weight of defoaming agent, and uniformly stirring to obtain the flame-retardant heat-resistant waterborne polyurethane coating.
The diisocyanate is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI) and Hexamethylene Diisocyanate (HDI) which are mixed in any proportion.
The preparation method of the flame-retardant polyester ether polyol comprises the following steps:
s1, mixing pyromellitic dianhydride, diethylene glycol and dibutyl tin oxide according to the mass ratio of 1-3: 2-5, 0.01-0.05, mixing and stirring under the protection of nitrogen, heating to 140 ℃ for reaction for 2-4h, wherein dibutyltin oxide is used as a catalyst, heating to 240 ℃ for reaction for 2-3h, then performing suction filtration for 2.5-3.5h, cooling to 65-80 ℃, and discharging to obtain a product, namely the pyromellitic acid polyester polyol;
s2, putting the pyromellitic acid polyester polyol and phosphorus oxychloride into a reactor according to the mass ratio of 1:3-5, controlling the temperature to be 60-80 ℃, reacting for 2-3h, finally heating to 100 ℃ and keeping the temperature at 120 ℃ for 3-4h, cooling, filtering, washing and drying to obtain pyromellitic acid flame-retardant polyester polyol;
s3, putting the pyromellitic acid flame-retardant polyester polyol and ethylenediamine into a reaction kettle according to the mass ratio of 1:0.05-0.1, taking the ethylenediamine as a catalyst, then putting propylene oxide which is 0.5-1 times of the mass of the pyromellitic acid polyester polyol into the reaction kettle, slowly heating to the temperature of 100-.
The micromolecule chain extender is one or a mixture of more than one of 1, 4-butanediol, glycol and diglycol in any proportion.
The filler comprises 3-5 parts by weight of tourmaline powder, 15-20 parts by weight of talcum powder, 10-15 parts by weight of kaolin and 5-10 parts by weight of expanded perlite.
The hydrophilic chain extender is one or a mixture of two of dimethylolpropionic acid, dimethylolbutyric acid and 1, 2-dihydroxy-3-sodium propane sulfonate.
The defoaming agent is prepared by the following method: mixing 1.5-3 parts by weight of dimethyl sulfoxide, 2-3 parts by weight of diphenyl azo carbohydrazide, 1-2 parts by weight of sodium tripolyphosphate, 3-7 parts by weight of sodium polynaphthalene formaldehyde sulfonate and 3-5 parts by weight of polyethylene glycol through a rubber mixing mill, and then extruding and granulating to obtain the polyethylene glycol.
The invention has the beneficial effects that:
1. the flame-retardant heat-resistant waterborne polyurethane coating disclosed by the invention has the advantages that the flame-retardant polyester ether polyol is added into the raw materials, and the flame-retardant polyester ether polyol contains benzene ring groups and phosphorus flame-retardant elements, so that the coating is endowed with excellent flame-retardant performance; and the dimethyl silicone oil is added into the system, and the formed polymer can gradually penetrate into polyurethane macromolecules to form a block or graft structure, so that the length of a molecular chain is increased, and the intermolecular force is improved.
2. The matching of the hollow glass microspheres, the tourmaline powder, the talcum powder, the kaolin and the expanded perlite in the coating greatly improves the consistency and the touch resistance of the coating, so that the coating has excellent strength, toughness, wear resistance and corrosion resistance during curing; tourmaline powder, talcum powder, kaolin and expanded perlite have strong specific surface area and a surface multi-medium open pore structure, so that the tourmaline powder has strong adsorption capacity, harmful dust in air is adsorbed after the tourmaline powder is solidified, negative ions are released by the tourmaline, the air is further purified, and the heat conductivity coefficient is reduced due to the internal porous structures of the tourmaline powder, the talcum powder, the kaolin and the expanded perlite, so that the flame retardant capacity of the tourmaline powder is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The flame-retardant heat-resistant waterborne polyurethane coating is prepared from a prepolymer and a dispersing agent, wherein the mass ratio of the prepolymer to the dispersing agent is 3: 1;
the prepolymer is prepared from the following raw materials: 20 parts of polytetrahydrofuran ether glycol, 25 parts of flame-retardant polyester ether polyol, 10 parts of diisocyanate, 2 parts of dimethyl silicone oil, 1 part of micromolecular chain extender, 60 parts of acetone, 2 parts of hollow glass beads and 3 parts of filler;
the dispersing agent is prepared from the following raw materials: 2 parts by weight of a hydrophilic chain extender, 0.1 part by weight of a defoaming agent, 25 parts by weight of deionized water and 0.1 part by weight of ethylenediamine;
the preparation method of the flame-retardant heat-resistant waterborne polyurethane coating comprises the following steps:
step one, putting 20 parts by weight of polytetrahydrofuran ether glycol and 25 parts by weight of flame-retardant polyester ether polyol into a reaction kettle, uniformly stirring, heating to 100 ℃, carrying out vacuum dehydration under the condition of-0.1 MPa until the water content is 0.03%, putting 10 parts by weight of diisocyanate, heating to 85 ℃, carrying out heat preservation reaction for 1 hour, and cooling to 40 ℃ to obtain a mixture A;
secondly, adding 2 parts by weight of dimethyl silicone oil, 1 part by weight of micromolecule chain extender and 60 parts by weight of acetone into the mixture A, heating to 50 ℃, uniformly stirring and mixing, then adding 2 parts by weight of hollow glass beads and 3 parts by weight of filler, and stirring for 3 hours to obtain a prepolymer;
thirdly, transferring the prepolymer into an emulsifier, adding 25 parts by weight of deionized water and 0.1 part by weight of ethylenediamine into the prepolymer under the high-speed stirring of 1000r/min, continuing to stir for 5min, then adjusting the rotation speed to 400r/min, adding 2 parts by weight of hydrophilic chain extender, and continuing to stir for 3h to obtain a mixture B;
and fourthly, removing acetone from the mixture B at the temperature of 40 ℃ and under the pressure of-0.09 MPa, adding 0.1 part by weight of defoaming agent, and uniformly stirring to obtain the flame-retardant heat-resistant waterborne polyurethane coating.
The diisocyanate is a mixture of Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI) in any proportion.
The preparation method of the flame-retardant polyester ether polyol comprises the following steps:
s1, mixing pyromellitic dianhydride, diethylene glycol and dibutyl tin oxide according to the mass ratio of 1: 2:0.01, mixing and stirring under the protection of nitrogen, heating to 120 ℃, reacting for 2 hours, heating to 220 ℃, reacting for 2 hours, then performing suction filtration for 2.5 hours, cooling to 65 ℃, discharging, and obtaining a product, namely the pyromellitic polyester polyol;
s2, putting the pyromellitic acid polyester polyol and phosphorus oxychloride into a reactor according to the mass ratio of 1:3, controlling the temperature to be 60 ℃, reacting for 2 hours, finally heating to 100 ℃, preserving the temperature for 3 hours, cooling, filtering, washing and drying to obtain pyromellitic acid flame-retardant polyester polyol;
s3, putting the pyromellitic acid flame-retardant polyester polyol and ethylenediamine into a reaction kettle according to the mass ratio of 1:0.05, then putting epoxypropane with the mass of 0.5 time that of the pyromellitic acid polyester polyol into the reaction kettle, slowly heating to 100 ℃, keeping the pressure in the reaction kettle at 0.1MPa, reacting for 2 hours at the temperature and the pressure, vacuumizing, and carrying out filter pressing and discharging when the temperature is reduced to 80 ℃ to obtain the pyromellitic acid flame-retardant polyester ether polyol.
The micromolecular chain extender is 1, 4-butanediol.
The filler comprises 3 parts by weight of tourmaline powder, 15 parts by weight of talcum powder, 10 parts by weight of kaolin and 5 parts by weight of expanded perlite.
The hydrophilic chain extender is a mixture of dimethylolpropionic acid and dimethylolbutyric acid in any proportion.
The defoaming agent is prepared by the following method: mixing 1.5 parts by weight of dimethyl sulfoxide, 2 parts by weight of diphenyl azo carbohydrazide, 1 part by weight of sodium tripolyphosphate, 3 parts by weight of sodium polynaphthalenesulfonate and 3 parts by weight of polyethylene glycol through a rubber mixing mill, and then extruding and granulating to obtain the polyethylene glycol.
Example 2
The flame-retardant heat-resistant waterborne polyurethane coating comprises a prepolymer and a dispersing agent, wherein the mass ratio of the prepolymer to the dispersing agent is 4: 1;
the prepolymer comprises 23 parts by weight of polytetrahydrofuran ether glycol, 28 parts by weight of flame-retardant polyester ether polyol, 15 parts by weight of diisocyanate, 3 parts by weight of simethicone, 1.5 parts by weight of micromolecule chain extender, 70 parts by weight of acetone, 3 parts by weight of hollow glass beads and 5 parts by weight of filler;
the dispersing agent comprises 4 parts by weight of hydrophilic chain extender, 0.5 part by weight of defoaming agent, 30 parts by weight of deionized water and 1 part by weight of ethylenediamine;
the preparation method of the flame-retardant heat-resistant waterborne polyurethane coating comprises the following steps:
step one, putting 23 parts by weight of polytetrahydrofuran ether glycol and 28 parts by weight of flame-retardant polyester ether polyol into a reaction kettle, uniformly stirring, heating to 113 ℃, carrying out vacuum dehydration under the condition of-0.1 MPa until the water content is 0.02%, putting 15 parts by weight of diisocyanate, heating to 85-95 ℃, carrying out heat preservation reaction for 1.5h, and cooling to 40 ℃ to obtain a mixture A;
secondly, adding 3 parts by weight of simethicone, 1.5 parts by weight of micromolecule chain extender and 70 parts by weight of acetone into the mixture A, heating to 53 ℃, stirring and mixing uniformly, adding 3 parts by weight of hollow glass beads and 5 parts by weight of filler, and stirring for 4 hours to obtain a prepolymer;
thirdly, transferring the prepolymer into an emulsifier, adding 30 parts by weight of deionized water and 0.8 part by weight of ethylenediamine into the prepolymer under the high-speed stirring of 1200r/min, continuing to stir for 5min, then adjusting the rotation speed to 500r/min, adding 4 parts by weight of hydrophilic chain extender, and continuing to stir for 4h to obtain a mixture B;
and fourthly, removing acetone from the mixture B at the temperature of 43 ℃ and under the pressure of-0.09 MPa, adding 0.5 part by weight of defoaming agent, and uniformly stirring to obtain the flame-retardant heat-resistant waterborne polyurethane coating.
The diisocyanate is Toluene Diisocyanate (TDI).
The preparation method of the flame-retardant polyester ether polyol comprises the following steps:
s1, mixing pyromellitic dianhydride, diethylene glycol and dibutyl tin oxide according to the mass ratio of 2: 3:0.03, mixing and stirring under the protection of nitrogen, heating to 130 ℃, reacting for 3 hours, then heating to 230 ℃, reacting for 2.5 hours, then performing suction filtration for 3 hours, cooling to 70 ℃, discharging, and obtaining a product, namely the pyromellitic polyester polyol;
s2, putting the pyromellitic polyester polyol and phosphorus oxychloride into a reactor according to the mass ratio of 1:4, controlling the temperature to be 70 ℃, reacting for 2.5 hours, finally heating to 110 ℃, preserving the temperature for 3.5 hours, cooling, filtering, washing and drying to obtain pyromellitic flame-retardant polyester polyol;
s3, putting the pyromellitic acid flame-retardant polyester polyol and ethylenediamine into a reaction kettle according to the mass ratio of 1:0.05, then putting epoxypropane with the mass of 0.6 time that of the pyromellitic acid polyester polyol into the reaction kettle, slowly heating to 120 ℃, keeping the pressure in the reaction kettle at 0.15MPa, reacting for 3 hours at the temperature and the pressure, vacuumizing, and carrying out filter pressing and discharging when the temperature is reduced to 80 ℃ to obtain the pyromellitic acid flame-retardant polyester ether polyol.
The micromolecular chain extender is 1, 4-butanediol.
The filler comprises 4 parts by weight of tourmaline powder, 18 parts by weight of talcum powder, 12 parts by weight of kaolin and 7 parts by weight of expanded perlite.
The hydrophilic chain extender is a mixture of dimethylolpropionic acid and dimethylolbutyric acid in any proportion.
The defoaming agent is prepared by the following method: mixing 1.8 parts by weight of dimethyl sulfoxide, 3 parts by weight of diphenyl azo carbohydrazide, 2 parts by weight of sodium tripolyphosphate, 4 parts by weight of sodium polynaphthalenesulfonate and 4 parts by weight of polyethylene glycol through a rubber mixing mill, and then extruding and granulating to obtain the polyethylene glycol.
Example 3
The flame-retardant heat-resistant waterborne polyurethane coating comprises a prepolymer and a dispersing agent, wherein the mass ratio of the prepolymer to the dispersing agent is 5: 2;
the prepolymer comprises 25 parts by weight of polytetrahydrofuran ether glycol, 30 parts by weight of flame-retardant polyester ether polyol, 20 parts by weight of diisocyanate, 5 parts by weight of simethicone, 2 parts by weight of micromolecule chain extender, 80 parts by weight of acetone, 4 parts by weight of hollow glass beads and 8 parts by weight of filler;
the dispersing agent comprises 6 parts by weight of hydrophilic chain extender, 0.8 part by weight of defoaming agent, 35 parts by weight of deionized water and 1.5 parts by weight of ethylenediamine;
the preparation method of the flame-retardant heat-resistant waterborne polyurethane coating comprises the following steps:
firstly, putting 25 parts by weight of polytetrahydrofuran ether glycol and 30 parts by weight of flame-retardant polyester ether polyol into a reaction kettle, uniformly stirring, heating to 115 ℃, carrying out vacuum dehydration under the condition of-0.1 MPa until the water content is 0.03%, putting 20 parts by weight of diisocyanate, heating to 95 ℃, carrying out heat preservation reaction for 3 hours, and cooling to 40 ℃ to obtain a mixture A;
secondly, adding 5 parts by weight of dimethyl silicone oil, 2 parts by weight of micromolecular chain extender and 80 parts by weight of acetone into the mixture A, heating to 55 ℃, uniformly stirring and mixing, adding 4 parts by weight of hollow glass beads and 8 parts by weight of filler, and stirring for 5 hours to obtain a prepolymer;
thirdly, transferring the prepolymer into an emulsifier, adding 35 parts by weight of deionized water and 1.5 parts by weight of ethylenediamine into the prepolymer under the high-speed stirring of 1500r/min, continuing to stir for 5min, then adjusting the rotation speed to 600r/min, adding 6 parts by weight of hydrophilic chain extender, and continuing to stir for 5h to obtain a mixture B;
and fourthly, removing acetone from the mixture B at the temperature of 45 ℃ and under the pressure of-0.09 MPa, adding 0.8 part by weight of defoaming agent, and uniformly stirring to obtain the flame-retardant heat-resistant waterborne polyurethane coating.
The diisocyanate is Toluene Diisocyanate (TDI).
The preparation method of the flame-retardant polyester ether polyol comprises the following steps:
s1, mixing pyromellitic dianhydride, diethylene glycol and dibutyl tin oxide according to the mass ratio of 3: 0.05, mixing and stirring under the protection of nitrogen, heating to 140 ℃, reacting for 4 hours, heating to 240 ℃, reacting for 3 hours, then performing suction filtration for 3.5 hours, cooling to 80 ℃, discharging, and obtaining a product, namely the pyromellitic polyester polyol;
s2, putting the pyromellitic acid polyester polyol and phosphorus oxychloride into a reactor according to the mass ratio of 1:5, controlling the temperature to 80 ℃, reacting for 3 hours, finally heating to 120 ℃, preserving the heat for 4 hours, cooling, filtering, washing and drying to obtain pyromellitic acid flame-retardant polyester polyol;
s3, putting the pyromellitic acid flame-retardant polyester polyol and ethylenediamine into a reaction kettle according to the mass ratio of 1:0.1, then putting the same mass of propylene oxide of the pyromellitic acid polyester polyol into the reaction kettle, slowly heating to 130 ℃, keeping the pressure in the reaction kettle at 0.3MPa, reacting for 4 hours at the temperature and the pressure, vacuumizing, and carrying out filter pressing after the temperature is reduced to below 85 ℃, thus obtaining the pyromellitic acid flame-retardant polyester ether polyol.
The micromolecular chain extender is 1, 4-butanediol.
The hydrophilic chain extender is a mixture of dimethylolpropionic acid and dimethylolbutyric acid in any proportion.
The filler comprises 5 parts by weight of tourmaline powder, 20 parts by weight of talcum powder, 15 parts by weight of kaolin and 10 parts by weight of expanded perlite.
The defoaming agent is prepared by the following method: mixing 3 parts by weight of dimethyl sulfoxide, 3 parts by weight of diphenylazocarbohydrazide, 2 parts by weight of sodium tripolyphosphate, 7 parts by weight of sodium polynaphthalene formaldehyde sulfonate and 5 parts by weight of polyethylene glycol through a rubber mixing mill, and then extruding and granulating to obtain the polyethylene glycol.
Comparative example 1
The flame-retardant polyester ether polyol in example 1 was removed and the rest of the preparation process was unchanged.
Comparative example 2
The filler in example 2 was removed and the rest of the preparation was unchanged.
Comparative example 3
The flame retardant polyester ether polyol and filler of example 3 were removed and the remaining preparation was unchanged.
The flame retardant performance of the waterborne polyurethane coatings prepared in examples 1-3 and comparative examples 1-3 in the invention is detected, and the oxygen index is tested according to GB/T2406-1993; carrying out a vertical combustion performance test according to GB/T2408-1994; the test results are shown in the following table:
| test items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Oxygen index/% | 35.7 | 33.4 | 37.6 | 25.3 | 26.1 | 27.4 |
| Total combustion time | 3s | 2s | 3s | 15s | 18s | 30s |
| Flame retardant rating | V-0 | V-0 | V-0 | V-1 | V-1 | V-2 |
The above table shows that the flame-retardant polyester ether polyol and the filler are added into the raw materials of the waterborne polyurethane coating prepared by the invention, the flame-retardant polyester ether polyol contains benzene ring groups and phosphorus flame-retardant elements, so that the coating is endowed with excellent flame-retardant performance, and the filler comprises tourmaline powder, talcum powder, kaolin and expanded perlite which have strong specific surface area and surface multi-medium open pore structure, so that the heat conductivity coefficient of the waterborne polyurethane coating is reduced, and the flame-retardant capability of the waterborne polyurethane coating is further improved.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions may be made in the specific embodiments described by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (8)
1. The flame-retardant heat-resistant waterborne polyurethane coating is characterized by being prepared from a prepolymer and a dispersing agent, wherein the mass ratio of the prepolymer to the dispersing agent is (3-5): 1-2;
the prepolymer is prepared from the following raw materials: 20-25 parts of polytetrahydrofuran ether glycol, 25-30 parts of flame-retardant polyester ether polyol, 10-20 parts of diisocyanate, 2-5 parts of dimethyl silicone oil, 1-2 parts of small molecular chain extender, 60-80 parts of acetone, 2-4 parts of hollow glass beads and 3-8 parts of filler;
the dispersing agent is prepared from the following raw materials: 2-6 parts of hydrophilic chain extender, 0.1-0.8 part of defoaming agent, 25-35 parts of deionized water and 0.1-1.5 parts of ethylenediamine.
2. The flame-retardant heat-resistant aqueous polyurethane coating according to claim 1, wherein the diisocyanate is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), and Hexamethylene Diisocyanate (HDI) mixed in an arbitrary ratio.
3. The flame-retardant heat-resistant waterborne polyurethane coating as claimed in claim 1, wherein the small-molecular chain extender is one or a mixture of 1, 4-butanediol, ethylene glycol and diethylene glycol in any proportion.
4. The flame-retardant heat-resistant waterborne polyurethane coating as claimed in claim 1, wherein the preparation method of the flame-retardant polyester ether polyol comprises the following steps:
s1, mixing pyromellitic dianhydride, diethylene glycol and dibutyl tin oxide according to the mass ratio of 1-3: 2-5, 0.01-0.05, mixing and stirring under the protection of nitrogen, heating to 140 ℃ for reaction for 2-4h, wherein dibutyltin oxide is used as a catalyst, heating to 240 ℃ for reaction for 2-3h, then performing suction filtration for 2.5-3.5h, cooling to 65-80 ℃, and discharging to obtain a product, namely the pyromellitic acid polyester polyol;
s2, putting the pyromellitic acid polyester polyol and phosphorus oxychloride into a reactor according to the mass ratio of 1:3-5, controlling the temperature to be 60-80 ℃, reacting for 2-3h, finally heating to 100 ℃ and keeping the temperature at 120 ℃ for 3-4h, cooling, filtering, washing and drying to obtain pyromellitic acid flame-retardant polyester polyol;
s3, putting the pyromellitic acid flame-retardant polyester polyol and ethylenediamine into a reaction kettle according to the mass ratio of 1:0.05-0.1, taking the ethylenediamine as a catalyst, then putting propylene oxide which is 0.5-1 times of the mass of the pyromellitic acid polyester polyol into the reaction kettle, slowly heating to the temperature of 100-.
5. The flame-retardant heat-resistant waterborne polyurethane coating as claimed in claim 1, wherein the filler comprises 3-5 parts by weight of tourmaline powder, 15-20 parts by weight of talcum powder, 10-15 parts by weight of kaolin and 5-10 parts by weight of expanded perlite.
6. The preparation method of the flame-retardant heat-resistant waterborne polyurethane coating as claimed in claim 1, wherein the method comprises the following steps:
firstly, putting 20-25 parts by weight of polytetrahydrofuran ether glycol and 25-30 parts by weight of flame-retardant polyester ether polyol into a reaction kettle, uniformly stirring, heating to 100-115 ℃, dehydrating in vacuum under the condition of-0.1 MPa until the water content is below 0.04%, putting 10-20 parts by weight of diisocyanate, heating to 85-95 ℃, keeping the temperature for reaction for 1-3h, and cooling to 40 ℃ to obtain a mixture A;
secondly, adding 2-5 parts by weight of simethicone, 1-2 parts by weight of micromolecule chain extender and 60-80 parts by weight of acetone into the mixture A, heating to 50-55 ℃, uniformly stirring and mixing, then adding 2-4 parts by weight of hollow glass beads and 3-8 parts by weight of filler, and stirring for 3-5 hours to obtain a prepolymer;
thirdly, transferring the prepolymer into an emulsifier, adding 25-35 parts by weight of deionized water and 0.1-1.5 parts by weight of ethylenediamine into the prepolymer under the high-speed stirring of 1000-1500r/min, continuing to stir for 5min, then adjusting the rotating speed to 400-600r/min, adding 2-6 parts by weight of hydrophilic chain extender, and continuing to stir for 3-5h to obtain a mixture B;
and fourthly, removing acetone from the mixture B at the temperature of 40-45 ℃ and under the pressure of-0.09 MPa, adding 0.1-0.8 part by weight of defoaming agent, and uniformly stirring to obtain the flame-retardant heat-resistant waterborne polyurethane coating.
7. The flame-retardant heat-resistant aqueous polyurethane coating according to claim 1, wherein the hydrophilic chain extender is one or a mixture of two of dimethylolpropionic acid, dimethylolbutyric acid and sodium 1, 2-dihydroxy-3-propanesulfonate.
8. The flame-retardant heat-resistant aqueous polyurethane coating according to claim 1, wherein the defoaming agent is prepared from 1.5 to 3 parts by weight of dimethyl sulfoxide, 2 to 3 parts by weight of diphenylazocarbohydrazide, 1 to 2 parts by weight of sodium tripolyphosphate, 3 to 7 parts by weight of sodium polynaphthalenesulfonate, and 3 to 5 parts by weight of polyethylene glycol.
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