CN102241931A - Environment-friendly type flame-retarding and smoke-suppressing paint and preparation method thereof - Google Patents
Environment-friendly type flame-retarding and smoke-suppressing paint and preparation method thereof Download PDFInfo
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- CN102241931A CN102241931A CN2011101590445A CN201110159044A CN102241931A CN 102241931 A CN102241931 A CN 102241931A CN 2011101590445 A CN2011101590445 A CN 2011101590445A CN 201110159044 A CN201110159044 A CN 201110159044A CN 102241931 A CN102241931 A CN 102241931A
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- Prior art keywords
- nano
- agent
- magnesium hydroxide
- retardant
- speed
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003973 paint Substances 0.000 title claims abstract description 17
- 239000003063 flame retardant Substances 0.000 claims abstract description 73
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 49
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 48
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 48
- 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 claims abstract description 47
- 239000000839 emulsion Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000000498 ball milling Methods 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000005855 radiation Effects 0.000 claims abstract description 21
- 230000002195 synergetic effect Effects 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000012757 flame retardant agent Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 60
- 238000000576 coating method Methods 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 38
- 230000004048 modification Effects 0.000 claims description 32
- 238000012986 modification Methods 0.000 claims description 32
- 239000013530 defoamer Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000000779 smoke Substances 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 235000019504 cigarettes Nutrition 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000080 wetting agent Substances 0.000 claims description 14
- 230000008719 thickening Effects 0.000 claims description 13
- 230000003750 conditioning effect Effects 0.000 claims description 10
- 230000007613 environmental effect Effects 0.000 claims description 8
- 238000000875 high-speed ball milling Methods 0.000 claims description 8
- 238000009775 high-speed stirring Methods 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- LJCJRRKKAKAKRV-UHFFFAOYSA-N (2-amino-2-methylpropyl) 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(N)COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 LJCJRRKKAKAKRV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 41
- 238000009413 insulation Methods 0.000 abstract description 29
- 239000000843 powder Substances 0.000 abstract description 8
- 238000011049 filling Methods 0.000 abstract description 4
- 230000000979 retarding effect Effects 0.000 abstract description 2
- 239000011020 iolite Substances 0.000 abstract 2
- 239000012528 membrane Substances 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 21
- -1 be to have fillings Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 230000006870 function Effects 0.000 description 8
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical group CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 7
- 239000011805 ball Substances 0.000 description 7
- 239000007888 film coating Substances 0.000 description 7
- 238000009501 film coating Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 235000019832 sodium triphosphate Nutrition 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002341 toxic gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000283986 Lepus Species 0.000 description 4
- 210000000481 breast Anatomy 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- XAGABUIHVMEMHG-UHFFFAOYSA-N 2-methoxyethanol;propyl acetate Chemical compound COCCO.CCCOC(C)=O XAGABUIHVMEMHG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
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- 238000002955 isolation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 2
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000003340 retarding agent Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
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- 230000004523 agglutinating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to a green environment-friendly type flame-retarding and smoke-suppressing paint and a preparation method thereof. For the preparation of the paint, acrylic emulsion is used as a film forming material, iolite and zirconia are used as near-infrared radiation functional filling materials, nano-sized magnesium hydroxide having organically modified surfaces is used as a flame-retarding and smoke-suppressing filling material, a synergistic flame retardant and auxiliary agents are also used, and compound processes of ball milling, high speed dispersing and stirring are carried out, wherein, the particle size of zirconia powder is 30 to 100 nm, the particle size of iolite powder is 3 to 10 mu m, and the average particle size of nano-sized magnesium hydroxide is 50 to 100 nm. The paint prepared in the invention has a good thermal insulation property; addition of nano-sized magnesium hydroxide and the synergistic flame retardant enables the oxygen index of the dry membrane of the paint to reach 23 to 30, producing a good flame-retarding effect and a significant smoke-suppressing effect; the paint not only achieves the purpose of retarding flames, but also is green and environmentally friendly.
Description
Technical field
The present invention relates to a kind ofly have well heat insulation, heat insulation effect and have compound aqueous functional coatings of fire-retardant, smoke suppressing and preparation method thereof concurrently.
Background technology
Along with progress of science and technology and development, people increase day by day to the demand of the energy, and traditional Nonrenewable energy resources are fewer and feweri.And, not only cause the supply of the energy gradually nervous, and aggravated the deterioration of environment to Nonrenewable energy resources excessive exploitation and waste.Therefore, how to develop the green energy resource that makes new advances and oneself the unusual urgent subject in becoming China and even world wide that cuts down the consumption of energy.
Building energy consumption occupies critical role in the total energy consumption of society, and wherein the overwhelming majority is the energy consumption of heating and air-conditioning, relevant statistic data shows, the electric weight that national air-conditioning is used up every year equals whole generated energy an of the three gorges hydropower plant, so building energy conservation is significant.In China, the data presentation that nation-building portion announces recently, the annual 2000000000 newly-increased m in the whole nation
280% belongs to the high energy consumption building in the floor area of building; And the unit surface of dwelling house class building uses energy consumption to compare with the country of equal weather condition, and China will exceed 2～3 times, so building energy conservation has crucial meaning.Heat-insulating (thermal insulation) insulation is an importance of save energy, the inhabitation of raising buildings and functions of use.
Thermal isolation technique has become one of research focus of effective utilization of the energy in recent years and energy-saving field extensive concern, and this technology is to utilize the obstruct principle that reduces heat passage and thermal radiation capability, and the minimizing sunlight absorbs the purpose that reaches heat-insulation and heat-preservation.As everyone knows, being radiated the solar energy on the earth surface, approximately is per second 750w/m
2, wherein the energy of visible region accounts for 45%, and the near-infrared region accounts for 45%, and other electromagnetic radiation energy accounts for 5%.As seen, sun power mainly concentrates on visible region and infrared region.And have 95% infrared energy to concentrate on wavelength in the scope of 0.72～2.5 μ m, promptly in the near infrared range.Under irradiation of sunlight, heat constantly accumulates on the radiation exposed body surface, and its surface temperature is constantly raise.In theory, by the energy to near-infrared band in the sunlight effectively intercept, reflection and radiation, can realize the purpose of shone thing heat insulation and heat control.
Aquosity heat insulating heat preserving paint is the present maximum class of research, yet effect of heat insulation is bad when directly to restrict one of its key in application problem be exactly single use, and one of main method that addresses this problem is exactly to adopt compound thermal isolation technique.Publication number is that one or more have prepared a kind of compound water-based building heat preservation thermal insulating coating in the heat-insulation and heat-preservation fillers such as hollow glass micropearl, AHS-2500 heat-reflecting heat-insulating powder and aluminum oxide by filling in polywater based acrylic resin system for the patent of invention of CN102010641A.Publication number is that the patent of invention of CN101967331A then is to have prepared and be used for the insulating mold coating that the railcar is used by add hollow ceramic microspheres, glass microballon or closed-cell expanded perlite in acrylic emulsions, VAE emulsion, fluorine carbon emulsion; Publication number be patents such as CN101831229A, CN101760108A, CN101696336A, CN101555377 and CN101108931 also be mainly by in acrylic resin emulsion, epoxy emulsion or water glass, add hollow glass microbead (adding slightly different) with array mode reach in the heat insulating effect of outer wall water-based coating.
The thermal insulation technology of as seen present coating mainly concentrates on the pearlstone that uses the silicates material or pottery or hollow glass micropearl and waits and realize.Yet, this type of material production process complexity, cost height, energy consumption is big, has problems such as environmental pollution, and owing to be subjected to dimensional constraints (micron order), the room for promotion of its heat insulating effect is less, and all there is certain negative impact in machinery, coating and the bond performance of resin base material.
In addition, along with the demand in coating market constantly increases, coating itself also exists some potential safety hazards, such as, organic composition in the coating is a lot, organic materials is heat-resisting poor, easy firing, and the time discharge a large amount of heats in burning, produce a large amount of poison gas, not only can quicken big fire spreading, and cause trapped personnel and rescue personnel's injures and deaths easily, for improving its fire retardancy, often interpolation contains bromide fire retardant in traditional coating, though this has improved fire retardancy to a certain extent, but in a single day also brought serious environmental destruction simultaneously, particularly serious fire has taken place, these bromated materials have more increased the harm of toxic smoke.Numerous fire failures prove that the toxic gas that building, finishing material burning produce is the maximum killer in the fire, sucks the lethal number of poison gas and accounts for more than 70 ~ 75% of fire fatality total number of persons.Therefore, develop the high strength that has, performance such as wear-resisting, weather-proof is excellent, and environmentally safe, low toxicity and catch fire dangerous little, the environmental friendliness coating that the amount of being fuming is few seems significant.
Magnesium hydroxide Mg (OH)
2/ MH belongs to the property dosed inorganic combustion inhibitor, be to have fillings, fire-retardant and press down the inorganic chemistry auxiliary agent of cigarette triple functions, and the smog that produces nontoxic, do not have and corrode.Its fire retardant mechanism can be from reaction equation Mg (OH)
2Δ MgO+H
2O ↑-Q finds out, the base material that has added this kind fire retardant is being heated when reaching certain temperature, the MH decomposition discharges moisture, absorb a large amount of latent heat (MH decomposition temperature 340 ~ 490oC simultaneously, absorb heat 900 ~ 1200J/g), thereby reduced the flame actual temperature of material surface, made base material heated be degraded to low molecular speed and reduce, reduced the release of inflammable gas; Produce the concentration of flue gas when simultaneously a large amount of water vapors that discharge in the decomposition course have watered down combustionmaterial near surface oxygen, inflammable gas and base burn, make surface combustion difficulty carry out; MH also has the extremely strong cigarette effect-Mg (OH) of pressing down
2Help forming surface char, stop entering of oxygen and heat, decomposing the MgO that generates simultaneously is good refractory materials, can improve the ability of base material opposing flame, plays secluding air and stops the incendiary purpose.Because Mg (OH)
2Decomposes can make burning three elements (temperature, oxygen and combustiblematerials) be controlled simultaneously, has played fire retardation, in case promptly burning things which may cause a fire disaster disappears, burning can be from horizontal blanking.Compare with conventional flame retardant (bromine system, phosphorus system, nitrogen system and expansion type flame retardant etc.), that magnesium hydroxide not only has is nontoxic, press down cigarette, low burn into prepares advantages such as simple, cheap, its flame mechanism is simple relatively, controllability is strong, and products of combustion is single (to be MgO and H
2O) can not produce secondary pollution, thereby environmental protection more.
Research and report at the fire-retardant and smoke suppressing of heat insulating water-borne coatings are also few, still are in the desk study stage.In the recent period, publication number be CN101302396 patent disclosure a kind of preparation method of the high temperature-resistant flame-retardant insulating paint of forming by silicone resin, hollow glass micro-ball thermal insulating filling, composite flame-retardant agent and auxiliary agent.This invention is by adopting the compositional flame-retardant system of common commercially available micron-sized aluminium hydroxide and magnesium hydroxide, though make the high temperature resistant and flame retardant properties of product obtain certain raising, whole smoke suppressing effect does not improve.
Nano-sized magnesium hydroxide is meant the magnesium hydrate powder (see our patent ZL 200710124792.3) of grain graininess between l～100 nm, as a kind of nano material, except characteristic with common micron order flame retardant of magnesium hydroxide, also have the advantage that granularity is little, specific surface area is big, can reduce loading level, improve flame retarding efficiency and smoke suppressing effect; Reduce advantages such as matrix machinery, coating, agglutinating value(of coal) loss of energy.Therefore, at the problems of the prior art, the invention provides a kind of environmental type fire-retardant, press down cigarette, incubation and thermal insulation function coating and preparation method thereof, by in coating matrix, adding trichroite, zirconium white, titanium dioxide, nano-sized magnesium hydroxide efficient flame-retarding agent and auxiliary agent, have flame retardancy, self-extinguishing and smoke-suppressing when making it reach heat insulating effect concurrently, thereby improve the fire safety performance of product, reduce possibility and harm thereof that fire takes place.This functional paint has advantages such as high insulating effect, good, the fire-retardant and smoke suppressing effect of stability are obvious, and the fire retardant that is added does not have toxic substance and produces when burning, HUMAN HEALTH is not had potential harm, can not produce secondary pollution to environment.
Summary of the invention
It is fire-retardant that the present invention aims to provide a kind of environmental type, press down cigarette, insulation, heat insulating function coating and preparation method thereof, the trichroite that it is stable with physical and chemical performance, zirconium white, cenosphere and Rutile type Titanium Dioxide, and effectively be compounded in the coating emulsion matrix through the environmentally friendly nano-sized magnesium hydroxide and the synergistic flame retardant of surface modification, to avoid existing infrared radiation coating heat insulating effect not good, hinder right poor performance, the complicated poor controllability of flame-retardant system, products of combustion is detrimental to health, produce defectives such as secondary pollution, further excavate the application potential of infra red radiation function coating, widen its Application Areas.
Environmental-protection flame-retardant of the present invention presses down the hood preparation method for coating, comprises the steps:
S1, will be as acrylic emulsions 40-100 part (mass parts of film forming material, nano-magnesium hydrate fire retardant 10-60 part and synergistic flame retardant 1-10 part of water 10-30 part, zirconium white 5-20 part, trichroite 5-20 part, Rutile type Titanium Dioxide 5-20 part, surface organic modification down together),, mechanical stirring 10-30min under 100-500rpm speed carries out just mixing; In mixed system, add wetting agent 0.1-0.5 part, dispersion agent 1-5 part and defoamer A 0.1-0.5 part then, utilize clarifixator to carry out high-speed stirring under 6000-15000rpm speed and further mix 3-15min, the ball milling speed high speed ball milling with 200-400rpm mixes, disperses 1.5-5h again;
S2, in the blend that step S1 obtains, add defoamer B 0.1-0.5 part, PH conditioning agent 0.3-1 part, membrane-forming agent 1-5 part and flow agent 0.3-2 part, and then by ball mill with the ball milling speed low speed mixing of 50-180rpm, disperse 1-3h; And
S3, add thickening material 0.5-5 part again in the blend that step S2 obtains, the ball milling speed low speed ball milling 0.5-1h with 50-180rpm obtains finished product coating.
Wherein, acrylic emulsions is selected a kind of at least two kinds composition in pure-acrylic emulsion, elasticity acrylic emulsion, benzene emulsion, organosilicon crylic acid latex and the acrylate and vinyl acetate emulsion for use.Synergistic flame retardant is selected at least a in red phosphorus, zinc oxide, weisspiessglanz, stannic oxide, molybdenum oxide, ammonium molybdate, the zinc borate for use.
The particle diameter of described Zirconium powder is 30-100nm, and the particle diameter of described trichroite is 3-10 μ m, and described nano-sized magnesium hydroxide median size is 50-100nm.
Wetting agent adopts aniorfic surfactant (as: Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium stearate, butyl oleate sodium sulfate etc.), nonionic surface active agent (as: alkylene oxide copolymers wetting agent AMJ Wet CF-10, alkyl ethoxy ether compound wetting agent AMJ Wet PE-100, secondary alkyl alcohol Soxylat A 25-7 wetting agent AMJ
TMWet DF-16 etc.) or the anionic/nonionic compound surfactant.
Dispersion agent can be selected inorganic dispersant (as: tripoly phosphate sodium STPP, Sodium hexametaphosphate 99 etc.), polymer dispersant (comprising: poly amic acid salt dispersant A MJ Dispers H-942, polycarboxylate sodium's class dispersant A MJ Dispers H-940 and poly carboxylic acid ammonium salt terpolymer dispersant A MJ Dispers H-943) or compound dispersion agent (as: dispersion agent that mineral dye dispersion agent and BYK-182 are composite).
Defoamer A adopts organic defoamer, and this organic defoamer mainly comprises: mineral oils (AMJ
TMDefoam 8110), DF-691 defoamer, amine and the amides (as diamylamine, halo fatty amide) formed by lipid acid, mineral oil, emulsifying agent etc., alcohols (as hexalin), phosphoric acid ester (as tributyl phosphate), metallic soap class (as aluminum stearate) etc., use one or more composition wherein.
Defoamer B adopts silicone based defoamer (as: CX-470 organo-siloxane recombiner, AMJ Defoam 8010 organosilicon emulsion defoaming agents, to contain silicone antifoam agent AMJ Defoam 8040, the AMJ of the modified polyorganosiloxane froth breaking factor
TMDefoam 8112 has double base hydrophobic structure modified silicon oil mixture) or compound defoamer (as: the BEK-750 compound defoamer of forming by silicon, ester, emulsifying agent etc.).The PH conditioning agent is AMP-95, i.e. 2-amino-2-methyl propyl alcohol.
Membrane-forming agent can adopt one or more the composition among alcohol ester-12, glycol ether, glycol ether N-BUTYL ACETATE, ethylene glycol vinyl acetic monomer, ethylene glycol monomethyl ether propyl acetate or the AMJ AGSE-IB.
Flow agent adopts modified organic silicon type flow agent, as: the prosperous prosperous chemical industry of organic silicon modified by polyether oxygen alkane flow agent CX-103(), the prompt chemistry of polyether-modified polysiloxane copolymer flow agent Flowstar FL309(Amy), the aryl polyethers is the polysiloxane copolymer flow agent Flowstar FL-333H of modification altogether, the polydimethylsiloxanecopolymer copolymer flow agent Flowstar FL-333G of alkyl, polyether modification etc. use one or more composition wherein.
Thickening material can be selected associative thickener (as: non-ionic associative type thickening material AMJ HEUR 3020, AMJ HEUR 3050 and the AMJ HEUR 3040 of hydrophobic grouping modification), urethane (as: prosperous prosperous chemical industry RM2020, PU-8080, RM-8W) or polyacrylic ester (as: hydrophobic alkali swelling vinylformic acid rheology agent AMJ HASE 420 for use; AMJ HASE 430 hydrophobic alkali swelling vinylformic acid rheology agent) composition of one or both in thickening material etc.
Adopt a kind of environmental-protection flame-retardant of method for preparing to press down hood coating, it is characterized in that: this coating is as film forming material with acrylic emulsions, with trichroite and zirconium white as the near-infrared radiation functional stuffing, with the Rutile type Titanium Dioxide is pigment, with the nano-sized magnesium hydroxide of surface organic modification as fire-retardant and press down the cigarette filler, add synergistic flame retardant and auxiliary agent, be composited through ball milling, high speed dispersion, stirring technique; In mass parts, comprise in this coating: nano-magnesium hydrate fire retardant 10-60 part of acrylic emulsions 40-100 part, water 10-30 part, zirconium white 5-20 part, trichroite 5-20 part, Rutile type Titanium Dioxide 5-20 part, surface organic modification and synergistic flame retardant 1-10 part.The oxygen index that this finished product coating is made the thick dry film of 1.5-3mm with film pulling device reaches 23-30, and smoke suppressing effect is remarkable.
The present invention is the film forming matrix with the acrylic emulsions, stable with physicochemical property, cheap trichroite and zirconium white are as the near-infrared radiation functional stuffing, widespread use on the market, the good Rutile type Titanium Dioxide of chemical stability is a pigment, and the modified Nano magnesium hydroxide of handling by organic modification of surface is fire-retardant, press down the cigarette filler, preparation has fire-retardant, the compound aqueous functional coatings of heat-insulation and heat-preservation that presses down the cigarette characteristic, this coating is coated on body surface, radiation to near-infrared band in the sun projection has good iris action, the heat energy that absorbs can be radiated surrounding space with the form of long wave, therefore outstanding to the heat insulating effect that covers substrate, and have tangible flame retardant properties, and in combustion processes, have fabulous smoke suppressing effect and naked light from putting out function.
Compare with powder coating, high solid coating and radiation curable coating, the application of the functional paint (water-borne coatings) of the present invention's preparation generally is not subjected to the restriction of occasion, also not needing special-purpose coating tool and equipment, is one of ideal substitute of the solvent based coating habitually practised.And it is simple to have construction, merges good characteristics with existing operating technique.
Acrylate of the present invention is the serial water-base resin of main film forming substance, be that present water-borne coatings art is the most ripe, one of most widely used one-tenth film base material, the advantage but also the low production cost that not only have low VOC and low toxicity, snappiness, physical strength, wear resistance, guarantor's light and tint retention, anticorrosion, alkaline-resisting and over-all propertieies such as water tolerance and weathering resistance are very excellent.This type of water-base resin contains multiple functional group, thereby multiple matrix is all had good adaptability, has stronger sticking power; Kind by regulating different acrylate (comprising the carbochain length, cladodification degree of its ester group etc.) and molecular weight and distribution thereof can be given film different snappinesies and hardness, and this multiple requirement at the different application field is particularly important; Simultaneously, the esters of acrylic acid dry solidification is typical free radical mechanism, and it is fast to have a rate of drying, is subjected to characteristics such as ectocine is less, easy construction.This resinoid contains certain polar group, has very strong bonding force with the inorganic powder that adds, and is not easy to produce the microfacies ununiformity.
The HLB value of its molecular structure and common inorganic powder is more approaching, and according to the principle of similar compatibility, both soak into easily, has reduced the workload and the difficulty of inorganic powder being carried out surface modification.
The present invention with trichroite and zirconium white as the near-infrared radiation functional stuffing.Trichroite has higher infrared emittance, especially in the mid and far infrared district, also has good thermal-shock resistance, thermal expansivity is very low, and coking property is good, and synthetic method is a lot, raw material sources are extensive, thereby are the practicality of product and the exploitation condition of providing convenience.In addition, the nano zircite particle is little, and density is little, and specific surface area is big, the surface atom number is many, the surface energy height, the serious coordination deficiency of surface atom has very strong surfactivity and superpower adsorptive power, in near infrared whole wave band, has stronger infra red radiation function, be added in the coating, very easily with resin in oxygen play bonding action, improve intermolecular bonding force and execution of coating performance and film and matrix between bonding strength.
Compare with the flame-retarded technology of existing heat insulating water-based exterior wall paint, the present invention adopts the nano-magnesium hydrate fire retardant through organic modification of surface, and median size is at 50-100nm.Nano-sized magnesium hydroxide belongs to inorganic addition type efficient flame-retarding agent, have advantages such as purity height, the super refinement of granularity, flame retardant properties be good, after organic modification of surface is handled, effectively solve the interface problem with other organic fillers or base material, and then realized reducing the purpose that loading level improves flame retardant effect.Compare with the flame-retardant system (bromine system, phosphorus system, nitrogen system level expansion type flame retardant etc.) that prior art adopts usually, its fire retardant mechanism is simple relatively efficiently, controllability is strong, and magnesium hydroxide (340-490 degree) when being heated absorption combustionmaterial surface heat (decomposition absorbs heat 900-1200J/g) takes place to decompose plays fire retardation; Discharge the oxygen on large quantity of moisture dilution combustion thing surface simultaneously, the activated magnesia that decomposes generation is attached to the combustiblematerials surface and has further stoped incendiary to carry out again.Magnesium hydroxide not only produces without any objectionable impurities in whole fire-retardant process, and the product of its decomposition can also absorb obnoxious flavour and smog that polymer burnings such as rubber, plastics are produced in a large number in fire-retardant, activated magnesia constantly absorbs imperfect combustion fusing residue, eliminate smog when burning is stopped very soon, stop molten drop, play secluding air and stop the incendiary purpose.In addition, also have nontoxic poison arranged, low cigarette or press down cigarette, low burn into prepares advantages such as simple, cheap, products of combustion is single (to be MgO and H
2O) no toxic substance produces, and can not produce secondary pollution environmental protection more to environment.
The present invention adopts the coating blending technology, advantage such as have that processing conditions is wide in range, technology is easily controlled, productivity height, system are stable.In addition, environmental-protection flame-retardant of the present invention, press down cigarette, insulation, heat insulating function coating, its main stuffing resource is wide, physicochemical property stable and cheap; Preparation technology is simple relatively, controllability is strong, utilize the technology of existing scale operation coating, almost cost free increases, improved production efficiency greatly, the heat insulating effect of the existing coating that improves, improved its poor heat stability, inflammable, drawback such as the burning fuming amount is big, be applicable to that commercial scale production promotes.
Description of drawings
The self-control nano-sized magnesium hydroxide SEM photo that Fig. 1 adopts for the present invention;
Fig. 2 is the subsidence curve of modified Nano magnesium hydroxide in organic system (paraffin) that organic modification of surface is handled that pass through shown in Fig. 1 nano-sized magnesium hydroxide;
Fig. 3 is the modified Nano magnesium hydroxide photo in kind behind the sedimentation 4h in organic system (paraffin) that organic modification of surface is handled that passes through shown in Fig. 1 nano-sized magnesium hydroxide;
Fig. 4 makes the time temperature curve of coating dry film for the pure elasticity third newborn dry film and the embodiment of the invention 3;
Live photo when the dry film material object that Fig. 5 makes for pure elasticity third breast burns;
Live photo when Fig. 6 is the functional paint dry film burning for preparing among the embodiment 3;
Fig. 7 is the burning residue photo of various coating dry films later, and the left side is pure elasticity third breast, and the centre is the binary third newborn dry film of embodiment 6 preparations, and the right is the dry film of embodiment 3 preparations.
Embodiment
Further specify below in conjunction with embodiment 1-6, accompanying drawing.
Nano-sized magnesium hydroxide among the embodiment 1-6 all adopts the nano-magnesium hydrate fire retardant of self-control surface organic modification.Fig. 1 is the SEM photo of self-control nano-magnesium hydrate fire retardant, and can be observed magnesium hydroxide in the SEM photo is sheet structure, and size distribution is even, median size 50-100nm.
This nano-sized magnesium hydroxide adopts following nano-sized magnesium hydroxide organic modification of surface treatment process to produce, and this method comprises: the nano-sized magnesium hydroxide slurry that makes is cleaned, filters; Properties-correcting agent in this slurry after a certain amount of hydrolysis of adding carries out high temperature coupling modification; Centrifugation, drying obtain the nano-magnesium hydrate fire retardant of surface modification; Wherein, described properties-correcting agent addition is the 2-10% of the nano-sized magnesium hydroxide quality in this slurry, and described properties-correcting agent is silane coupling agent, stearate, titanic acid ester, aluminic acid ester or aluminium titanium composite coupler.
Fig. 2, the 3rd, this self-control modified Nano magnesium hydroxide is at the settling test curve of organic system (the 1g magnesium hydroxide is dispersed in the whiteruss of 15ml) and the photo in kind behind the sedimentation 4h, in Fig. 2 subsidence curve as can be seen through the magnesium hydroxide of organic modification of surface and organic system than undressed avidity strong (settling velocity is obviously slack-off), significantly improved the dispersiveness of nano-sized magnesium hydroxide in organic system.Adopt the incandescence of solar simulated irradiation intermediate infrared radiation, the adjusting light source is 15cm to the distance of dry film, and then the dry film sample that obtains among the irradiation embodiment under the identical ambient conditions, the temperature registration at every 30s record dry film back side, the time temperature curve that record obtains, test average for three times after, the data that obtain are (Fig. 4 makes the time temperature curve of coating dry film for the pure elasticity third newborn dry film and following embodiment 3) as shown in Figure 4.As seen, the heat insulation curve of the dry film sample that is obtained by this embodiment 3 as can be seen, adding nano-sized magnesium hydroxide not have significantly to influence to the heat-proof quality of coating: the dry film sample of making than pure elastic emulsion, under the condition of starting temperature unanimity, the environmental-protection flame-retardant that this invention makes, press down cigarette, (infrared insulation, heat insulation) functional paint, in the time of 8.5min, heat-proof quality has the clear superiority of nearly 11 ℃ of temperature heads.
When Fig. 5 is the burning in kind of the dry film made of pure elasticity third breast live photo, can find out obviously that combustion processes produces a large amount of dense smokes and, in actual fire, form the secondary burning things which may cause a fire disaster easily with low phenomenon.
Fig. 6 is the live photo in functional paint dry film when burning of preparation among this embodiment 3, after can observing sample leave burning things which may cause a fire disaster in air, rapidly from putting out, and does not have dense smoke to produce.
Fig. 7 has showed pure elasticity third breast and this embodiment 3 and 6 preparation dry films respectively through the incendiary residual condition, and the left side is the pure elasticity third newborn L, and the centre is the binary third newborn dry film M of these embodiment 6 preparations, and the right is the dry film R of these embodiment 3 preparations.As seen compare with the pure elasticity third newborn dry film, embodiment 3 and 6 dry film product have all kept the shape before the burning, do not occur low phenomenon in the whole combustion processes.
With 100 parts of (massfractions, pure-acrylic emulsion down together), 30 parts water, 20 parts zirconium white, 20 parts trichroite, 20 parts titanium dioxide, and modified Nano flame retardant of magnesium hydroxide and 1 part of zinc oxide synergistic flame retardant that 10 parts organic modification of surface is handled carry out just mixing, and first silver mixing spare is mechanical stirring 30min under the 100rpm speed; The sodium lauryl sulphate wetting agent, 2 parts AMJ Dispers H-940 dispersion agent and 0.5 part the defoamer A that in mixed system, add 0.1 part then, utilize clarifixator under 15000rpm speed, to carry out high-speed stirring and further mix 3min, mix, disperse 3h by the high speed ball milling again, ball milling speed is 400rpm; Wherein, 0.5 part defoamer A is by 0.3 part AMJ
TMDefoam 8110 and 0.2 part of diamylamine are formed.
Adding 0.5 part of CX-470(in the blend that obtains is defoamer B), the Flowstar FL-333G flow agent of 0.3 part AMP-95 PH conditioning agent (being 2-amino-2-methyl propyl alcohol), 2 parts of AMJ AGSE-IB membrane-forming agents and 0.3 part, and then by ball mill low speed mixing dispersion 2h, ball milling speed is 50rpm; And then in the blend that obtains, add 5 parts thickening material again, and low speed ball milling 0.5h, speed is 50rpm; Wherein, 5 parts thickening material is made up of 2.5 parts AMJ HASE 420 and 2.5 parts RM2020.Final product by film pulling device, is made the dry film coating of 2mm thickness.
The flame retardant properties of material is measured and is adopted oxygen index method (down together), the volumetric concentration of oxygen is that 21%(is an oxygen index 21 in the nature air), theoretically, as long as the oxygen index of material is greater than 21, and it just has self-extinguishing can reach prevention incendiary purpose in air.
Make the dry film of 2mm thickness by pure-acrylic emulsion, its oxygen index that records is lower than 18, and low phenomenon is arranged in combustion processes, and emits with a large amount of dense smokes.And by the dry film coating that above-mentioned prepared obtains, because the magnesium hydroxide addition is on the low side, do not improve so oxygen index is obvious, the incendiary phenomenon still appears in air, but the amount of being fuming has obtained better controlled, has only a spot of flue gas to produce, and smoke suppressing effect is preferably arranged.
The effect of heat insulation aspect, under the incandescence illuminate condition of solar simulated irradiation intermediate infrared radiation (light source is 15cm to the distance of dry film), in the time of 8.5min, compare with the dry film that pure-acrylic emulsion is made, the back temperature of the coating dry film that this embodiment obtains has reduced about 14 ℃, and tangible heat insulation and preservation effect is arranged.
Embodiment 2
With 60 parts benzene emulsions, 25 parts water, 5 parts zirconium white, 5 parts trichroite, 5 parts titanium dioxide, and modified Nano flame retardant of magnesium hydroxide and 6 parts of stannic oxide synergistic flame retardants that 60 parts organic modification of surface is handled carry out just mixing, and first silver mixing spare is mechanical stirring 20min under the 400rpm speed; The wetting agent, 4 parts tripoly phosphate sodium STPP dispersion agent and 0.4 part the aluminum stearate (being defoamer A) that in mixed system, add 0.5 part then, utilize clarifixator under 12000rpm speed, to carry out high-speed stirring and further mix 5min, mix, disperse 3h by the high speed ball milling again, ball milling speed is 200rpm; Wherein, 0.5 part wetting agent is by 0.3 part of sodium stearate and 0.2 part of AMJ
TMWet DF-16 forms.
In the blend that obtains, add 0.4 part of AMJ Defoam 8010(defoamer B), the Flowstar FL309 flow agent of 1.0 parts AMP-95 PH conditioning agent, 4.5 parts of glycol ether N-BUTYL ACETATE membrane-forming agents and 1.5 parts, and then by ball mill low speed mixing dispersion 2h, ball milling speed is 150rpm; And then in the blend that obtains, add 2.5 parts AMJ HEUR 3020 thickening materials, and low speed ball milling 0.5h, speed is 150rpm.Final product by film pulling device, is made the dry film coating of 2mm thickness.
Make the dry film of 2mm thickness by the purified petroleum benzin acrylic emulsion, its oxygen that records refers to less than 17, and low phenomenon is arranged in combustion processes, and emits with a large amount of dense smokes and toxic gas.And obtaining the thick dry film of 2mm by above-mentioned prepared, oxygen index surpasses 30, improves a lot, and can significant flame retardant effect be arranged, and do not have the low generation that manifests the shape before sample can keep burning fully rapidly from putting out leave burning things which may cause a fire disaster in air after; Also do not have obvious flue gas in the combustion processes and produce, its smoke suppressing effect is very obvious.
The effect of heat insulation aspect, under the incandescence illuminate condition of solar simulated irradiation intermediate infrared radiation (light source is 15cm to the distance of dry film), in the time of 8.5min, compare with the dry film that the purified petroleum benzin acrylic emulsion is made, the back temperature of the coating dry film that this embodiment obtains has reduced about 5 ℃, has played certain heat-insulation and heat-preservation effect.
With 40 parts elasticity acrylic emulsions, 20 parts water, 5 parts zirconium white, 15 parts trichroite, 15 parts titanium dioxide, and the modified Nano flame retardant of magnesium hydroxide handled of 20 parts organic modification of surface and 2 parts red phosphorus synergistic flame retardant carry out just mixing, and first silver mixing spare is mechanical stirring 10min under the 300rpm speed; The AMJ Wet CF-10 wetting agent, 1 part dispersion agent and 0.3 part the tributyl phosphate (defoamer A) that in mixed system, add 0.2 part then, utilize clarifixator under 9000rpm speed, to carry out high-speed stirring and further mix 9min, mix, disperse 3h by the high speed ball milling again, ball milling speed is 300rpm; Wherein, 1 part dispersion agent by 0.5 part tripoly phosphate sodium STPP and 0.5 part BYK-182 forms.
In the blend that obtains, add 0.3 part of AMJ
TMDefoam 8112(defoamer B), CX-103 flow agent of 0.5 part AMP-95 PH conditioning agent, 1.5 parts of alcohol ester-12 membrane-forming agents and 0.6 part, and then disperse 2h by the ball mill low speed mixing, ball milling speed is 180rpm; And then in the blend that obtains, add 1 part thickening material again, and low speed ball milling 0.5h, speed is 180rpm.Final product by film pulling device, is made the dry film coating of 2mm thickness.Wherein, 1 part thickening material is made up of 0.5 part AMJ HEUR 3050 and 0.5 part AMJ HASE 430.
Make the dry film of 2mm thickness by pure elasticity acrylic emulsion, its oxygen that records refers to less than 17, and low phenomenon is arranged in combustion processes, and emits with a large amount of dense smokes.And obtaining the thick dry film of 2mm by above-mentioned prepared, oxygen index surpasses 24, is significantly improved, can put out certainly rapidly after in air, leaving burning things which may cause a fire disaster, significant flame retardant effect is arranged, and do not have the low generation that manifests, the shape (as shown in Figure 7) before sample can keep burning fully; Also do not have dense smoke in the combustion processes and produce, it is also satisfactory that it presses down the cigarette effect.
The effect of heat insulation aspect, under the incandescence illuminate condition of solar simulated irradiation intermediate infrared radiation (light source is 15cm to the distance of dry film), in the time of 8.5min, compare with the dry film that pure elasticity acrylic emulsion is made, the back temperature of the coating dry film that this embodiment obtains has reduced by 11 ℃, and tangible heat insulation and preservation effect (as shown in Figure 4) is arranged.
Embodiment 4
With 60 parts organosilicon crylic acid latexs, 25 parts water, 20 parts zirconium white, 5 parts trichroite, 5 parts titanium dioxide, and the modified Nano flame retardant of magnesium hydroxide handled of 50 parts organic modification of surface and 5 parts molybdenum oxide synergistic flame retardant carry out just mixing, and first silver mixing spare is mechanical stirring 30min under the 400rpm speed; The AMJ Wet PE-100 wetting agent, 5 parts Sodium hexametaphosphate 99 dispersion agent and 0.4 part the halo fatty amide (defoamer A) that in mixed system, add 0.5 part then, utilize clarifixator under 12000rpm speed, to carry out high-speed stirring and further mix 15min, mix, disperse 3h by the high speed ball milling again, ball milling speed is 400rpm.
In the blend that obtains, add 0.4 part of AMJ
TMDefoam 8112(is defoamer B), the flow agent of 0.8 part AMP-95 PH conditioning agent, 5 parts of membrane-forming agents and 2 parts, and then disperse 2h by the ball mill low speed mixing, ball milling speed is 120rpm; Wherein, 5 parts of membrane-forming agents are made up of 2 parts of alcohol ester-12 and 3 part glycol ethers, and 2 parts flow agent is made up of 0.8 part of CX-103 and 1.2 part Flowstar FL309.And then in the blend that obtains, add 1.5 parts AMJ HEUR 3040 thickening materials, and low speed ball milling 0.5h, speed is 120rpm.Final product by film pulling device, is made the dry film coating of 2mm thickness.
Make the dry film of 2mm thickness by the pure silicon acrylic emulsion, its oxygen that records refers to less than 20, and low phenomenon is arranged in combustion processes, and emits with dense smoke.And obtaining the thick dry film of 2mm by above-mentioned prepared, oxygen index surpasses 29, improves a lot, and can significant flame retardant effect be arranged, and do not have the low generation that manifests the shape before sample can keep burning fully rapidly from putting out leave burning things which may cause a fire disaster in air after; Do not have obvious dense smoke in the combustion processes yet and produce, reached good smoke suppressing effect yet.
The effect of heat insulation aspect, under the incandescence illuminate condition of solar simulated irradiation intermediate infrared radiation (light source is 15cm to the distance of dry film), in the time of 8.5min, compare with the dry film that the pure silicon acrylic emulsion is made, the back temperature of the coating dry film that this embodiment obtains has reduced by 7 ℃, and heat-insulation and heat-preservation effect is preferably arranged.
With 40 parts acrylate and vinyl acetate emulsions, 10 parts water, 15 parts zirconium white, 10 parts trichroite, 10 parts titanium dioxide, and the modified Nano flame retardant of magnesium hydroxide handled of 40 parts organic modification of surface and 4 parts zinc borate synergistic flame retardant carry out just mixing, and first silver mixing spare is mechanical stirring 20min under the 200rpm speed; The Sodium dodecylbenzene sulfonate wetting agent, 3 parts AMJ Dispers H-942 dispersion agent and 0.1 part the hexalin (defoamer A) that in mixed system, add 0.4 part then, utilize clarifixator under 6000rpm speed, to carry out high-speed stirring and further mix 12min, mix, disperse 3h by the high speed ball milling again, ball milling speed is 200rpm.
In the blend that obtains, add 0.1 part of BEK-750(defoamer B), the Flowstar FL-333G flow agent of 0.7 part AMP-95 PH conditioning agent, 3.5 parts of ethylene glycol vinyl acetic monomer membrane-forming agents and 0.8 part, and then by ball mill low speed mixing dispersion 2h, ball milling speed is 90rpm; And then in the blend that obtains, add 0.5 part RM-8W thickening material, and low speed ball milling 0.5h, speed is 90rpm.Final product by film pulling device, is made the dry film coating of 2mm thickness.
Make the dry film of 2mm thickness by pure acrylate and vinyl acetate emulsion, its oxygen that records refers to less than 18, and low phenomenon is arranged in combustion processes, and emits with dense smoke and acid gas.And obtaining the thick dry film of 2mm by above-mentioned prepared, oxygen index surpasses 26, is significantly improved, and can significant flame retardant effect be arranged, and do not have the low generation that manifests the shape before sample can keep burning fully rapidly from putting out leave burning things which may cause a fire disaster in air after; Do not have obvious flue gas in the combustion processes yet and produce, reached tangible smoke suppressing effect yet.
The effect of heat insulation aspect, under the incandescence illuminate condition of solar simulated irradiation intermediate infrared radiation (light source is 15cm to the distance of dry film), in the time of 8.5min, compare with the dry film that pure acrylate and vinyl acetate emulsion is made, the back temperature of the coating dry film that this embodiment obtains has reduced by 7.5 ℃, and heat-insulation and heat-preservation effect is preferably arranged.
Embodiment 6
With each water of 40 parts, 30 parts of elasticity acrylic emulsion and benzene emulsion, 10 parts zirconium white, 20 parts trichroite, 10 parts titanium dioxide, and the antimonous oxide of the modified Nano flame retardant of magnesium hydroxide handled of 30 parts organic modification of surface and 3 parts imitates fire retardant and carries out just mixing, and first silver mixing spare is mechanical stirring 10min under the 300rpm speed; The butyl oleate sodium sulfate wetting agent, 2.5 parts AMJ Dispers H-943 dispersion agent and 0.2 part the DF-691(defoamer A that in mixed system, add 0.3 part then), utilize clarifixator under 8000rpm speed, to carry out high-speed stirring and further mix 9min, mix, disperse 3h by the high speed ball milling again, ball milling speed is 300rpm.
In the blend that obtains, add 0.2 part of AMJ Defoam 8040(defoamer B), the Flowstar FL-333H flow agent of 0.6 part AMP-95 PH conditioning agent, 2.5 parts of ethylene glycol monomethyl ether propyl acetate membrane-forming agents and 1 part, and then by ball mill low speed mixing dispersion 2h, ball milling speed is 180rpm; And then in the blend that obtains, add 4 parts PU-8080 thickening material, and low speed ball milling 0.5h, speed is 180rpm.Final product by film pulling device, is made the dry film coating of 2mm thickness.
By the thick dry film of 2mm that pure elasticity acrylic emulsion and benzene emulsion binary system are made, its oxygen that records refers to less than 18, and low phenomenon is arranged in combustion processes, and emits with dense smoke and toxic gas.And obtaining the thick dry film of 2mm by above-mentioned prepared, oxygen index surpasses 23, is significantly improved, and can certain flame retardant effect be arranged, and do not have the low generation that manifests the shape (as shown in Figure 7) before sample can keep burning substantially in air rapidly from putting out; No obvious dense smoke produces in the combustion processes, has also reached certain smoke suppressing effect.
The effect of heat insulation aspect, under the incandescence illuminate condition of solar simulated irradiation intermediate infrared radiation (light source is 15cm to the distance of dry film), in the time of 8.5min, compare with the dry film that pure binary acrylic emulsion is made, the back temperature of the coating dry film that this embodiment obtains has reduced by 9 ℃, and gratifying heat-insulation and heat-preservation effect is arranged.
The coating of the foregoing description 1-6 is as film forming material with acrylic emulsions, with trichroite and zirconium white as the near-infrared radiation functional stuffing, with the nano-sized magnesium hydroxide of surface organic modification as fire-retardant and press down the cigarette filler, add synergistic flame retardant and auxiliary agent, be composited through ball milling, high speed dispersion and stirring technique; Wherein, the particle diameter of Zirconium powder is 30-100nm, and the particle diameter of trichroite is 3-10 μ m, and the nano-sized magnesium hydroxide median size is 50-100nm.Prepared functional paint all has good thermal and insulating performance, by adding nano-sized magnesium hydroxide, its oxygen index has also obtained raising in various degree, all surpassed 21 and can in air, realize self-gravitation, the oxygen index that finished product coating is made the thick dry film of 1.5-3mm with film pulling device reaches 23-30, reach the good flame effect, and all effectively suppressed the generation of flue gas, not only reached fire-retardant purpose and environmental protection.
Claims (10)
1. an environmental-protection flame-retardant presses down the hood preparation method for coating, it is characterized in that comprising the steps:
S1, will be as nano-magnesium hydrate fire retardant 10-60 part and synergistic flame retardant 1-10 part of acrylic emulsions 40-100 part of film forming material, water 10-30 part, zirconium white 5-20 part, trichroite 5-20 part, Rutile type Titanium Dioxide 5-20 part, surface organic modification, mechanical stirring 10-30min under 100-500rpm speed carries out just mixing; In mixed system, add wetting agent 0.1-0.5 part, dispersion agent 1-5 part and defoamer A 0.1-0.5 part then, utilize clarifixator to carry out high-speed stirring under 6000-15000rpm speed and further mix 3-15min, the ball milling speed high speed ball milling with 200-400rpm mixes, disperses 1.5-5h again;
S2, in the blend that step S1 obtains, add defoamer B 0.1-0.5 part, PH conditioning agent 0.3-1 part, membrane-forming agent 1-5 part and flow agent 0.3-2 part, and then by ball mill with the ball milling speed low speed mixing of 50-180rpm, disperse 1-3h; And
S3, add thickening material 0.5-5 part again in the blend that step S2 obtains, the ball milling speed low speed ball milling 0.5-1h with 50-180rpm obtains finished product coating;
Above umber is mass parts.
2. method according to claim 1 is characterized in that: described acrylic emulsions is selected the composition of a kind of in pure-acrylic emulsion, elasticity acrylic emulsion, benzene emulsion, organosilicon crylic acid latex and the acrylate and vinyl acetate emulsion or at least two kinds for use.
3. method according to claim 1 and 2 is characterized in that: the particle diameter of described Zirconium powder is 30-100nm, and the particle diameter of described trichroite is 3-10 μ m, and described nano-sized magnesium hydroxide median size is 50-100nm.
4. method according to claim 3 is characterized in that: described synergistic flame retardant is selected at least a in red phosphorus, zinc oxide, weisspiessglanz, stannic oxide, molybdenum oxide, ammonium molybdate, the zinc borate for use.
5. method according to claim 1 is characterized in that: among the step S1, described wetting agent adopts aniorfic surfactant, nonionic surface active agent or anionic/nonionic compound surfactant; Described dispersion agent is selected inorganic dispersant, polymer dispersant or compound dispersion agent; Described defoamer A adopts organic defoamer.
6. method according to claim 1 or 5, it is characterized in that: among the step S2, described flow agent adopts modified organic silicon type flow agent, and described PH conditioning agent is a 2-amino-2-methyl propyl alcohol, and described defoamer B adopts silicone based defoamer.
7. method according to claim 1 is characterized in that: the nano-sized magnesium hydroxide of described organic modification of surface adopts following organic modification of surface treatment process to produce, and this treatment process comprises: the nano-sized magnesium hydroxide slurry that makes is cleaned, filters; Properties-correcting agent in this slurry after a certain amount of hydrolysis of adding carries out high temperature coupling modification; Centrifugation, drying obtain the nano-magnesium hydrate fire retardant of surface modification; Wherein, described properties-correcting agent addition is the 2-10% of the nano-sized magnesium hydroxide quality in this slurry.
8. according to claim 1 or 7 described methods, it is characterized in that: the oxygen index that described finished product coating is made the thick dry film of 1.5-3mm with film pulling device reaches 23-30.
9. environmental type flame-retardant smoke inhibition functional paint, it is characterized in that: this coating is as film forming material with acrylic emulsions, with trichroite and zirconium white as the near-infrared radiation functional stuffing, with the Rutile type Titanium Dioxide is pigment, with the nano-sized magnesium hydroxide of surface organic modification as fire-retardant and press down the cigarette filler, add synergistic flame retardant and auxiliary agent, be composited through ball milling, high speed dispersion, stirring technique; In mass parts, comprise in this coating: nano-magnesium hydrate fire retardant 10-60 part of acrylic emulsions 40-100 part, water 10-30 part, zirconium white 5-20 part, trichroite 5-20 part, Rutile type Titanium Dioxide 5-20 part, surface organic modification and synergistic flame retardant 1-10 part.
10. functional paint according to claim 9 is characterized in that: the particle diameter of described Zirconium powder is 30-100nm, and the particle diameter of described trichroite is 3-10 μ m, and described nano-sized magnesium hydroxide median size is 50-100nm.
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| CN103275586A (en) * | 2013-06-13 | 2013-09-04 | 朱良菊 | Novel high-temperature resistant flame-retardant coating |
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Address after: Shenzhen Graduate School of Guangdong Province, Shenzhen City Xili 518055 Nanshan District University City Tsinghua University Patentee after: Tsinghua Shenzhen International Graduate School Address before: Shenzhen Graduate School of Guangdong Province, Shenzhen City Xili 518055 Nanshan District University City Tsinghua University Patentee before: GRADUATE SCHOOL AT SHENZHEN, TSINGHUA University |
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