CN100513495C - Aqueous environmental protection ultration expansion type steel structure fireproof paint and its preparation method - Google Patents
Aqueous environmental protection ultration expansion type steel structure fireproof paint and its preparation method Download PDFInfo
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- CN100513495C CN100513495C CNB2005101321693A CN200510132169A CN100513495C CN 100513495 C CN100513495 C CN 100513495C CN B2005101321693 A CNB2005101321693 A CN B2005101321693A CN 200510132169 A CN200510132169 A CN 200510132169A CN 100513495 C CN100513495 C CN 100513495C
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Abstract
The present invention provides a water environment-protecting superthin expanded type steel structure fire-retardant coating. Said fire-retardant coating uses water as dispersion medium, uses flake expandable graphite as expansion reinforcing material, uses one or several kinds of emulsions of acrylic emulsion and others as film-forming material, and its expansion system adopts the ingredients of polyammonium phosphate, pentaerythritol and tripolycyanamide. Said invention also provides its preparation method and concrete steps.
Description
Technical field
The present invention relates to a kind of aqueous environmental protection ultration expansion type steel structure fireproof paint and preparation method thereof.Specifically, the present invention relates to a kind of is dispersion medium with water, adopt emulsion as base-material, the aqueous environmental protection ultration expansion type steel structure fireproof paint that adopts expansible black lead to prepare as the expansion strongthener, and according to the different different preparation methods that adopt of its solids content.
Background technology
At present, the continuous upgrading and the replacement that has promoted construction timber that develop rapidly of economy and society, make heavy construction be on the increase, and the main supporting member of these heavy constructions depends on strong yet portable steel mostly, these steel have been given broad, slim and graceful, succinct smoothness of buildings and don't the solid style of unstability, are the principal modes of following heavy construction.Facilities such as present many Highrise buildingss, stadiums, large-scale theatre, platform have all adopted steel construction.But the fire performance of steel building is poor, and the physical strength of steel reduces with the rising of temperature, when temperature reaches a certain value, steel just lose supporting capacity, and this temperature is defined as the critical temperature of steel, and the critical temperature of the general structural steel of using always is about 540 ℃.For building fire, the temperature in the scene of a fire is mostly between 800 ℃～1200 ℃.For exposed steel, under such fire field of force, as long as several minutes just can rise to 540 ℃ and reach threshold value, supporting capacity descends and also causes buildings to collapse, thereby causes great loss of life and personal injury and financial loss.
Expansion steel-structure fireproofing coating is met the fire charing of promptly expanding, can form a porous carbonaceous layer than tens times of former thick coatings and even tens times, this layer carbonaceous layer has lower thermal conductivity, not only can completely cut off the direct effect of flame to steel, and can significantly reduce heat flux, keep steel construction in the time of nearly 2h, can not surpass 540 ℃, thereby the time enough fire extinguishing is arranged, guarantee that steel building does not cave in.
Frie retardant coating in the market mostly is oiliness, and organism such as employing dimethylbenzene can discharge objectionable impurities as solvent in construction, not only influence the healthy of staff, and contaminate environment.Also having with water on the market is the aqueous fire-proof coating of dispersion medium, no obnoxious flavour discharges, its usage quantity thicker type, thin section steel structure fire-resisting paint in engineering significantly reduces, thereby can reduce the engineering total expenses, easy construction keeps the succinct smooth outward appearance of steel construction, can also increase the exterior coating of brush different color and not influence fire resistance at skin, playing the beautifying and decorating effect, make its goods more competitive, is the kind that present fire department is widelyd popularize.
Expansible black lead is when being subjected to more than 200 ℃ high temperature, and beginning to expand can reach about 100 times, becomes the very low vermiform of density by original flakey, forms very good thermal insulation layer.Expansible black lead itself also is the charcoal source of intumescent system, and its rate of heat release in fire is low, and mass loss is little, and flue gas is few.
The correlation technique of this respect has Chinese patent CN 1030779A, and it discloses a kind of expansible fireproof decorative coating for steel structure, adopts cenosphere and aluminum silicate fiber to make strongthener, and coating 4 mm thick fire-resistantly can only reach 1 hour.A kind of oiliness steel structure fire-proof paint is disclosed in Chinese patent CN 1336403A, adopt dimethylbenzene and N-BUTYL ACETATE to make solvent, also used antimonous oxide, coating 3 mm thick, can reach 90 minutes fire endurance, but solvent evaporates can discharge objectionable impurities, and if presence of fire, antimonous oxide can produce carcinogenic substance and strong impulse gas.Chinese patent CN 1312848A discloses a kind of expanding fire-proof paint that is used for ligno-cellulosic materials, adopted the particulate state expansible black lead, consumption has accounted for 20% of gross weight, and it mainly acts on is to absorb the toxic gas that coating is emitted under the heating state, and prevents to produce " puffed rice " phenomenon.In addition, Chinese patent CN 1394923A discloses a kind of water thin type expanding steel structure fire-resisting paint, its same expansible black lead that adopts is as the expansion strongthener, but required large usage quantity, as 4-10%, this can influence ADHESION OF PAINTS power, may produce excessive internal stress and make the expanding layer cracking; In addition, when this fire protection coating was 3 mm thick, its fire endurance can only reach 75 minutes.
Summary of the invention
One object of the present invention is the flakey expansible black lead is applied in the steel structure fire-proof paint, become " worm " shape to be interspersed in the expansion carbonaceous layer after utilizing expansible black lead to expand, play the effect of fortifying fibre, remedied the fluffy caducous shortcoming of conventional expanded coating carbonaceous layer, stability is better, and expansible black lead itself also is the charcoal source, can prolong carbonaceous layer by the time of complete oxidation, have longer heat-insulating flame-retardant effect, significantly improve fire resistance.
Another object of the present invention provides a kind of preparation method of steel structure fire-proof paint.In the preparation method of steel structure fire-proof paint of the present invention, earlier tetramethylolmethane is dissolved in the water, and in dispersion process, in chuck, feed water coolant, make the tetramethylolmethane recrystallization obtain the crystal of particle diameter below 25 μ m, obtained than pulverizing and grind much thin tetramethylolmethane particle, and be dispersed in the coating system, can access more evenly tiny carbonaceous layer of pore after coating expands like this.
The invention provides a kind of environment-friendly aqueous expansion type steel structure fire-proof paint, with water compositing dispersion medium, no obnoxious flavour discharges in the construction.
The invention provides a kind of ultra-thin fire-resistant coating, decorate properties is good, and consumption is few, and construction thickness is not higher than 3mm, and cost is low.
A kind of according to steel structure fire-proof paint of the present invention, comprise following component (content is by weight percentage):
Water (10----30) %
Base-material (20----30) %
Expansible black lead (0.1----3) %
Polymerization degree n〉1000 ammonium polyphosphate (12----25) %
Tetramethylolmethane (5----15) %
Whipping agent (5----17) %
Mineral filler (4----10) %
Wetting agent (0.1----0.2) %
Dispersion agent (0.1----0.8) %
Sanitas (0.02----0.1) %
Defoamer (0.01----0.1) %
Film coalescence aid (0----4) %
Thickening material (0.5----3) %
Wherein, this steel structure fire-proof paint is sticky fluid, and solids content is 55---75%.
In steel structure fire-proof paint of the present invention, preferred prescription comprises following component (content is by weight percentage):
Water (15----25) %
Base-material (20----30) %
Expansible black lead (0.1----3) %
Polymerization degree n〉1000 ammonium polyphosphate (16----22) %
Tetramethylolmethane (10----15) %
Whipping agent (10----17) %
Mineral filler (6----9) %
Wetting agent (0.1----0.2) %
Dispersion agent (0.1----0.8) %
Sanitas (0.02----0.1) %
Defoamer (0.01----0.1) %
Film coalescence aid (1----4) %
Thickening material (1----3) %.
According to another object of the present invention, provide a kind of preparation method of steel structure fire-proof paint.Wherein, when the solids content of frie retardant coating was less than or equal to 70%, the consumption of dispersion medium water was big, tetramethylolmethane can be dissolved fully.In the case, this preparation method may further comprise the steps:
(1) prescription according to steel structure fire-proof paint takes by weighing auxiliary agents such as wetting agent, dispersion agent, sanitas, defoamer, film coalescence aid and ethylene glycol, and joins in the dispersion tank;
(2) take by weighing solid ingredients such as expansible black lead, trimeric cyanamide, titanium dioxide, ammonium polyphosphate;
(3) tetramethylolmethane is added to the water, and is warmed up to dissolving about 80 ℃;
(4) aqueous solution that will be dissolved with tetramethylolmethane is poured in the dispersion tank, and add the solid ingredient of above-mentioned steps (2) immediately, with the linear velocity high speed dispersion about 20m/s, connecting water coolant more slowly cools off, and keeping the coating temperature to be no more than 40 ℃, the tetramethylolmethane crystallization is separated out like this, is dispersed in the coating system, and granularity is below 25 μ m, and high speed dispersion is 5～60 minutes subsequently;
(5) regulate linear velocity to about the 6m/s, add as the emulsion of base-material and disperseed 5～40 minutes;
(6) add thickening material at last, stirred 2～15 minutes, viscosity adjustment discharging behind the desired value.
When the solids content of frie retardant coating 70% when above because the consumption of water significantly reduces, tetramethylolmethane need be pulverized and add with solid ingredient after being ground to certain fineness.In the case, this preparation method may further comprise the steps:
(1) prescription according to steel structure fire-proof paint takes by weighing water and base-material, adds auxiliary agents such as wetting agent, dispersion agent, sanitas, defoamer, film coalescence aid and ethylene glycol, then this mixture is joined in the dispersion tank;
(2) solid ingredients such as the tetramethylolmethane behind the crushing screening and trimeric cyanamide, titanium dioxide, ammonium polyphosphate, expansible black lead are mixed together evenly, stirring makes it evenly mixed after adding dispersion tank, restir behind other auxiliary agents such as an amount of interpolation thickening material mixes the back discharging.
Description of drawings
Fig. 1 is for being brushed to illustrating of steel construction (2) surperficial steel structure fire-proof paint of the present invention (1);
Fig. 2 begins the expansible synoptic diagram for steel structure fireproofing coating in fire;
After Fig. 3 is steel structure fire-proof paint complete expansion of the present invention, obtained the adiabatic carbonaceous layer (3) of porous of a floor height thickness, low thermal conductivity, it comprises the expansible black lead (5) after pore (4) and the expansion, and thermal source and steel are kept apart.
Embodiment
In superthin expansion steel structure fireproof coating of the present invention, with water as dispersion medium.
Can be used for base-material of the present invention and comprise ACRYLIC EMULSION and chlorine partial emulsion, and the mixture of these two kinds of emulsion different ratioss.These two kinds of emulsion commercializations, many companies are on sale, and for example, as unrestricted example, ACRYLIC EMULSION can be available from Beijing Orient ROHM AND HAAS scientific ﹠ technical corporation (AS261), and chlorine partial emulsion can be available from the two chemical industry company limiteds that reach in Shanghai.
The present invention adopts the flakey expansible black lead as the expansion strongthener, as unrestricted example, it can be available from the Beijing ChuangYi Biology Engineering New Materials Co., Ltd, and its length and width are between 0.5～3mm, thickness is 0.1-0.5mm, and the back thickness that expands can reach 4～10mm.
The polymerization degree n of ammonium polyphosphate of the present invention is greater than 1000, and as unrestricted example, it can be available from Nantong Lianhua Fire-resistant Science ﹠ Technology Co., Ltd..
Can be used for whipping agent of the present invention and comprise trimeric cyanamide, Dyhard RU 100, clorafin, urea.
Can be used for mineral filler of the present invention and comprise titanium dioxide, silicon-dioxide, zinc oxide, aluminum oxide, Calucium Silicate powder, pure aluminium silicate and talcum powder.
Can be used for wetting agent of the present invention and comprise 1,2-propylene glycol, ethylene glycol and glycerol.
Can be used for dispersion agent of the present invention and comprise 3-methacryloxy propylene Trimethoxy silane, two [tetra-sodium dialkoxy ester]-2 hydroxy propanoic acid titanium, Diisobutylene maleic acid sodium salt, two (phosphorous acid dilaurate ester) network four octyloxy titaniums and β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium, preferred 3-methacryloxy propylene Trimethoxy silane and two [tetra-sodium dialkoxy ester]-2 hydroxy propanoic acid titanium.
Can be used for sanitas of the present invention and comprise 1,2-benzisothiazole-3-ketone, benzisoxa imidazoles Urethylane, 2,4,5,6-first chlorine m-dicyanobenzene, benzisothiazole ketone, 2-(4-thiazolyl) benzoglyoxaline 2-n-octyl-4-isothiazoline-3-ketone etc., preferred 1, the 2-benzisothiazole-3-ketone.
Can be used for defoamer of the present invention and comprise poly-Union carbide A-162, methyl polysiloxane, dimethyl polysiloxane, propanediol polyoxypropylene Soxylat A 25-7 and polyoxyethylene nonyl phenylate, preferably poly-Union carbide A-162.
Can be used for film coalescence aid of the present invention and mainly comprise 1,2-propylene glycol, 1,6-hexylene glycol.
Can be used for the aqueous solution, methylcellulose gum and Natvosol that thickening material of the present invention comprises organic bentonite, polyacrylate, modified propylene hydrochlorate.
In addition, steel structure fire-proof paint of the present invention also randomly comprises other additive known in the field and auxiliary agent, for example hydrophobizing agent etc.
The solids content of frie retardant coating of the present invention is at 50%-75%, and preferred 65%.Except that expansible black lead, all the other solid matter particle diameters can adopt several different methods constructions such as spraying, roller coating all below 25 microns.
Frie retardant coating fineness of the present invention is lower, meeting is expanded foamed rapidly after meeting fire, forming the vermiform material after expansible black lead expands is interspersed in the expansion carbonaceous layer, strengthened the intensity of carbonaceous layer, not only can cut off the direct effect of flame, and can effectively hinder heat from the transmission of thermal source to base material to base material.This makes the steel construction temperature can not rise to 540 ℃ of critical temperatures in more than 2 hours time, thereby has the time enough fire extinguishing to guarantee the safety of buildings.This frie retardant coating is a water super-thin, and no toxic gas discharges in the construction, can be widely used in various steel buildings, as stadiums, theatre, Highrise buildings etc.
Described steel structure fire-proof paint is thick thick fluid in container, and does not have caking.By using method known in those skilled in the art to detect, this fire protection coating has following character:
Surface drying time:＜12h;
Dry splitting resistance of initial stage: flawless;
Cohesive strength/MP:0.4;
Water tolerance: no considerable change in 30 hours;
Freeze-thawing resistant cyclicity (inferior): 18;
Freedom from vibration: deflection L/200, coating is aliquation not, comes off;
Flex resistance: deflection L/200, coating is aliquation not, comes off.
Also in conjunction with the accompanying drawings the present invention is further specified below by following examples.
Embodiment 1
According to following component of listing and content (weight percent), prepare steel structure fire-proof paint of the present invention:
Water 17.35
ACRYLIC EMULSION 14.2
Chlorine partial emulsion 14.2
Expansible black lead 0.2
Polymerization degree n〉1000 ammonium polyphosphate 21
Tetramethylolmethane 8.5
Trimeric cyanamide 12.7
Titanium dioxide 8
Talcum powder 2
1,2-propylene glycol 0.17
3-methacryloxy propylene Trimethoxy silane 0.56
1,2-benzisothiazole-3-ketone 0.07
Poly-Union carbide A-162 0.05
Organic bentonite 1.
Above-mentioned auxiliary agent is joined in the dispersion tank, again tetramethylolmethane is added to the water and is warmed up to about 80 ℃, pour in the dispersion tank after the tetramethylolmethane dissolving, and add above-mentioned solid fireproof component and filler immediately, with the linear velocity high speed dispersion about 20m/s, connect water quench more subsequently, linear velocity be adjusted to about 6m/s thereafter, and added emulsion dispersion 30 minutes, and add organic bentonite at last and stir discharging after 10 minutes, can make solids content and be 67.6% frie retardant coating.
Adopt 10cm * 10cm * 0.25cm steel plate, the frie retardant coating brush on the one side and four edges of steel plate, every 12 hours brushes once, is brushed about 0.2mm at every turn, thickness reached behind the 3mm maintenance 30 days, made the steel plate of tool fire protection coating as shown in Figure 1 thus.This steel plate is put in the high-temperature electric resistance furnace, and to the positive heating of frie retardant coating, the steel plate bottom surface is plugged digital thermometer apart from furnace bottom 12cm in the steel plate back side with the furnace bottom electric stove wire, and around the electric furnace and the steel plate back side is heat insulation with the thermal insulation material of low thermal conductivity.As shown in Figure 2, behind the connection power supply, frie retardant coating begins to expand under the situation of being heated.Fig. 3 has shown that after the fire protection coating complete expansion expanding highly reaches 8.5cm, and expansible black lead becomes vermiform to be interspersed in the carbonaceous layer the inside, the intensity height, and not having comes off does not have cracking, has fully played heat-blocking action.Steel billet temperature rises slowly, reaches 540 ℃ after 130 minutes.
From the result of embodiment 1 as seen, content has only fully played the effect of expansion strongthener for 0.2% expansible black lead of total fire protection coating weight, have effective effect of heat insulation, and can not make adhesive force of coatings reduce and ftracture.
Embodiment 2
According to following component of listing and content (weight percent), prepare steel structure fire-proof paint of the present invention:
Water 13.35
ACRYLIC EMULSION 14.7
Chlorine partial emulsion 14.7
Expansible black lead 0.2
Polymerization degree n〉1000 ammonium polyphosphate 22
Tetramethylolmethane 9.5
Trimeric cyanamide 13.7
Titanium dioxide 8
Talcum powder 2
1,2-propylene glycol 0.17
3-methacryloxy propylene Trimethoxy silane 0.56
1,2-benzisothiazole-3-ketone 0.07
Poly-Union carbide A-162 0.05
Organic bentonite 1.
Auxiliary agent is joined in the dispersion tank, again solid ingredients such as the tetramethylolmethane behind the crushing screening and trimeric cyanamide, titanium dioxide, ammonium polyphosphate, expansible black lead are mixed together evenly, and stirring makes it evenly mixed behind the adding dispersion tank, added organic bentonite restir at last 10 minutes, mix the back discharging, can make solids content and be 71.1% frie retardant coating.
Employing is tested fire performance with embodiment 1 identical method, and the expansion of this fire protection coating highly reaches 8.2cm, and steel plate reached 540 ℃ after 126 minutes.
According to following component of listing and content (weight percent), prepare steel structure fire-proof paint of the present invention:
Water 20.35
ACRYLIC EMULSION 14.2
Chlorine partial emulsion 14.2
Expansible black lead 0.2
Polymerization degree n〉1000 ammonium polyphosphate 19
Tetramethylolmethane 7.5
Trimeric cyanamide 11.7
Titanium dioxide 8
Talcum powder 2
1,2-propylene glycol 0.17
3-methacryloxy propylene Trimethoxy silane 0.56
1,2-benzisothiazole-3-ketone 0.07
Poly-Union carbide A-162 0.05
Natvosol 1
Organic bentonite 1
Above-mentioned auxiliary agent is joined in the dispersion tank, again tetramethylolmethane is added to the water and is warmed up to about 80 ℃, pour in the dispersion tank after the tetramethylolmethane dissolving, and add above-mentioned solid fireproof component and filler immediately, subsequently with the linear velocity high speed dispersion about 20m/s, connect water quench again, regulate linear velocity to about the 6m/s thereafter, and added emulsion dispersion 30 minutes, add Natvosol and organic bentonite at last and stir discharging after 10 minutes, can make solids content and be 63.6% frie retardant coating.
Employing is tested fire performance with embodiment 1 identical method, and the expansion of this frie retardant coating highly is 8.9cm, and steel plate reached 540 ℃ after 127 minutes.
Should be appreciated that although the present invention is illustrated with the illustrational embodiment of this paper, the present invention also can implement with other ad hoc fashion or other particular form, and does not depart from main idea of the present invention or essential characteristic.For example, although the present invention is whipping agent in an embodiment with the trimeric cyanamide, other whipping agent known in the field, for example Dyhard RU 100, clorafin, urea etc. also can be used for fire protection coating of the present invention.Therefore, the embodiment of description all should be considered as illustrative from any aspect but not be determinate.Scope of the present invention should be by the explanation of additional claim, and the intention of any and claim and the variation of scope equivalence also will be within the scope of the present invention.
Claims (15)
1. aqueous environmental protection ultration expansion type steel structure fireproof paint, described frie retardant coating comprises by weight percentage:
Water (15----25) %
Base-material (20----30) %
Expansible black lead (0.1----3) %
Ammonium polyphosphate (16----22) %
Tetramethylolmethane (10----15) %
Whipping agent (10----17) %
Mineral filler 6----10) %
Wherein, described frie retardant coating is sticky fluid, and solids content is 55---75%.
2. steel structure fire-proof paint as claimed in claim 1 is characterized in that described base-material is selected from ACRYLIC EMULSION and chlorine partial emulsion, and the mixture of these two kinds of emulsion different ratioss.
3. steel structure fire-proof paint as claimed in claim 1 is characterized in that described expansible black lead adopts flakey, and its length and width are between 0.5～3mm, and thickness is 0.1-0.5mm, and the back thickness that expands can reach 4～10mm.
4. steel structure fire-proof paint as claimed in claim 1, the polymerization degree n that it is characterized in that described ammonium polyphosphate is greater than 1000.
5. steel structure fire-proof paint as claimed in claim 1 is characterized in that described whipping agent is selected from trimeric cyanamide, Dyhard RU 100, clorafin and urea.
6. steel structure fire-proof paint as claimed in claim 1 is characterized in that described mineral filler is selected from titanium dioxide, silicon-dioxide, zinc oxide, aluminum oxide, Calucium Silicate powder, pure aluminium silicate and talcum powder.
7. steel structure fire-proof paint as claimed in claim 1 is characterized in that described steel structure fire-proof paint comprises that further weight percentage is the wetting agent of 0.1-0.2%, the dispersion agent of 0.1-0.8%, the sanitas of 0.02-0.1%, the defoamer of 0.01-0.1%, the film coalescence aid of 0-4% and the thickening material of 0.5-3%.
8. steel structure fire-proof paint as claimed in claim 7 is characterized in that described thickening material is selected from the aqueous solution, methylcellulose gum and the Natvosol of organic bentonite, polyacrylate, modified propylene hydrochlorate.
9. steel structure fire-proof paint as claimed in claim 7 is characterized in that described wetting agent is selected from 1,2-propylene glycol, ethylene glycol and glycerol.
10. steel structure fire-proof paint as claimed in claim 7 is characterized in that described dispersion agent is selected from 3-methacryloxy propylene Trimethoxy silane, two [tetra-sodium dialkoxy ester]-2 hydroxy propanoic acid titanium, Diisobutylene maleic acid sodium salt, two (phosphorous acid dilaurate ester) network four octyloxy titaniums and β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium.
11. steel structure fire-proof paint as claimed in claim 7, it is characterized in that described sanitas is selected from 1,2-benzisothiazole-3-ketone, benzisoxa imidazoles Urethylane, 2,4,5,6-first chlorine m-dicyanobenzene, benzisothiazole ketone and 2-(4-thiazolyl) benzoglyoxaline 2-n-octyl-4-isothiazoline-3-ketone.
12. steel structure fire-proof paint as claimed in claim 7 is characterized in that described defoamer is selected from poly-Union carbide A-162, methyl polysiloxane, dimethyl polysiloxane, propanediol polyoxypropylene Soxylat A 25-7 and polyoxyethylene nonyl phenylate.
13. steel structure fire-proof paint as claimed in claim 7 is characterized in that described film coalescence aid is selected from 1,2-propylene glycol, 1,6-hexylene glycol.
14. a method for preparing steel structure fire-proof paint as claimed in claim 1 is characterized in that described preparation method may further comprise the steps: when solids content is less than or equal to 70%, earlier tetramethylolmethane is added to the water, is warmed up to 80 ℃ of dissolvings; In dispersion process, in chuck, feed water coolant, high speed dispersion 5～60 minutes; And adding described base-material, low speed disperseed 5～40 minutes again; After adding described thickening material adjusting viscosity, stirred 2～15 minutes at last.
15. method for preparing steel structure fire-proof paint as claimed in claim 1, it is characterized in that described preparation method may further comprise the steps: when solids content surpasses 70%, the tetramethylolmethane pulverizing is ground to certain fineness sieves later on, and add with other solid ingredient.
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