CN105802436A - Nano expanding type transparent fireproof paint and preparation method thereof - Google Patents
Nano expanding type transparent fireproof paint and preparation method thereof Download PDFInfo
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- CN105802436A CN105802436A CN201610327820.0A CN201610327820A CN105802436A CN 105802436 A CN105802436 A CN 105802436A CN 201610327820 A CN201610327820 A CN 201610327820A CN 105802436 A CN105802436 A CN 105802436A
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- phosphate ester
- grafting
- type transparent
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- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 239000003973 paint Substances 0.000 title abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 128
- 239000010452 phosphate Substances 0.000 claims abstract description 128
- -1 phosphate ester Chemical class 0.000 claims abstract description 126
- 239000011248 coating agent Substances 0.000 claims abstract description 117
- 238000000576 coating method Methods 0.000 claims abstract description 117
- 239000002253 acid Substances 0.000 claims abstract description 110
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 93
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims abstract description 76
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003063 flame retardant Substances 0.000 claims description 123
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 112
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 75
- 239000007864 aqueous solution Substances 0.000 claims description 52
- 229940059574 pentaerithrityl Drugs 0.000 claims description 40
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000011049 filling Methods 0.000 claims description 27
- 230000029936 alkylation Effects 0.000 claims description 25
- 238000005804 alkylation reaction Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 150000007974 melamines Chemical class 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000945 filler Substances 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000004640 Melamine resin Substances 0.000 abstract description 4
- 229920003180 amino resin Polymers 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract 2
- 239000012757 flame retardant agent Substances 0.000 abstract 1
- 239000000779 smoke Substances 0.000 description 41
- 229910052901 montmorillonite Inorganic materials 0.000 description 27
- 239000000047 product Substances 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 15
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 14
- 238000002464 physical blending Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000012512 characterization method Methods 0.000 description 12
- 239000004035 construction material Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000010998 test method Methods 0.000 description 12
- 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 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- 150000001557 benzodiazepines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 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 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C09D5/185—Intumescent paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses nano expanding type transparent fireproof paint and a preparation method thereof.The paint comprises a component A and a component B.The component A contains nano filler grafted phosphate ester acid, and the component B contains melamine resin.The paint has the advantages that nano silicon dioxide and organic montmorillonite are chemically grafted to phosphate ester acid, so that nano filler is evenly dispersed in a coating, and the coating transparency, mobility and compatibility problems caused by physical mixing are effectively avoided.The nano filler, phosphate ester acid and amino resin are introduced into the transparent fireproof paint so as to form a compact expanding carbon layer structure which has a good fireproof protective effect on a base material.Nano silicon dioxide, organic montmorillonite and an expanding flame-retardant agent have a synergistic effect and can obviously improve the fireproof protective effect of an expanding carbon layer.The nano expanding type transparent fireproof paint is wide in raw material resource, low in cost and convenient to operate.
Description
Technical field
The present invention relates to the fire proofing material field of Chemical Engineering Technology, particularly to a kind of nanometer expansion-type transparent fire-retardant coating and preparation method thereof.
Background technology
In today that science and technology is fast-developing, the fields such as modern architecture, ancient building, structural timber are more and more higher to the fire protection requirement of decorative coveringn, and traditional fireproof coating and decorative paint cannot meet modern architecture and the ancient building demand in fire prevention and decoration.Transparent fire-resisting paint can keep the base material texture of engineering structure, character pattern, quality aesthetic feeling, and fire protecting performance is excellent, can be widely applied to the fields such as ancient building, modern architecture, historical relic's protection and high-grade decoration.The fire protecting performance of expansion-type transparent fire-retardant coating relatively non-expansion type more preferably, is the emphasis of research work both at home and abroad at present.
Many reports are had about expansion-type transparent fire-retardant coating.Patent publication No. is the Flexible intumescent transparent fire-resisting paint that the patent documentation of CN104046201A discloses that a kind of flexible phosphate ester acid prepared for raw material with Polyethylene Glycol, polyphosphoric acids, butanediol, tetramethylolmethane is composite with methyl-etherified amino resins, the pliability of this coating, crack resistance and fire resistance preferably, and can cold curings.The patent documentation that patent publication No. is CN102746764A discloses a kind of transparent finishing fire retardant paint of double-component prepared for B component blending and stirring with the condensed phosphate of Polyethylene Glycol grafting for component A and water-compatible amino resin, wherein Polyethylene Glycol grafting condensed phosphate adopts polyphosphoric acids, tetramethylolmethane, Polyethylene Glycol to be prepared by solution synthetic method as raw material, and this transparent fire-resisting paint has good fire protecting performance and pliability concurrently.The patent documentation that patent publication No. is CN101503581 discloses a kind of radiation curable expansion type transparent anti-flaming nano composite coating and preparation method thereof, this coating with the acrylic resin of 60%-70%, the expansion type flame-retarding resin of 30%-40%, the light trigger of 2%-6%, the leveling auxiliary agent of 0.5%-2%, 0.5%-2% antifoam additives stir under 40-60 DEG C of condition, add the organically-modified laminated metal compound of 1%-10% afterwards, ultrasonic disperse prepares transparent flame-retardant coating to matrix resin, and this coating has good fire resistance and mechanical performance.The patent documentation that patent publication No. is CN104693923A discloses a kind of Nano-meter SiO_22The preparation method of ultrathin water-based expansion fire-proof Steel material, wherein fireproof coating be mainly composed of 10% nano silicon, 50% APP, 10% polyoxyethylene polyoxypropylene tetramethylolmethane ether, 5% tripolycyanamide, the titanium dioxide of 5%, the chlorine partial emulsion of 10% and acrylic emulsion.The patent documentation that patent publication No. is CN101914333A discloses a kind of water super-thin steel structure fire-proof paint and preparation method thereof, it is that the phyllosilicate nano complex emulsions prepared with in-situ emulsion polymerization method is for film forming binder, add according to a certain percentage and there is the carbonifying catalyst of fire protection flame retarding effect, carbon forming agent, foaming agent, filler, auxiliary agent and suitable quantity of water, it is fully ground and mixes, this coating can be formed uniform and stable expanded charred layer by after fire, has good flameproof effect.Patent publication No. is the preparation method that the patent documentation of CN1346855A discloses a kind of high-temp .-resisting fire-proof composite nano paint, and this coating is formed by physical blending with the high-molecular organic material added in the nanoparticles such as phosphate, oxide and nanometer aluminium silicate nanometer by nanometer silicon carbide, nano silicate clay etc..The patent documentation that patent publication No. is CN103805056A discloses a kind of nano fire-retardant coating and preparation method thereof, this coating is made up of inorganic nano-filler, film former, coalescents, plasticizer, cross-linking agent and drier, and wherein inorganic nano-filler is the modified Nano compound particle that surface is covered with the inorganic nano-particle of silicon dioxide.The patent documentation that patent publication No. is CN103435952B discloses a kind of Phosphate nano composite flame-retardant masterbatch and preparation method thereof, this flame-retardant master batch is prepared by physical blending method high-speed stirred 5h at 100 DEG C by the organic clay that Benzodiazepines double; two (diphenyl phosphoester) is coupling agent modified with KH550, in this flame-retardant master batch, phosphate ester and organic clay are by the blended preparation of simple physical, and the product transparency is poor.The patent documentation that patent publication No. is CN101092503A discloses a kind of flame retardant epoxy resin made from salt of phosphate bi melamine nano composite material, this material is prepared from by physical blending by organo montmorillonite, salt of phosphate bi melamine and epoxy resin, and organo montmorillonite is present among composite with physical form.The patent documentation that patent publication No. is CN104861497A discloses a kind of phosphate flame retardant and nano imvite blending and modifying PTT polymer blend, this compound is prepared by physical blending by triphenyl phosphate ester (TPP), bisphenol-A-bis-(diphenyl phosphate), nano imvite and PTT polymer blend, and wherein montmorillonite is present in compound with physical form.The patent documentation that patent publication No. is CN104194504A discloses a kind of nano fire-retardant coating and its preparation method and application, this nano fire-retardant coating is prepared from by physical blending by nano silicon, vinyl-vinyl acetate copolymer, melamine pyrophosphoric ester and Pulvis Talci etc., and nano silicon is present among fireproof coating with physical form.
Organo montmorillonite and nano silicon are generally white powder, and the nano composite material transparency of the organo montmorillonite prepared by physical blending and nano silicon is poor, it is impossible to be used for preparing transparent material.In existing report, the application in fireproof coating of nano silicon and organo montmorillonite is concentrated mainly on nontransparent fireproof coating field, and the applied research about Nano filling synergistic enhancing transparent fire-resisting paint is also less.In addition, nano silicon and organo montmorillonite in existing report add among nano fire-retardant coating mainly through physical blending form, and adopt the blended form of simple physical to add Nano filling and can increase the power of covering of fireproof coating, cause that transparent fire-resisting paint decorative effect is deteriorated, it is impossible to meet the application demand of transparent fire-resisting paint.
Nano filling chemical graft is prepared nanometer expansion-type transparent fire-retardant coating by the present invention on phosphate ester acid strand, while keeping coating transparent, strengthens the fire-retardant and smoke suppressing of transparent fire-resisting paint.
Summary of the invention
In order to improve the fire protecting performance of expansion-type transparent fire-retardant coating, the invention provides a kind of nanometer expansion-type transparent fire-retardant coating and preparation method thereof.Nano filling is grafted on phosphate ester acid strand to prepare nanometer expansion-type transparent fire-retardant coating by the present invention, on the basis of the transparency ensureing coating, improves the fire-retardant and smoke suppressing of coating.
In order to realize foregoing invention purpose, the invention provides a kind of nanometer expansion-type transparent fire-retardant coating, described coating includes component A and B component；Described component A comprises Nano filling grafting phosphate ester acid, and B component comprises melmac.
Nano filling grafting phosphate ester acid in described coating: melmac mass ratio is 1:1-2.
Described melmac is methyl-etherified melmac or butylated melamine resins.
Wherein melmac is also known as melamine resin,
Methyl-etherified melmac also known as methyl-etherified melamine resin,
Butylated melamine resins is also known as butylated melamine-formaldehyde resin.
Described Nano filling grafting phosphate ester acid is nano organic montmorillonite grafting phosphate ester acid or nano silicon grafting phosphate ester acid or nano organic montmorillonite and the common grafting phosphate ester acid of nano silicon;
Described component A is the aqueous solution of Nano filling grafting phosphate ester acid.
Described B component is the aqueous solution of melmac.
In order to realize goal of the invention better, the preparation method that the present invention provides a kind of nanometer of expansion-type transparent fire-retardant coating, described preparation method comprises the following steps:
(1) described Nano filling grafting phosphate ester acid is nano organic montmorillonite grafting phosphate ester acid or nano silicon grafting phosphate ester acid or nano organic montmorillonite and the common grafting phosphate ester acid of nano silicon;
The preparation of Nano filling grafting phosphate ester acid:
A. the preparation of nano organic montmorillonite grafting phosphate ester acid:
By nano imvite Na+-MMT is placed in the suspension making nano imvite in the deionized water of nano imvite 2-3 mass times, then the cetyl trimethylammonium bromide CTAB of nano imvite 2-3 mass times is completely dissolved in deionized water and prepares into solution one, suspension is heated under water bath with thermostatic control and stirs 0.5h-1h, heating-up temperature is 70 DEG C-90 DEG C, it is subsequently adding solution one to react, after reaction 3h-5h, stop heating, stand after 24h, remove the product sucking filtration after upper solution, washing repeatedly to product without Br-(use AgNO afterwards3Inspection is without light-yellow precipitate), dry 72h at 80 DEG C, and the powder of 150 order-300 orders is become with ball mill grinding, make nano organic montmorillonite OMMT；
Then, by nano organic montmorillonite OMMT, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h-6h at 120 DEG C-140 DEG C, obtain flaxen nano organic montmorillonite grafting acidic phosphate ester compounds, wherein in reactant, each constituent mass percent is that nano organic montmorillonite accounts for 2%-8%, tetramethylolmethane accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butyl alcohol accounts for 4%-5%, and each component gross mass percent is 100%；
Or the preparation of nano silicon grafting phosphate ester acid b.:
Weigh 90-110g nano silicon dry >=24h at 100-110 DEG C, it is then added in container, the 5%-10% of 500-600ml toluene and 5g-10gKH-550(nano silicon consumption is added in container) in 110 DEG C of-130 DEG C of heated and stirred 1h-3h, afterwards product cooled down, filter, (utilize absolute ethanol washing 3-5 time with absolute ethanol washing, each dehydrated alcohol amount is 500ml), then at 100-120 DEG C of dry 8-12h, alkylation nano silicon is obtained；
Then, by alkylation nano silicon, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h-6h at 120 DEG C-140 DEG C, obtain flaxen nano silicon grafting acidic phosphate ester compounds, wherein reactant each component mass percent is that alkylation nano silicon accounts for 2%-8%, tetramethylolmethane accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butyl alcohol accounts for 4%-5%, and each component gross mass percent is 100%；
Or the preparation of nano organic montmorillonite and the common grafting phosphate ester acid of nano silicon c.:
Alkylation nano silicon prepared by nano organic montmorillonite OMMT a step prepared and b step, with tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h-6h at 120 DEG C-140 DEG C, obtain flaxen nano organic montmorillonite and the common grafting acid phosphate of nano silicon, wherein reactant each component mass percent is that alkylation nano silicon accounts for 1%-5%, nano organic montmorillonite OMMT accounts for 2%-6%, tetramethylolmethane accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butyl alcohol accounts for 4%-5%, and each component gross mass percent is 100%.
(2) preparation of nanometer expansion-type transparent fire-retardant coating
Component A and B component, as component A, using melmac as B component, are made into aqueous solution by Nano filling grafting phosphate ester acid respectively that a or b or step c in step (1) are prepared；And according to Nano filling grafting phosphate ester acid: the ratio of melmac mass ratio 1:1-2 is uniform by the aqueous solution blending and stirring of component A and B component, namely obtains a nanometer expansion-type transparent fire-retardant coating；
Or the solution that is each configured to of the Nano filling grafting acid phosphide a or b or step c in step (1) prepared is as component A, using the solution of melmac as B component, and according to Nano filling grafting phosphate ester acid: the ratio of melmac mass ratio 1:1-2, by uniform to component A and B component blending and stirring, namely obtains a nanometer expansion-type transparent fire-retardant coating.
The Nano filling grafting acid phosphate a or b or step c in step (1) prepared is as component A, and being configured to component A mass percent in aqueous during aqueous solution is 60%.
Using melmac as B component, when melmac is made into aqueous solution, wherein B component mass percent in aqueous is 60%.
Described melmac includes methyl-etherified melmac, butylated melamine resins.
The infrared spectrum of nano organic montmorillonite grafting phosphate ester acid and phosphate ester acid is shown in Figure 1, and wherein nano organic montmorillonite grafting phosphate ester acid is at 800-1400cm-1Between substantially the broadening and strengthen of absworption peak, it was shown that nano organic montmorillonite has been grafted on phosphate ester acid strand.
The infrared spectrum of nano silicon grafting phosphate ester acid is shown in Figure 2, and wherein nano silicon grafting phosphate ester acid is at 800-1400cm-1Between absworption peak substantially broaden and strengthen, 1100cm-1Near the antisymmetric stretching vibration peak of Si-O-Si occurs, this shows Nano-meter SiO_22It is grafted on phosphate ester acid strand.
The technical scheme that the embodiment of the present invention provides has the benefit that
(1) nano silicon and organo montmorillonite are chemically grafted on phosphate ester acid by the present invention nanometer expansion-type transparent fire-retardant coating, Nano filling is uniformly dispersed in the coating, and is prevented effectively from the problems such as coating transparent, animal migration and the compatibility that physical blending causes.
(2) Nano filling, phosphate ester acid and amino resins are incorporated among transparent fire-resisting paint by the present invention nanometer expansion-type transparent fire-retardant coating; the foamed char structure of densification can be formed; base material is had good flameproof protection effect; wherein nano silicon and organo montmorillonite and expanding fire retardant have synergistic effect, it is possible to significantly improve the flameproof protection effect of foamed char.
(3) raw material sources of the present invention nanometer expansion-type transparent fire-retardant coating are extensive, with low cost, easy to operate.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of nano organic montmorillonite grafting phosphate ester acid and non-grafted phosphate ester acid.
Fig. 2 is the infrared spectrum of nano silicon grafting phosphate ester acid and non-grafted phosphate ester acid.
Detailed description of the invention
Following example are further illustrating the present invention, and specifically details are as follows:
Na+-MMT montmorillonite, Zhejiang Feng Hong clay Chemical Co., Ltd., CASNo.1318-93-0
Cetyl trimethylammonium bromide CTAB, Shanghai Audemars Pigeut chemical reagents corporation, ARCASNo.57-09-0
AgNO3, silver nitrate, Xiamen seamark Science and Technology Ltd., CASNo.7761-88-8
Tetramethylolmethane, purity >=98%, Shanghai is by force along chemical reagent company limited, CASNo.115-77-5
Phosphoric acid, content >=85%, Hunan Hui Hong reagent company limited, CASNo.7664-38-2
N-butyl alcohol, Chemical Reagent Co., Ltd., Sinopharm Group, ARCASNo.71-36-3
Methyl-etherified melmac Xinhua Resin Factory, Shanghai, model 5386-60
Nano-meter SiO_22, purity 99.5%, particle diameter 15 ± 5nm, Chengdu Gracia chemical technology company limited, CASNo.7631-86-9
KH-550, silane coupler, Jinan multidimensional bridge company limited, CASNo.919-30-2
Dehydrated alcohol, Chemical Reagent Co., Ltd., Sinopharm Group, CASNo.64-17-5
Butylated melamine resins Xinhua Resin Factory, Shanghai, model 582-2
Embodiment 1:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano organic montmorillonite grafting phosphate ester acid
By 100g nano imvite Na among the there-necked flask of 1L+-MMT is placed in the deionized water of 200g to make the suspension of montmorillonite, then by nano imvite 2 mass again be 200g cetyl trimethylammonium bromide CTAB be completely dissolved in deionized water and prepare into solution one, suspension is heated under 90 DEG C of waters bath with thermostatic control and stirs 0.5h, it is subsequently adding solution one to react, after reaction 3h, stop heating, stand after 24h, remove the product sucking filtration after upper solution, washing repeatedly to product without Br-(check without light-yellow precipitate with AgNO3) afterwards, dry 72h at 80 DEG C, and become the powder of 150 orders with ball mill grinding, make nano organic montmorillonite OMMT；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by nano organic montmorillonite OMMT, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 6h at 120 DEG C, obtain flaxen nano organic montmorillonite grafting acidic phosphate ester compounds, wherein each constituent mass percent is that nano organic montmorillonite accounts for 2%, tetramethylolmethane accounts for 26%, phosphoric acid accounts for 67%, n-butyl alcohol accounts for 5%, and each component gross mass percent is 100%；
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, formed according to mass ratio 1:2 is blended by the methyl-etherified melmac of component A nano organic montmorillonite grafting phosphate ester acid Yu B component, wherein component A is made into the organo montmorillonite grafting acid phosphate aqueous solution of ester of mass percent 60%, B component is made into the aqueous solution of the methyl-etherified melmac that mass percent is 60%, and two kinds of aqueous solutions are uniform according to 1:2 blending and stirring.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.92g, char volume is 2.95cm3, foamed char height be 13.50mm, flame propagation ratio is 13.56, and smoke density grade is 6.01%.
Embodiment 2:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano organic montmorillonite grafting phosphate ester acid
By 100g nano imvite Na among the there-necked flask of 1L+-MMT is placed in the deionized water of 300g to make the suspension of montmorillonite, then by montmorillonite 3 mass again be 300g cetyl trimethylammonium bromide CTAB be completely dissolved in deionized water and prepare into solution one, suspension is heated under 70 DEG C of waters bath with thermostatic control and stirs 1h, it is subsequently adding solution one to react, after reaction 5h, stop heating, stand after 24h, remove the product sucking filtration after upper solution, washing repeatedly to product without Br-(check without light-yellow precipitate with AgNO3) afterwards, dry 72h at 80 DEG C, and become the powder of 300 orders with ball mill grinding, make nano organic montmorillonite OMMT；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by nano organic montmorillonite OMMT, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h at 140 DEG C, obtain flaxen nano organic montmorillonite grafting acidic phosphate ester compounds, wherein each constituent mass percent is that nano organic montmorillonite accounts for 8%, tetramethylolmethane accounts for 24%, phosphoric acid accounts for 63%, n-butyl alcohol accounts for 5%, and each component gross mass percent is 100%；
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, formed according to mass ratio 1:1 is blended by the methyl-etherified melmac of component A nano organic montmorillonite grafting phosphate ester acid Yu B component, wherein component A is made into the organo montmorillonite grafting acid phosphate aqueous solution of ester of mass percent 60%, and B component is made into the aqueous solution of the methyl-etherified melmac that mass percent is 60%；Two kinds of aqueous solutions are uniform according to 1:2 blending and stirring.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.31g, char volume is 1.30cm3, foamed char height be 15.50mm, flame propagation ratio is 8.56, and smoke density grade is 3.92%.
Embodiment 3:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano organic montmorillonite grafting phosphate ester acid
Among the there-necked flask of 1L, it is placed in the deionized water of 250g by 100g nano imvite Na+-MMT to make the suspension of montmorillonite, then the i.e. 200g cetyl trimethylammonium bromide CTAB of montmorillonite 2 mass times is completely dissolved in deionized water and prepares into solution one, suspension is heated under 80 DEG C of waters bath with thermostatic control and stirs 1h, it is subsequently adding solution one to react, after reaction 4h, stop heating, stand after 24h, remove the product sucking filtration after upper solution, washing repeatedly to product without Br-(check without light-yellow precipitate with AgNO3) afterwards, dry 72h at 80 DEG C, and become the powder of 200 orders with ball mill grinding, make nano organic montmorillonite OMMT；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by nano organic montmorillonite OMMT, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 4h at 130 DEG C, obtain flaxen nano organic montmorillonite grafting acidic phosphate ester compounds, wherein each constituent mass percent is that nano organic montmorillonite accounts for 5%, tetramethylolmethane accounts for 25%, phosphoric acid accounts for 66%, n-butyl alcohol accounts for 4%, and each component gross mass percent is 100%；
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, formed according to mass ratio 1:1.5 is blended by the butylated melamine resins of component A nano organic montmorillonite grafting phosphate ester acid Yu B component, wherein component A is made into the organo montmorillonite grafting acid phosphate aqueous solution of ester of mass percent 60%, B component is made into the aqueous solution of the butylated melamine resins that mass percent is 60%, and two kinds of aqueous solutions are uniform according to 1:1.5 blending and stirring.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.52g, char volume is 1.71cm3, foamed char height be 14.67mm, flame propagation ratio is 10.56, and smoke density grade is 4.25%.
Embodiment 4:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano silicon grafting phosphate ester acid
Weigh 90g nano silicon dry 24h at 100 DEG C, it is then added in the 1000mL there-necked flask container with thermometer, agitator and division box, 500ml toluene and 5gKH-550 is added in 110 DEG C of heated and stirred 3h in container, afterwards product cooled down, filter, (utilize absolute ethanol washing 3 times with absolute ethanol washing, each dehydrated alcohol amount is 500ml), then at 100 DEG C of dry 12h, alkylation nano silicon is obtained；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by alkylation nano silicon, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 6h at 120 DEG C, obtain flaxen nano silicon grafting acidic phosphate ester compounds, wherein reactant each component mass percent is that alkylation nano silicon accounts for 2%, tetramethylolmethane accounts for 26%, phosphoric acid accounts for 67%, n-butyl alcohol accounts for 5%, and each component gross mass percent is 100%；
It is dissolved in distilled water by nano silicon grafting phosphate ester acid again to be made into the aqueous solution that mass percent is 60%, be component A.
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, component A and B component forming according to mass ratio 1:2 is blended, wherein component A is the nano silicon grafting acid phosphate aqueous solution of ester of mass percent 60%, B component is mass percent be 60% the aqueous solution of methyl-etherified melmac.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.85g, char volume is 2.10cm3, foamed char height be 13.00mm, flame propagation ratio is 12.79, and smoke density grade is 4.54%.
Embodiment 5:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano silicon grafting phosphate ester acid
Weigh 110g nano silicon dry 24h at 110 DEG C, it is then added in the 1000mL there-necked flask container with thermometer, agitator and division box, 600ml toluene and 10gKH-550 is added in 130 DEG C of heated and stirred 1h in container, afterwards product cooled down, filter, (utilize absolute ethanol washing 5 times with absolute ethanol washing, each dehydrated alcohol amount is 500ml), then at 120 DEG C of dry 8h, alkylation nano silicon is obtained；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by alkylation nano silicon, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h at 140 DEG C, obtain flaxen nano silicon grafting acidic phosphate ester compounds, wherein reactant each component mass percent is that alkylation nano silicon accounts for 8%, tetramethylolmethane accounts for 24%, phosphoric acid accounts for 63%, n-butyl alcohol accounts for 5%, and each component gross mass percent is 100%；
It is dissolved in distilled water by nano silicon grafting phosphate ester acid again to be made into the aqueous solution that mass percent is 60%, be component A.
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, component A and B component forming according to mass ratio 1:1 is blended, wherein component A is the nano silicon grafting acid phosphate aqueous solution of ester of mass percent 60%, B component is mass percent be 60% the aqueous solution of methyl-etherified melmac.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.35g, char volume is 1.45cm3, foamed char height be 14.50mm, flame propagation ratio is 9.39, and smoke density grade is 3.95%.
Embodiment 6:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano silicon grafting phosphate ester acid
Weigh 100g nano silicon dry 24h at 105 DEG C, it is then added in the 1000mL there-necked flask container with thermometer, agitator and division box, 550ml toluene and 6gKH-550 is added in 110 DEG C of heated and stirred 2h in container, afterwards product cooled down, filter, (utilize absolute ethanol washing 4 times with absolute ethanol washing, each dehydrated alcohol amount is 500ml), then at 110 DEG C of dry 10h, alkylation nano silicon is obtained；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by alkylation nano silicon, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 4h at 130 DEG C, obtain flaxen nano silicon grafting acidic phosphate ester compounds, wherein reactant each component mass percent is that alkylation nano silicon accounts for 5%, tetramethylolmethane accounts for 25%, phosphoric acid accounts for 66%, n-butyl alcohol accounts for 4%, and each component gross mass percent is 100%；
It is dissolved in distilled water by nano silicon grafting phosphate ester acid again to be made into the aqueous solution that mass percent is 60%, be component A.
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, component A: B component mass ratio 1:1.5, wherein component A is for nano silicon grafting phosphate ester acid, B component is butylated melamine resins, component A and B component are each configured to the aqueous solution that mass fraction is 60%, by two kinds of aqueous solutions according to mass ratio 1:1.5 mixing and stirring.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.57g, char volume is 1.80cm3, foamed char height be 14.00mm, flame propagation ratio is 10.39, and smoke density grade is 4.24%.
Embodiment 7:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano silicon and organo montmorillonite grafting phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, using the nano organic montmorillonite of preparation in embodiment 1 and embodiment 4 and alkylation nano silicon as raw material, with tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 6h at 120 DEG C, obtaining flaxen nano organic montmorillonite and the common grafting acid phosphate ester admixture of nano silicon, wherein in reactant, nano organic montmorillonite accounts for 2%, alkylation nano silicon accounts for 5%, tetramethylolmethane accounts for 24%, phosphoric acid accounts for 65%, n-butyl alcohol accounts for 4%.Afterwards, then nano silicon grafting acid phosphate is dissolved in distilled water and is made into the aqueous solution that mass percent is 60%, is component A.
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, formed according to mass ratio 1:2 is blended by the aqueous solution of the aqueous solution of the nano organic montmorillonite of component A and nano silicon common grafting phosphate ester acid Yu the methyl-etherified melmac of B component, wherein component A is the aqueous solution of mass percent 60%, B component is mass percent be 60% the aqueous solution of methyl-etherified melmac.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.26g, char volume is 1.35cm3, foamed char height be 15.00mm, flame propagation ratio is 8.59, and smoke density grade is 3.66%.
Embodiment 8:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano silicon and organo montmorillonite grafting phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, using the nano organic montmorillonite of preparation in embodiment 2 and embodiment 5 and alkylation nano silicon as raw material, with tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h at 140 DEG C, obtaining flaxen nano organic montmorillonite and the common grafting acid phosphate ester admixture of nano silicon, wherein in reactant, nano organic montmorillonite accounts for 6%, alkylation nano silicon accounts for 1%, tetramethylolmethane accounts for 26%, phosphoric acid accounts for 63%, n-butyl alcohol accounts for 4%.Afterwards, then nano silicon grafting acid phosphate is dissolved in distilled water and is made into the aqueous solution that mass percent is 60%, is component A.
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, formed according to mass ratio 1:1 is blended by the aqueous solution of the aqueous solution of the mixture of the nano organic montmorillonite of component A and nano silicon common grafting phosphate ester acid Yu the butylated melamine resins of B component, wherein component A is the aqueous solution of mass percent 60%, and B component is mass percent is the aqueous solution of the butylated melamine resins of 60%.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.15g, char volume is 1.15cm3, foamed char height be 15.80mm, flame propagation ratio is 7.85, and smoke density grade is 3.45%.
Embodiment 9:
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of nano silicon and organo montmorillonite grafting phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, using the nano organic montmorillonite of preparation in embodiment 3 and embodiment 6 and alkylation nano silicon as raw material, with tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 4h at 130 DEG C, obtaining flaxen nano organic montmorillonite and the common grafting acid phosphate ester admixture of nano silicon, wherein in reactant, nano organic montmorillonite accounts for 2%, alkylation nano silicon accounts for 2%, tetramethylolmethane accounts for 24%, phosphoric acid accounts for 67%, n-butyl alcohol accounts for 5%.Afterwards, then nano silicon grafting acid phosphate is dissolved in distilled water and is made into the aqueous solution that mass percent is 60%, is component A.
(2) preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, the methyl-etherified melmac mass ratio 1:1.5 of the mixture of the nano organic montmorillonite of component A and the common grafting phosphate ester acid of nano silicon and B component, wherein component A is configured to the aqueous solution of mass percent 60%, B component is configured to the aqueous solution of the methyl-etherified melmac that mass percent is 60%, and two kinds of aqueous solutions are uniform according to mass ratio 1:1.5 blending and stirring.
(3) nanometer expansion-type transparent fire-retardant coating performance characterization
Adopt GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " the smoke density test method of construction material burning or decomposition " that the fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating prepared in the present embodiment is measured: the mass loss in cell method of this coating is 2.45g, char volume is 1.80cm3, foamed char height be 14.95mm, flame propagation ratio is 10.15, and smoke density grade is 3.85%.
Comparative example 1
In the present embodiment, formed according to mass ratio 1:1.5 is blended with the methyl-etherified melmac in B component by the phosphate ester acid in component A, wherein component A is the acid phosphate aqueous solution of ester of mass percent 60%, B component is mass percent be 60% the aqueous solution of methyl-etherified melmac.
(1) preparation of phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, phosphoric acid, tetramethylolmethane, n-butyl alcohol are reacted at 130 DEG C 4h, obtaining flaxen phosphate ester acid product liquid, wherein tetramethylolmethane accounts for 26.3%, phosphoric acid accounts for 68.4%, n-butyl alcohol accounts for 5.3%.Afterwards, it is dissolved in distilled water by phosphate ester acid preparation quality percent and is the aqueous solution of 60%, be component A.
(2) preparation of expansion-type transparent fire-retardant coating
Component A and B component are uniformly prepared expansion-type transparent fire-retardant coating so that mass ratio 1:1.5 is blended, wherein B component to be mass percent be 60% the aqueous solution of methyl ether melmac.
(3) expansion-type transparent fire-retardant coating performance characterization
According to GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " construction material burning or the smoke density test method decomposed ", the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured: in cell method, mass loss is 4.07g, char volume is 5.84cm3, layer of charcoal height be 2.50mm, flame propagation ratio is 23.31, and smoke density grade is 17.97%.
In conjunction with the embodiments and comparative example 1 it is found that there is good cooperative flame retardant effect between nano silicon and organo montmorillonite and phosphate ester acid, the fire-retardant of transparent fire-resisting paint and smoke suppressing can be significantly improved.
Comparative example 2
In the present embodiment, A, B component forming according to mass ratio 1:1.5 is blended, wherein component A is formed by physical blending by phosphate ester acid and unmodified montmorillonite, and B component is methyl-etherified melmac.
(1) preparation of montmorillonite and acid phosphate ester blend
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 4h at 130 DEG C, obtain flaxen acidic phosphate ester compounds；Afterwards, adding unmodified montmorillonite and at room temperature carry out physical blending, obtain the phosphate ester acid of milky montmorillonoid-containing, wherein montmorillonite accounts for 5%, tetramethylolmethane accounts for 25%, phosphoric acid accounts for 65%, n-butyl alcohol accounts for 5%.Afterwards, then the phosphate ester acid of montmorillonoid-containing is dissolved in distilled water and is made into the aqueous solution that mass percent is 60%, is component A.Owing to montmorillonite is distributed in phosphate ester acid with physical form, product is creamy white.
(2) preparation of expansion-type transparent fire-retardant coating
Component A and B component are uniformly prepared expansion-type transparent fire-retardant coating so that mass ratio 1:1.5 is blended, wherein B component to be mass percent be 60% the aqueous solution of methyl ether melmac.The transparency decline of the expansion-type transparent fire-retardant coating of the montmorillonoid-containing prepared with physical blending, it is impossible to application.
(3) expansion-type transparent fire-retardant coating performance characterization
According to GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " construction material burning or the smoke density test method decomposed ", the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured: in cell method, mass loss is 3.98g, char volume is 3.96cm3, layer of charcoal height be 8.33mm, flame propagation ratio is 20.35, and smoke density grade is 15.35%.
Be can be seen that by comparative example 1 and comparative example 2, there is between montmorillonite and phosphate ester acid synergistic fire retardation, the fire-retardant of transparent fire-resisting paint and smoke suppressing can be improved, but the transparent fire-resisting paint that cooperative flame retardant efficiency and the transparency are prepared significantly lower than organo montmorillonite grafting phosphate ester acid, and the product transparency is also decreased obviously, it is impossible to application.
Comparative example 3
In the present embodiment, A, B component forming according to mass ratio 1:1.5 is blended, wherein component A is formed by physical blending by phosphate ester acid and nano silicon, and B component is methyl-etherified melmac.
(1) preparation of nano silicon and acid phosphate ester blend
Equipped with magnetic stir bar, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 4h at 130 DEG C, obtain flaxen acidic phosphate ester compounds；Afterwards, adding unmodified nano silicon and at room temperature carry out physical blending, obtain the phosphate ester acid of milky nano-silica-containing, wherein nano silicon accounts for 5%, tetramethylolmethane accounts for 25%, phosphoric acid accounts for 65%, n-butyl alcohol accounts for 5%.Afterwards, then the phosphate ester acid of nano-silica-containing is dissolved in distilled water and is made into the aqueous solution that mass percent is 60%, is component A.Owing to nano silicon is distributed in phosphate ester acid with physical form, product is creamy white.
(2) preparation of expansion-type transparent fire-retardant coating
Component A and B component are uniformly prepared expansion-type transparent fire-retardant coating so that mass ratio 1:1.5 is blended, wherein B component to be mass percent be 60% the aqueous solution of methyl ether melmac.The transparency decline of the expansion-type transparent fire-retardant coating of the nano-silica-containing prepared with physical blending, is not suitable for application.
(3) expansion-type transparent fire-retardant coating performance characterization
According to GB12441-2005 " finishing fire retardant paint " and GB/T8626-2007 " construction material burning or the smoke density test method decomposed ", the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured: in cell method, mass loss is 3.84g, char volume is 4.41cm3, layer of charcoal height be 9mm, flame propagation ratio is 18.05, and smoke density grade is 14.45%.
Be can be seen that with embodiment by comparative example 1 and comparative example 3, there is between nano silicon and phosphate ester acid synergistic fire retardation, the fire-retardant of transparent fire-resisting paint and smoke suppressing can be improved, but the transparent fire-resisting paint that cooperative flame retardant efficiency and the transparency are prepared significantly lower than nano silicon grafting phosphate ester acid, and the product transparency is also decreased obviously, it is impossible to enough application.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (10)
1. one kind of nanometer of expansion-type transparent fire-retardant coating, it is characterised in that described coating includes component A and B component；Described component A comprises Nano filling grafting phosphate ester acid, and B component comprises melmac.
2. according to claim 1 nanometer of expansion-type transparent fire-retardant coating, it is characterised in that Nano filling grafting phosphate ester acid in described coating: melmac mass ratio is 1:1-2.
3. according to claim 1 and 2 nanometer of expansion-type transparent fire-retardant coating, it is characterised in that described melmac is methyl-etherified melmac or butylated melamine resins.
4. according to the arbitrary described nanometer expansion-type transparent fire-retardant coating of claim 1-3, it is characterised in that described Nano filling grafting phosphate ester acid is nano organic montmorillonite grafting phosphate ester acid；
Or nano silicon grafting phosphate ester acid；
Or nano organic montmorillonite and the common grafting phosphate ester acid of nano silicon.
5. according to the arbitrary described nanometer expansion-type transparent fire-retardant coating of claim 1-4, it is characterised in that described B component is the aqueous solution of melmac.
6. according to the arbitrary described nanometer expansion-type transparent fire-retardant coating of claim 1-5, it is characterised in that described component A is the aqueous solution of Nano filling grafting phosphate ester acid.
7. the preparation method according to the arbitrary described nanometer expansion-type transparent fire-retardant coating of claim 16, it is characterised in that described preparation method comprises the following steps:
(1) described Nano filling grafting phosphate ester acid is nano organic montmorillonite grafting phosphate ester acid；Or nano silicon grafting phosphate ester acid；Or nano organic montmorillonite and the common grafting phosphate ester acid of nano silicon;
A. the preparation of nano organic montmorillonite grafting phosphate ester acid:
By nano imvite Na+-MMT is placed in the suspension making nano imvite in the deionized water of nano imvite 2-3 mass times, then the cetyl trimethylammonium bromide CTAB of nano imvite 2-3 mass times is completely dissolved in deionized water and prepares into solution one, suspension is heated under water bath with thermostatic control and stirs 0.5h-1h, heating-up temperature is 70 DEG C-90 DEG C, it is subsequently adding solution one to react, after reaction 3h-5h, stop heating, stand after 24h, remove the product sucking filtration after upper solution, washing repeatedly to product without Br-After, dry 72h at 80 DEG C, and the powder of 150 order-300 orders is become with ball mill grinding, make nano organic montmorillonite OMMT；
Then, by nano organic montmorillonite OMMT, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h-6h at 120 DEG C-140 DEG C, obtain nano organic montmorillonite grafting acidic phosphate ester compounds, wherein in reactant, each constituent mass percent is that nano organic montmorillonite accounts for 2%-8%, tetramethylolmethane accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butyl alcohol accounts for 4%-5%, and each component gross mass percent is 100%；
Or the preparation of nano silicon grafting phosphate ester acid b.:
Weigh 90-110g nano silicon dry >=24h at 100-110 DEG C, it is then added in container, 500-600ml toluene and 5g-10gKH-550 is added in 110 DEG C of-130 DEG C of heated and stirred 1h-3h in container, afterwards product cooled down, filter, use absolute ethanol washing, then at 100-120 DEG C of dry 8-12h, alkylation nano silicon is obtained；
Then, by alkylation nano silicon, tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h-6h at 120 DEG C-140 DEG C, obtain nano silicon grafting acidic phosphate ester compounds, wherein reactant each component mass percent is that alkylation nano silicon accounts for 2%-8%, tetramethylolmethane accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butyl alcohol accounts for 4%-5%, and each component gross mass percent is 100%；
Or the preparation of nano organic montmorillonite and the common grafting phosphate ester acid of nano silicon c.:
Alkylation nano silicon prepared by nano organic montmorillonite OMMT a step prepared and b step, with tetramethylolmethane, phosphoric acid and n-butyl alcohol hybrid reaction 3h-6h at 120 DEG C-140 DEG C, obtain nano organic montmorillonite and the common grafting phosphate ester acid of nano silicon, wherein reactant each component mass percent is that alkylation nano silicon accounts for 1%-5%, nano organic montmorillonite OMMT accounts for 2%-6%, tetramethylolmethane accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butyl alcohol accounts for 4%-5%, and each component gross mass percent is 100%;
(2) preparation of nanometer expansion-type transparent fire-retardant coating
Component A and B component, as component A, using melmac as B component, are made into aqueous solution by Nano filling grafting phosphate ester acid respectively that a or b or step c in step (1) are prepared；And according to Nano filling grafting phosphate ester acid: the ratio of melmac mass ratio 1:1-2 is uniform by the aqueous solution blending and stirring of component A and B component, namely obtains a nanometer expansion-type transparent fire-retardant coating；
Or the solution that is each configured to of the Nano filling grafting acid phosphide a or b or step c in step (1) prepared is as component A, using the solution of melmac as B component, and according to Nano filling grafting phosphate ester acid: the ratio of melmac mass ratio 1:1-2, by uniform to component A and B component blending and stirring, namely obtains a nanometer expansion-type transparent fire-retardant coating.
8. the preparation method according to the arbitrary described nanometer expansion-type transparent fire-retardant coating of claim 1-7, it is characterized in that, the Nano filling grafting acid phosphate a or b or step c in step (1) prepared is as component A, and being configured to component A mass percent in aqueous during aqueous solution is 60%.
9. the preparation method according to the arbitrary described nanometer expansion-type transparent fire-retardant coating of claim 1-8, it is characterized in that, using melmac as B component, when melmac is made into aqueous solution, wherein B component mass percent in aqueous is 60%.
10. the preparation method according to the arbitrary described nanometer expansion-type transparent fire-retardant coating of claim 1-9, it is characterised in that described melmac is methyl-etherified melmac or butylated melamine resins.
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