CN102241931B - 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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- CN102241931B CN102241931B CN201110159044.5A CN201110159044A CN102241931B CN 102241931 B CN102241931 B CN 102241931B CN 201110159044 A CN201110159044 A CN 201110159044A CN 102241931 B CN102241931 B CN 102241931B
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- 239000003973 paint Substances 0.000 title claims abstract 7
- 238000002360 preparation method Methods 0.000 title claims abstract 4
- 239000003063 flame retardant Substances 0.000 claims abstract 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract 10
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract 10
- 238000000034 method Methods 0.000 claims abstract 10
- 239000002105 nanoparticle Substances 0.000 claims abstract 10
- 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 9
- 239000000839 emulsion Substances 0.000 claims abstract 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000002245 particle Substances 0.000 claims abstract 7
- 230000002195 synergetic effect Effects 0.000 claims abstract 7
- 238000000498 ball milling Methods 0.000 claims abstract 6
- 239000000463 material Substances 0.000 claims abstract 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 3
- 239000001301 oxygen Substances 0.000 claims abstract 3
- 239000012752 auxiliary agent Substances 0.000 claims abstract 2
- 239000012757 flame retardant agent Substances 0.000 claims abstract 2
- 230000005855 radiation Effects 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims 15
- 230000004048 modification Effects 0.000 claims 12
- 238000012986 modification Methods 0.000 claims 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 9
- 239000011248 coating agent Substances 0.000 claims 6
- 238000000576 coating method Methods 0.000 claims 6
- 239000013530 defoamer Substances 0.000 claims 6
- 239000002002 slurry Substances 0.000 claims 6
- 239000000203 mixture Substances 0.000 claims 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 4
- 239000006185 dispersion Substances 0.000 claims 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000004094 surface-active agent Substances 0.000 claims 3
- 239000004408 titanium dioxide Substances 0.000 claims 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims 2
- 150000004645 aluminates Chemical class 0.000 claims 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 2
- 239000011609 ammonium molybdate Substances 0.000 claims 2
- 229940010552 ammonium molybdate Drugs 0.000 claims 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims 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 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 2
- 230000003750 conditioning effect Effects 0.000 claims 2
- 230000008878 coupling Effects 0.000 claims 2
- 238000010168 coupling process Methods 0.000 claims 2
- 238000005859 coupling reaction Methods 0.000 claims 2
- 239000002270 dispersing agent Substances 0.000 claims 2
- 230000007062 hydrolysis Effects 0.000 claims 2
- 238000006460 hydrolysis reaction Methods 0.000 claims 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 2
- 238000004381 surface treatment Methods 0.000 claims 2
- -1 titanic acid ester Chemical class 0.000 claims 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- 239000000080 wetting agent Substances 0.000 claims 2
- 239000011787 zinc oxide Substances 0.000 claims 2
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 235000019504 cigarettes Nutrition 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- 238000000875 high-speed ball milling Methods 0.000 claims 1
- 238000009775 high-speed stirring Methods 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 claims 1
- 239000004816 latex Substances 0.000 claims 1
- 229920000126 latex Polymers 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 239000000049 pigment Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000779 smoke Substances 0.000 claims 1
- 230000008719 thickening Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract 2
- 239000011020 iolite Substances 0.000 abstract 2
- 239000000843 powder Substances 0.000 abstract 2
- 238000009413 insulation Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
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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 there is 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 scientific and technical progress and development, people increase day by day to the demand of the energy, and traditional Nonrenewable energy resources are fewer and feweri.And to Nonrenewable energy resources excessive exploitation and waste, not only cause the supply of the energy gradually nervous, and aggravate the deterioration of environment.Therefore, how to develop the green energy resource that makes new advances and reduce oneself very urgent problem in becoming China and even world wide of energy consumption.
Building energy consumption occupies very important status 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, therefore building energy conservation is significant.In China, the data presentation that Minstry of Housing and Urban-Rural Development of People Republic of China (MOHURD) announces recently, the annual 2000000000 newly-increased m in the whole nation
2in floor area of building, 80% belongs to high energy consumption building; And the unit surface Energy in use of house class building is compared with the country of equal weather condition, and China will exceed 2～3 times, and therefore building energy conservation tool is of great significance.Heat-insulating (thermal insulation) insulation is the importance that function was lived and used to save energy, raising buildings.
Thermal isolation technique has become one of study hotspot of the effective utilization of the energy in recent years and energy-saving field extensive concern, and this technology is to utilize the obstruct principle of falling low heat transfer and thermal radiation capability, and minimizing sunlight absorbs to reach the object of heat-insulation and heat-preservation.As everyone knows, being radiated the solar energy on earth surface, is approximately 750w/m per second
2, wherein the energy of visible region accounts for 45%, and near-infrared region accounts for 45%, and other electromagnetic radiation energy accounts for 5%.Visible, 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, near infrared range.Under the irradiation of sunlight, heat constantly accumulates on radiation exposed body surface, can make its surface temperature constantly raise.In theory, by the energy of near-infrared band in sunlight is effectively intercepted, reflection and radiation, can realize the object of shone thing heat insulation and heat control.
Aquosity heat insulating heat preserving paint is a class of current most study, however one of key issue that directly restricts its application while being exactly single use effect of heat insulation bad, one of main method addressing this problem is exactly to adopt compound thermal isolation technique.Publication number is that one or more have prepared a kind of composite water-borne building insulation coating by fill the heat-insulation and heat-preservation fillers such as hollow glass micropearl, AHS-2500 heat-reflecting heat-insulating powder and aluminum oxide in polywater based acrylic resin system in for the patent of invention of CN102010641A.Publication number is that the patent of invention of CN101967331A is to have prepared by add hollow ceramic microspheres, glass microballon or closed-cell expanded perlite in acrylic emulsions, VAE emulsion, fluorine carbon emulsion the insulating mold coating of using for railcar; Publication number is that the patents such as CN101831229A, CN101760108A, CN101696336A, CN101555377 and CN101108931 are also the heat insulating effects that mainly reaches interior outer wall water-based coating by add hollow glass microbead (add and array mode slightly difference) in acrylic resin emulsion, epoxy emulsion or water glass.
The thermal insulation technology of visible current coating mainly concentrates on to be realized with pearlstone or pottery or the hollow glass micropearl etc. of silicates material.But, this type of material production process complexity, cost is high, energy consumption is large, has the problems such as environmental pollution, and owing to being subject to dimensional constraints (micron order), the room for promotion of its heat insulating effect is less, and machinery, coating and bond performance to resin base material all exists certain negative impact.
In addition, along with the demand of Coating Market constantly increases, coating itself also exists some potential safety hazards, such as, organic composition in coating is a lot, organic materials is heat-resisting poor, easy firing, and discharge amount of heat in when burning, produce a large amount of poison gas, not only can accelerate large fire spreading, and easily cause trapped personnel and rescue personnel's injures and deaths, it in traditional coating, is its fire retardancy of raising, often add containing bromide fire retardant, although this has improved fire retardancy to a certain extent, but also bring serious environmental disruption simultaneously, once particularly there is serious fire, these brominated materials have more increased the harm of toxic smoke.Numerous fire failures prove, the toxic gas that building, finishing material burning produce is the maximum killer in fire, sucks the lethal number of poison gas and accounts for the more than 70 ~ 75% of fire fatality total number of persons.Therefore, develop the high strength that has, the performance such as wear-resisting, weather-proof is excellent, and environmentally safe, low toxicity and the danger of catching fire 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 of generation is nontoxic, corrosion-free.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 of fire retardant is being heated while reaching certain temperature, MH decomposition discharges moisture, absorb a large amount of latent heat (MH decomposition temperature 340 ~ 490oC simultaneously, absorb heat 900 ~ 1200J/g), thereby reduce the flame actual temperature of material surface, made base material heated be degraded to low molecular Speed Reduction, reduced the release of inflammable gas; A large amount of water vapors of simultaneously discharging in decomposition course produce the concentration of flue gas while having watered down combustionmaterial near surface oxygen, inflammable gas and base burn, make that surface combustion is more difficult to be carried out; MH also has the extremely strong cigarette effect-Mg (OH) of pressing down
2be conducive to form surface char, stop entering of oxygen and heat, decompose the MgO generating is good refractory materials simultaneously, can improve the ability of base material opposing flame, plays the object that isolated air stops burning.Due to Mg (OH)
2the decomposes three elements (temperature, oxygen and combustiblematerials) that can make to burn are controlled simultaneously, have played fire retardation, once burning things which may cause a fire disaster disappears, burning can be from horizontal blanking.Compared 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 is prepared the advantages such as simple, cheap, its flame mechanism is relatively simple, controllability is strong, and products of combustion is single (is MgO and H
2o) can not produce secondary pollution, thereby environmental protection more.
Research and report for the fire-retardant and smoke suppressing of heat insulating water-borne coatings are also few, still in the desk study stage.In the recent period, the patent that publication number is CN101302396 discloses a kind of preparation method of the high temperature-resistant flame-retardant insulating paint being made up of 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, although make the high temperature resistant and flame retardant properties of product obtain certain raising, the smoke suppressing effect of entirety does not improve.
Nano-sized magnesium hydroxide refers to the magnesium hydrate powder (see our patent ZL 200710124792.3) of grain graininess between the nm of l～100, as a kind of nano material, except having the characteristic of common micron order flame retardant of magnesium hydroxide, also have advantages of that granularity is little, specific surface area is large, can reduce loading level, improve flame retarding efficiency and smoke suppressing effect; Reduce the advantages such as matrix machinery, coating, agglutinating value(of coal) loss of energy.Therefore, for 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 add trichroite, zirconium white, titanium dioxide, nano-sized magnesium hydroxide efficient flame-retarding agent and auxiliary agent in coating matrix, when making it reach heat insulating effect, have flame retardancy, self-extinguishing and smoke-suppressing concurrently, thereby improve the fire safety performance of product, reduce possibility and harm thereof that fire occurs.This functional paint has the advantages such as high insulating effect, good stability, fire-retardant and smoke suppressing effect be obvious, and the fire retardant adding produces without toxic substance in the time of burning, without potential harm, can not produce secondary pollution to environment to HUMAN HEALTH.
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, it is by trichroite stable physical and chemical performance, zirconium white, cenosphere and Rutile type Titanium Dioxide, and be effectively compounded in coating emulsion matrix through 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 the defects 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 hood preparation method for coating, comprises the steps:
S1, using the acrylic emulsions 40-100 part (mass parts as 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 mixed; Then in mixed system, add wetting agent 0.1-0.5 part, dispersion agent 1-5 part and defoamer A 0.1-0.5 part, utilize clarifixator under 6000-15000rpm speed, to carry out high-speed stirring and further mix 3-15min, then mix, disperse 1.5-5h with the ball milling speed high speed ball milling of 200-400rpm;
In S2, the blend that obtains to step S1, 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, again to step S2 obtain blend in add thickening material 0.5-5 part, with the ball milling speed low speed ball milling 0.5-1h of 50-180rpm, obtain finished product coating.
Wherein, acrylic emulsions is selected the composition of a kind of at least two kinds in pure-acrylic emulsion, elasticity acrylic emulsion, benzene emulsion, organosilicon crylic acid latex and acrylate and vinyl acetate emulsion.Synergistic flame retardant is selected at least one in red phosphorus, zinc oxide, weisspiessglanz, stannic oxide, molybdenum oxide, ammonium molybdate, zinc borate.
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 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) that are formed by lipid acid, mineral oil, emulsifying agent etc., alcohols (as hexalin), phosphoric acid ester (as tributyl phosphate), metal soap (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, the silicone antifoam agent AMJ Defoam 8040, the AMJ that contain 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 being formed by silicon, ester, emulsifying agent etc.).PH conditioning agent is AMP-95, i.e. 2-amino-2-methyl propyl alcohol.
Membrane-forming agent can adopt one or more the composition in alcohol ester-12, glycol ether, glycol ether N-BUTYL ACETATE, ethylene glycol vinyl acetic monomer, ethylene glycol monomethyl ether propyl acetate or 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 Siloxane-Oxyalkylene Copolymers multipolymer flow agent Flowstar FL309(Amy), 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: the swelling vinylformic acid rheology of hydrophobic alkali agent AMJ HASE 420; The swelling vinylformic acid rheology of the hydrophobic alkali of AMJ HASE 430 agent) one or both composition in thickening material etc.
Adopt a kind of environmental-protection flame-retardant prepared by aforesaid method to press down hood coating, it is characterized in that: this coating is using acrylic emulsions as film forming material, using trichroite and zirconium white as near-infrared radiation functional stuffing, take Rutile type Titanium Dioxide as pigment, using the nano-sized magnesium hydroxide of surface organic modification as fire-retardant and press down cigarette filler, add synergistic flame retardant and auxiliary agent, be composited through ball milling, high speed dispersion, stirring technique; In mass parts, in this coating, comprise: 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.This finished product coating reaches 23-30 with the oxygen index that film pulling device is made the thick dry film of 1.5-3mm, and smoke suppressing effect is remarkable.
The present invention is take acrylic emulsions as film forming matrix, stable with physicochemical property, cheap trichroite and zirconium white are as near-infrared radiation functional stuffing, widespread use on market, the good Rutile type Titanium Dioxide of chemical stability is pigment, and be fire-retardant by the modified Nano magnesium hydroxide of organic modification of surface processing, press down cigarette filler, preparation has fire-retardant, press down the compound aqueous functional coatings of heat-insulation and heat-preservation of cigarette characteristic, this coating is coated on body surface, radiation to near-infrared band in sun projection has good iris action, the heat energy of absorption can be radiated to surrounding space with the form of long wave, therefore the heat insulating effect that covers substrate is given prominence to, and there is obvious flame retardant properties, and in combustion processes, there is 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 functional paint (water-borne coatings) prepared by the present invention is not generally subject to the restriction of occasion, also not needing special coating tool and equipment, is one of ideal substitute of usual solvent based coating.And it is simple to have construction, the feature having merged with existing operating technique.
Acrylate of the present invention is the serial water-base resin of main film forming substance, that current water-borne coatings art is the most ripe, one of most widely used one-tenth film base material, not only have advantage but also the low production cost of low VOC and low toxicity, snappiness, physical strength, wear resistance, guarantor's light and tint retention, anticorrosion, alkaline-resisting and the over-all properties such as water tolerance and weathering resistance is very excellent.This type of water-base resin contains multiple functional group, thereby multiple matrix is all had to good adaptability, has stronger sticking power; By regulating kind (comprising carbochain length, the cladodification degree etc. of its ester group) and molecular weight and the distribution thereof of different acrylate, can give the different snappiness of film and hardness, this multiple requirement for different application field is particularly important; Meanwhile, esters of acrylic acid dry solidification is typical free radical mechanism, has rate of drying fast, is subject to the features such as ectocine is less, easy construction.This resinoid contains certain polar group, has very strong bonding force with the inorganic powder adding, and is not easy to produce 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 easily infiltrate, and has reduced workload and the difficulty of inorganic powder being carried out to surface modification.
The present invention is using trichroite and zirconium white as near-infrared radiation functional stuffing.Trichroite has higher infrared emittance, especially in 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, nano zircite particle is little, and density is little, and specific surface area is large, surface atom number is many, surface can be high, and the serious coordination deficiency of surface atom, has very strong surfactivity and superpower adsorptive power, in near infrared whole wave band, there is stronger infra red radiation function, be added in coating, very easily with resin in oxygen play bonding action, improve the bonding strength between workability and film and the matrix of intermolecular bonding force and coating.
Compared 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 that purity is high, the advantage such as the super refinement of granularity, flame retardant properties are good, after organic modification of surface is processed, effectively solve and the interface problem of other organic fillers or base material, and then realized the object that reduces loading level and improve flame retardant effect.Conventionally compared with the flame-retardant system (bromine system, phosphorus system, nitrogen system level expansion type flame retardant etc.) adopting with prior art, its fire retardant mechanism is relatively simple efficiently, controllability is strong, and magnesium hydroxide (340-490 degree) in the time being heated absorption combustionmaterial surface heat (decomposition absorbs heat 900-1200J/g) occurs to decompose and plays fire retardation; Discharge the oxygen on large quantity of moisture dilution combustion thing surface simultaneously, decompose the activated magnesia generating and be attached to the carrying out that combustiblematerials surface has further stoped again burning.Magnesium hydroxide not only produces without any objectionable impurities in whole fire-retardant process, and the product of its decomposition can also absorb in a large number the polymer such as rubber, plastics the burn obnoxious flavour and the smog that produce in fire-retardant, activated magnesia constantly absorbs imperfect combustion fusing residue, when stopping very soon from making to burn, eliminate smog, stop molten drop, play the object that isolated air stops burning.In addition, also have and have nontoxic poison, low cigarette or press down cigarette, low burn into and prepare the advantages such as simple, cheap, products of combustion is single (is MgO and H
2o) produce without toxic substance, can not produce secondary pollution environmental protection more to environment.
The present invention adopts coating blending technology, has the advantages such as processing conditions is wide in range, technique is easily controlled, productivity is high, stable system.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 relatively simple, controllability is strong, utilize the technique of existing scale operation coating, almost cost free increases, greatly improve production efficiency, heat insulating effect of the existing coating improving, improve the drawbacks such as its poor heat stability, inflammable, burning fuming amount is large, be applicable to commercial scale production and promote.
Accompanying drawing explanation
Fig. 1 is the self-control nano-sized magnesium hydroxide SEM photo that the present invention adopts;
Fig. 2 is the subsidence curve of the modified Nano magnesium hydroxide that passes through organic modification of surface processing shown in Fig. 1 nano-sized magnesium hydroxide in organic system (paraffin);
Fig. 3 is the photo in kind after sedimentation 4h in organic system (paraffin) of the modified Nano magnesium hydroxide that passes through organic modification of surface processing shown in Fig. 1 nano-sized magnesium hydroxide;
Fig. 4 is the time temperature curve that the newborn dry film of pure elasticity third and the embodiment of the present invention 3 make coating dry film;
Live photo when Fig. 5 is the burning in kind of the dry film made of pure elasticity the third breast;
Live photo when Fig. 6 is the functional paint dry film burning of preparing in embodiment 3;
Fig. 7 is the burning residue photo of various coating dry films later, and the left side is pure elasticity the third breast, the middle newborn dry film of binary third of preparing for embodiment 6, and the right is dry film prepared by embodiment 3.
Embodiment
Further illustrate below in conjunction with embodiment 1-6, accompanying drawing.
Nano-sized magnesium hydroxide in 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 in SEM photo, can be observed magnesium hydroxide 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 the method comprises: the nano-sized magnesium hydroxide slurry making is cleaned, filtered; In this slurry, add the properties-correcting agent after a certain amount of hydrolysis to carry out high temperature coupling modification; Centrifugation, the dry nano-magnesium hydrate fire retardant that obtains 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, Aluminate or aluminium titanium composite coupler.
Fig. 2, the 3rd, the in kind photo of this self-control modified Nano magnesium hydroxide after settling test curve and the sedimentation 4h of organic system (1g magnesium hydroxide is dispersed in the whiteruss of 15ml), in Fig. 2 subsidence curve, can find out magnesium hydroxide through organic modification of surface with 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 solar simulated to irradiate the incandescence of intermediate infrared radiation, regulating light source is 15cm to the distance of dry film, and then under identical ambient conditions, irradiate the dry film sample obtaining in embodiment, every 30s records the temperature registration at the dry film back side, the time temperature curve that record obtains, after testing and averaging for three times, the data that obtain are (Fig. 4 is the time temperature curve that the newborn dry film of pure elasticity third and following embodiment 3 make coating dry film) as shown in Figure 4.Visible, the heat insulation curve of the dry film sample being obtained by this embodiment 3 can be found out, add nano-sized magnesium hydroxide there is no significantly impact to the heat-proof quality of coating: the dry film sample of making than pure elastic emulsion, under the consistent condition of starting temperature, environmental-protection flame-retardant that this invention makes, press down cigarette, (infrared insulation, heat insulation) functional paint, within 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 the third breast live photo, can obviously find out that combustion processes produces a large amount of dense smoke and with low phenomenon, in actual fire, easily form secondary burning things which may cause a fire disaster.
Live photo when Fig. 6 is the functional paint dry film burning of preparing in this embodiment 3, can observe sample and in air, leave after burning things which may cause a fire disaster, rapidly from putting out, and does not have dense smoke to produce.
Fig. 7 has shown that respectively pure elasticity the third breast and this embodiment 3 and 6 prepare the residual condition of dry film through burning, and the left side is the newborn L of pure elasticity third, the middle newborn dry film M of binary third preparing for this embodiment 6, and the right is dry film R prepared by this embodiment 3.Compared with the newborn dry film of visible and pure elasticity third, the dry film product of embodiment 3 and 6 has all kept the shape before burning, does not occur low phenomenon in whole combustion processes.
embodiment 1
By 100 parts of (massfractions, pure-acrylic emulsion down together), the water of 30 parts, the zirconium white of 20 parts, the trichroite of 20 parts, the titanium dioxide of 20 parts, and the modified Nano flame retardant of magnesium hydroxide of the organic modification of surface processing of 10 parts and 1 part of zinc oxide synergistic flame retardant carry out just mixedly, first silver mixing part is mechanical stirring 30min under 100rpm speed; Then in mixed system, add the sodium lauryl sulphate wetting agent of 0.1 part, the AMJ Dispers H-940 dispersion agent of 2 parts and the defoamer A of 0.5 part, utilize clarifixator under 15000rpm speed, to carry out high-speed stirring and further mix 3min, mixed, disperseed 3h by high speed ball milling again, ball milling speed is 400rpm; Wherein, the defoamer A of 0.5 part is by the AMJ of 0.3 part
tM8110 and 0.2 part of diamylamine composition of Defoam.
Be defoamer B to adding 0.5 part of CX-470(in the blend obtaining), the Flowstar FL-333G flow agent of the AMP-95 PH conditioning agent (being 2-amino-2-methyl propyl alcohol) of 0.3 part, 2 parts of AMJ AGSE-IB membrane-forming agents and 0.3 part, and then disperse 2h by ball mill low speed mixing, ball milling speed is 50rpm; And then to the thickening material that adds again 5 parts in the blend obtaining, low speed ball milling 0.5h, speed is 50rpm; Wherein, the thickening material of 5 parts is made up of the RM2020 of 420 and 2.5 parts of the AMJ HASE of 2.5 parts.Final product, by film pulling device, is made to the dry film coating of 2mm thickness.
The flame retardant properties of material is measured and is adopted oxygen index method (lower same), in nature air, the volumetric concentration of oxygen is that 21%(is oxygen index 21), theoretically, the oxygen index of material is only greater than 21, and it just has self-extinguishing can reach the object that stops burning in air.
Be made up the dry film of 2mm thickness of pure-acrylic emulsion, its oxygen index recording is lower than 18, and in combustion processes, has low phenomenon, and emits with a large amount of dense smoke.And the dry film coating preparing by above-mentioned technique, because magnesium hydroxide addition is on the low side, so oxygen index is not significantly improved, in air, still there is the phenomenon of burning, measure good control but be fuming, only had a small amount of flue gas to produce, had good smoke suppressing effect.
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), within the time of 8.5min, compared with the dry film made from pure-acrylic emulsion, the back temperature of the coating dry film that this embodiment obtains has reduced approximately 14 ℃, has obvious heat insulation and preservation effect.
By the benzene emulsion of 60 parts, the water of 25 parts, the zirconium white of 5 parts, the trichroite of 5 parts, the titanium dioxide of 5 parts, and the modified Nano flame retardant of magnesium hydroxide of the organic modification of surface processing of 60 parts and 6 parts of stannic oxide synergistic flame retardants carry out just mixedly, first silver mixing part is mechanical stirring 20min under 400rpm speed; Then in mixed system, add the wetting agent of 0.5 part, the tripoly phosphate sodium STPP dispersion agent of 4 parts and the aluminum stearate (being defoamer A) of 0.4 part, utilize clarifixator under 12000rpm speed, to carry out high-speed stirring and further mix 5min, mixed, disperseed 3h by high speed ball milling again, ball milling speed is 200rpm; Wherein, the wetting agent of 0.5 part is by 0.3 part of sodium stearate and 0.2 part of AMJ
tMwet DF-16 composition.
In the blend obtaining, add 0.4 part of AMJ Defoam 8010(defoamer B), the Flowstar FL309 flow agent of the AMP-95 PH conditioning agent of 1.0 parts, 4.5 parts of glycol ether N-BUTYL ACETATE membrane-forming agents and 1.5 parts, and then disperse 2h by ball mill low speed mixing, ball milling speed is 150rpm; And then to AMJ HEUR 3020 thickening materials that add 2.5 parts in the blend obtaining, low speed ball milling 0.5h, speed is 150rpm.Final product, by film pulling device, is made to the dry film coating of 2mm thickness.
Be made up the dry film of 2mm thickness of purified petroleum benzin acrylic emulsion, its oxygen recording refers to be less than 17, and in combustion processes, has low phenomenon, and emits with a large amount of dense smoke and toxic gas.And prepare by above-mentioned technique the dry film that 2mm is thick, and oxygen index exceedes 30, improves a lot, and in air, leaving after burning things which may cause a fire disaster rapidly from putting out, to have significant flame retardant effect, and manifests generation without low, the shape before sample can keep burning completely; In combustion processes, also without obviously flue gas generation, its smoke suppressing effect is very obvious.
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), within the time of 8.5min, compared with the dry film made from purified petroleum benzin acrylic emulsion, the back temperature of the coating dry film that this embodiment obtains has reduced approximately 5 ℃, has played certain thermal insulation function.
By the elasticity acrylic emulsion of 40 parts, the water of 20 parts, the zirconium white of 5 parts, the trichroite of 15 parts, the titanium dioxide of 15 parts, and the red phosphorus synergistic flame retardant of the modified Nano flame retardant of magnesium hydroxide of the organic modification of surface processing of 20 parts and 2 parts carries out just mixedly, first silver mixing part is mechanical stirring 10min under 300rpm speed; Then in mixed system, add the AMJ Wet CF-10 wetting agent of 0.2 part, the dispersion agent of 1 part and the tributyl phosphate (defoamer A) of 0.3 part, utilize clarifixator under 9000rpm speed, to carry out high-speed stirring and further mix 9min, mixed, disperseed 3h by high speed ball milling again, ball milling speed is 300rpm; Wherein, the dispersion agent of 1 part by 0.5 part tripoly phosphate sodium STPP and 0.5 part BYK-182 forms.
In the blend obtaining, add 0.3 part of AMJ
tMdefoam 8112(defoamer B), CX-103 flow agent of the AMP-95 PH conditioning agent of 0.5 part, 1.5 parts of alcohol ester-12 membrane-forming agents and 0.6 part, and then disperse 2h by ball mill low speed mixing, ball milling speed is 180rpm; And then to the thickening material that adds again 1 part in the blend obtaining, low speed ball milling 0.5h, speed is 180rpm.Final product, by film pulling device, is made to the dry film coating of 2mm thickness.Wherein, the thickening material of 1 part is made up of the AMJ HASE 430 of 3050 and 0.5 part of the AMJ HEUR of 0.5 part.
Be made up the dry film of 2mm thickness of pure elasticity acrylic emulsion, its oxygen recording refers to be less than 17, and in combustion processes, has low phenomenon, and emits with a large amount of dense smoke.And preparing by above-mentioned technique the dry film that 2mm is thick, oxygen index exceedes 24, is significantly improved, leave burning things which may cause a fire disaster in air after, can certainly put out rapidly, have significant flame retardant effect, and manifest generation without low, sample can keep the shape (as shown in Figure 7) before burning completely; In combustion processes, also produce without dense smoke, it is also satisfactory that it presses down cigarette effect.
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), within the time of 8.5min, compared with the dry film made from pure elasticity acrylic emulsion, the back temperature of the coating dry film that this embodiment obtains has reduced by 11 ℃, has obvious heat insulation and preservation effect (as shown in Figure 4).
By the organosilicon crylic acid latex of 60 parts, the water of 25 parts, the zirconium white of 20 parts, the trichroite of 5 parts, the titanium dioxide of 5 parts, and the molybdenum oxide synergistic flame retardant of the modified Nano flame retardant of magnesium hydroxide of the organic modification of surface processing of 50 parts and 5 parts carries out just mixedly, first silver mixing part is mechanical stirring 30min under 400rpm speed; Then in mixed system, add the AMJ Wet PE-100 wetting agent of 0.5 part, the Sodium hexametaphosphate 99 dispersion agent of 5 parts and the halo fatty amide (defoamer A) of 0.4 part, utilize clarifixator under 12000rpm speed, to carry out high-speed stirring and further mix 15min, mixed, disperseed 3h by high speed ball milling again, ball milling speed is 400rpm.
In the blend obtaining, add 0.4 part of AMJ
tMdefoam 8112(is defoamer B), the flow agent of the AMP-95 PH conditioning agent of 0.8 part, 5 parts of membrane-forming agents and 2 parts, and then disperse 2h by 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 parts of glycol ethers, and the flow agent of 2 parts is made up of 0.8 part of CX-103 and 1.2 parts of Flowstar FL309.And then to AMJ HEUR 3040 thickening materials that add 1.5 parts in the blend obtaining, low speed ball milling 0.5h, speed is 120rpm.Final product, by film pulling device, is made to the dry film coating of 2mm thickness.
Be made up the dry film of 2mm thickness of pure silicon acrylic emulsion, its oxygen recording refers to be less than 20, and in combustion processes, has low phenomenon, and emits with dense smoke.And prepare by above-mentioned technique the dry film that 2mm is thick, and oxygen index exceedes 29, improves a lot, and in air, leaving after burning things which may cause a fire disaster rapidly from putting out, to have significant flame retardant effect, and manifests generation without low, the shape before sample can keep burning completely; In combustion processes, also without obviously dense smoke generation, also reach good smoke suppressing effect.
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), within the time of 8.5min, compared with the dry film made from pure silicon acrylic emulsion, the back temperature of the coating dry film that this embodiment obtains has reduced by 7 ℃, has good thermal insulation function.
embodiment 5
By the acrylate and vinyl acetate emulsion of 40 parts, the water of 10 parts, the zirconium white of 15 parts, the trichroite of 10 parts, the titanium dioxide of 10 parts, and the zinc borate synergistic flame retardant of the modified Nano flame retardant of magnesium hydroxide of the organic modification of surface processing of 40 parts and 4 parts carries out just mixedly, first silver mixing part is mechanical stirring 20min under 200rpm speed; Then in mixed system, add the Sodium dodecylbenzene sulfonate wetting agent of 0.4 part, the AMJ Dispers H-942 dispersion agent of 3 parts and the hexalin (defoamer A) of 0.1 part, utilize clarifixator under 6000rpm speed, to carry out high-speed stirring and further mix 12min, mixed, disperseed 3h by high speed ball milling again, ball milling speed is 200rpm.
In the blend obtaining, add 0.1 part of BEK-750(defoamer B), the Flowstar FL-333G flow agent of the AMP-95 PH conditioning agent of 0.7 part, 3.5 parts of ethylene glycol vinyl acetic monomer membrane-forming agents and 0.8 part, and then disperse 2h by ball mill low speed mixing, ball milling speed is 90rpm; And then to the RM-8W thickening material that adds 0.5 part in the blend obtaining, low speed ball milling 0.5h, speed is 90rpm.Final product, by film pulling device, is made to the dry film coating of 2mm thickness.
Be made up the dry film of 2mm thickness of pure acrylate and vinyl acetate emulsion, its oxygen recording refers to be less than 18, and in combustion processes, has low phenomenon, and emits with dense smoke and acid gas.And prepare by above-mentioned technique the dry film that 2mm is thick, and oxygen index exceedes 26, is significantly improved, and in air, leaving after burning things which may cause a fire disaster rapidly from putting out, to have significant flame retardant effect, and manifests generation without low, the shape before sample can keep burning completely; In combustion processes, also without obviously flue gas generation, also reach obvious smoke suppressing effect.
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), within the time of 8.5min, compared with the dry film made from pure acrylate and vinyl acetate emulsion, the back temperature of the coating dry film that this embodiment obtains has reduced by 7.5 ℃, has good thermal insulation function.
By the water of each 40 parts, 30 parts of elasticity acrylic emulsion and benzene emulsions, the zirconium white of 10 parts, the trichroite of 20 parts, the titanium dioxide of 10 parts, and the antimonous oxide of the modified Nano flame retardant of magnesium hydroxide of the organic modification of surface processing of 30 parts and 3 parts effect fire retardant carries out just mixedly, first silver mixing part is mechanical stirring 10min under 300rpm speed; Then in mixed system, add the butyl oleate sodium sulfate wetting agent of 0.3 part, the AMJ Dispers H-943 dispersion agent of 2.5 parts and the DF-691(defoamer A of 0.2 part), utilize clarifixator under 8000rpm speed, to carry out high-speed stirring and further mix 9min, mixed, disperseed 3h by high speed ball milling again, ball milling speed is 300rpm.
In the blend obtaining, add 0.2 part of AMJ Defoam 8040(defoamer B), the Flowstar FL-333H flow agent of the AMP-95 PH conditioning agent of 0.6 part, 2.5 parts of ethylene glycol monomethyl ether propyl acetate membrane-forming agents and 1 part, and then disperse 2h by ball mill low speed mixing, ball milling speed is 180rpm; And then to the PU-8080 thickening material that adds 4 parts in the blend obtaining, low speed ball milling 0.5h, speed is 180rpm.Final product, by film pulling device, is made to the dry film coating of 2mm thickness.
The thick dry film of 2mm of being made up of pure elasticity acrylic emulsion and benzene emulsion binary system, its oxygen recording refers to be less than 18, and in combustion processes, has low phenomenon, and emits with dense smoke and toxic gas.And prepare by above-mentioned technique the dry film that 2mm is thick, oxygen index exceedes 23, is significantly improved, can be rapidly in air from putting out, have certain flame retardant effect, and manifest generation without low, the shape (as shown in Figure 7) before sample can keep burning substantially; In combustion processes, without obviously dense smoke generation, also reach certain smoke suppressing effect.
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), within the time of 8.5min, compared with the dry film made from pure binary acrylic emulsion, the back temperature of the coating dry film that this embodiment obtains has reduced by 9 ℃, has gratifying thermal insulation function.
The coating of above-described embodiment 1-6 is using acrylic emulsions as film forming material, using trichroite and zirconium white as near-infrared radiation functional stuffing, using the nano-sized magnesium hydroxide of surface organic modification as fire-retardant and press down 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 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 exceed 21 and can in air, realize self-gravitation, finished product coating reaches 23-30 with the oxygen index that film pulling device is made the thick dry film of 1.5-3mm, reach good flame retardant effect, and all effectively suppressed the generation of flue gas, not only reached fire-retardant object and environmental protection.
Claims (6)
1. environmental-protection flame-retardant presses down a hood preparation method for coating, it is characterized in that comprising the steps:
S1, using nano-magnesium hydrate fire retardant 10-60 part and synergistic flame retardant 1-10 part as trichroite 5-20 part of zirconium white 5-20 part of acrylic emulsions 40-100 part of film forming material, water 10-30 part, particle diameter 30-100nm, particle diameter 3-10 μ m, Rutile type Titanium Dioxide 5-20 part, surface organic modification, mechanical stirring 10-30min under 100-500rpm speed, carries out just mixed; Then in mixed system, add wetting agent 0.1-0.5 part, dispersion agent 1-5 part and defoamer A 0.1-0.5 part, utilize clarifixator under 6000-15000rpm speed, to carry out high-speed stirring and further mix 3-15min, then mix, disperse 1.5-5h with the ball milling speed high speed ball milling of 200-400rpm;
Wherein, described synergistic flame retardant is selected at least one in red phosphorus, zinc oxide, weisspiessglanz, stannic oxide, molybdenum oxide, ammonium molybdate, zinc borate;
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 making is cleaned, filtered; In this slurry, add the properties-correcting agent after a certain amount of hydrolysis to carry out high temperature coupling modification; Centrifugation, the dry nano-magnesium hydrate fire retardant that obtains surface modification; Described properties-correcting agent addition is the 2-10% of the nano-sized magnesium hydroxide quality in this slurry; Described properties-correcting agent is silane coupling agent, stearate, titanic acid ester, Aluminate or aluminium titanium composite coupler.
In S2, the blend that obtains to step S1, 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, again to step S2 obtain blend in add thickening material 0.5-5 part, with the ball milling speed low speed ball milling 0.5-1h of 50-180rpm, obtain finished product coating; Described finished product coating reaches 23-30 with the oxygen index that film pulling device is made the thick dry film of 1.5-3mm;
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, benzene emulsion, organosilicon crylic acid latex and acrylate and vinyl acetate emulsion or at least two kinds.
3. method according to claim 1 and 2, is characterized in that: the nano-magnesium hydrate fire retardant median size of described surface organic modification is 50-100nm.
4. method according to claim 1, is characterized in that: in 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.
5. according to the method described in claim 1 or 4, it is characterized in that: in step S2, described flow agent adopts modified organic silicon type flow agent, and described PH conditioning agent is 2-amino-2-methyl propyl alcohol, and described defoamer B adopts silicone based defoamer.
6. an environmental type flame-retardant smoke inhibition functional paint, it is characterized in that: this coating is using acrylic emulsions as film forming material, using the trichroite of particle diameter 3-10 μ m and the zirconium white of particle diameter 30-100nm as near-infrared radiation functional stuffing, take Rutile type Titanium Dioxide as pigment, the nano-sized magnesium hydroxide of the surface organic modification using median size as 50-100nm as fire-retardant and press down cigarette filler, add synergistic flame retardant and auxiliary agent, be composited through ball milling, high speed dispersion, stirring technique; In mass parts, in this coating, comprise: 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; This coating reaches 23-30 with the oxygen index that film pulling device is made the thick dry film of 1.5-3mm;
Wherein, described synergistic flame retardant choosing is at least one in red phosphorus, zinc oxide, weisspiessglanz, stannic oxide, molybdenum oxide, ammonium molybdate, zinc borate;
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 making is cleaned, filtered; In this slurry, add the properties-correcting agent after a certain amount of hydrolysis to carry out high temperature coupling modification; Centrifugation, the dry nano-magnesium hydrate fire retardant that obtains surface modification; Described properties-correcting agent addition is the 2-10% of the nano-sized magnesium hydroxide quality in this slurry; Described properties-correcting agent is silane coupling agent, stearate, titanic acid ester, Aluminate or aluminium titanium composite coupler.
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| CN101280142A (en) * | 2007-04-04 | 2008-10-08 | 中山市孙大化工科技有限公司 | Environment-friendly water-based nano fireproof flame-retardant coating and preparation method thereof |
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| CN102241931A (en) | 2011-11-16 |
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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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