CN105385310B - A kind of steel structure fireproofing anti-corrosion function integrative paint and preparation method thereof - Google Patents
A kind of steel structure fireproofing anti-corrosion function integrative paint and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
A kind of steel structure fireproofing anti-corrosion function integrative paint and preparation method thereof, the coating is made by benzoic acid functionalization graphene, aqueous epoxy resins, waterborne curing agent and water are compound；The benzoic acid functionalization graphene is made up of graphene and p-aminobenzoic acid.The preparation method prepares graphene using hydro-thermal method, generation benzoic acid functionalization graphene after an one-step functional of going forward side by side, as Nano filling, steel structure fireproofing anti-corrosion function Integrative Coating material is combined into aqueous epoxy resins, small with amount of filler, preparation process environmental protection, the characteristics of energy consumption is low；Filler has fine compatibility with aqueous epoxy resins in the preparation method, and then increase the crosslink density of coating, so as to improve the heat rejection and corrosion resistance of epoxy resin to the full extent, reach more preferably fire retardant, anticorrosive effect, so as to the short shortcoming of the barrier difference and anti-corrosion cycle that overcome generally existing in current water-repellent preservation coating, with preferable application prospect and practical significance.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of steel structure fireproofing anti-corrosion function integrative paint and its system
Preparation Method.
Background technology
Steel construction is one of relatively common structure type in modern construction engineering, is most removed from office after armored concrete
The building new development of life property and new opplication.Steel building is compared with traditional architecture, due to substituting reinforcing bar using steel plate or shaped steel
Concrete, makes that its intensity is higher, shock resistance is more preferable.
At present, Chinese steel building engineering technology is increasingly mature, and the utilization on skyscraper is increasingly extensive, Shenzhen
DiWang Building, the Jin Mao Tower of PVG, and Pekinese Jing Guang Center, Bird's Nest, the new building of CCTV, the Water Cube etc. be large-scale
Building all employs Steel Structural Design.Meanwhile, the provinces and cities such as Beijing, Shanghai, Shandong, Anhui, Inner Mongol have started to carry out the steel construction people
House pilot is used, this also imply that steel construction, by the spine as the new building epoch, is the developing direction of future architecture.
Although many advantages, such as steel building has energy-saving and environmental protection, light body, antidetonation, there is also shortcomings,
Such as unstability, burn into not fire resisting.For the destabilization problems of steel construction, it can be solved in architectural design by technological means
Certainly, it is then that steel construction has two big considerable safeties urgently to be resolved hurrily in actual applications for corroding with nonfireproof problem
Hidden danger.Thus, the coating protection measure of construction steel structure needs to pay the utmost attention to.
In recent years, due to the limitation that the raising and national legislation of national environmental consciousness are volatilized to organic solvent, water-repellent preservation is applied
Material increasingly attracts attention, especially the water borne epoxy resin anticorrosive paint of excellent performance.But, because common water borne epoxy is anti-
Rotten coating thermal resistance separating performance and Corrosion Protection are poor, its development is received certain obstruction.People would generally introduce it is inorganic or
Organic granular is combined with it, but due to nano inoganic particle be easy to reunite and with the poor compatibility of organic resin, it is poly- in particle
Ji Chu is also easy to produce stress cracking and protection defect, it is impossible to reach good modification of complementarity effect.It is, thus, sought for a kind of and water
The property good nanometer barrier anti-corrosion particle of epoxy resin compatibility, to develop the coating of new steel structure fire retardant anticorrosion function integration
Material.
The content of the invention
In view of the above-mentioned problems, the present invention provides a kind of steel structure fireproofing anti-corrosion function integrative paint and preparation method thereof,
The heat rejection and anticorrosive property of aqueous matrix coating are can effectively improve, the fire retardant, anticorrosive performance of coating is improved.
To realize the above-mentioned purpose of the present invention, the present invention provides a kind of steel structure fireproofing anti-corrosion function integrative paint, by
Benzoic acid functionalization graphene, aqueous epoxy resins, waterborne curing agent and water are compound to be made；The benzoic acid functionalization graphene
It is made up of graphene and p-aminobenzoic acid.
The present invention also provides a kind of preparation method of steel structure fireproofing anti-corrosion function integrative paint, comprises the following steps.
Step 1, addition 0.5~3g graphite under the conditions of ice-water bath（325 mesh）With 1~3g NaNO3；Pour into 20~50ml
Refrigeration（0℃）Dense H2SO4And stir 30~60min under conditions of rotor speed is 350 turns/min；Add 2~5g KMnO4And
Stir 2~4h；Then remove ice-water bath and the temperature of reaction system risen to 30~50 DEG C, at this temperature continue stir 30~
60min；Then 150~300 ml deionized waters are slowly added to, 98 DEG C is then heated to and stirs 15~30min；It is slowly added to
Preheating（60℃）100~200ml deionized waters are simultaneously stirred；Then hydrogen peroxide is added dropwise into solution until no bubble is produced；It is quiet
Put up to being layered and pouring out supernatant liquor, lower floor's solution is washed to neutrality with distillation, graphene oxide is made.
Step 2, the solution that graphene oxide is made into 1~2mg/ml with deionized water, and every gram of graphene oxide needs
Add 10~20ml hydrazine hydrates；The graphene oxide solution for adding hydrazine hydrate is poured into three-necked flask and by reaction system liter
Temperature persistently stirs 2~4h to 98 DEG C at 98 DEG C；Pour out solution to be washed till after neutrality with distilled water and ethanol, filtration drying（80
℃）, graphene is made.
Step 3,0.96g p-aminobenzoic acid, 0.28g sodium hydroxides and 0.526g natrium nitrosums be added to reaction vessel
In, 80ml distilled water is then added, 6ml concentration is slowly added at 0~5 DEG C and is 20% HCl, and 45min is stirred, solution
Color becomes light yellow；The graphene of 0.2~0.5g by ultrasound is added in pale yellow solution and stirs 4h at 0~5 DEG C,
The pH value of regulation solution is 2~3 and filtered that products therefrom washes neutrality with ethanol and organic solvent DMF, produces benzoic acid function
Graphite alkene.
Step 4, take 3~10 parts of benzoic acid functionalization graphenes as filler by weight, be added to 50~100 parts of water
In the mixed liquor of 100~200 parts of aqueous epoxy resins, 0.5~1h of dispersed with stirring produces steel structure fireproofing anti-corrosion function one
Change the mother liquor of coating.
Step 5, take by weight after 25~50 parts of waterborne curing agents are well mixed with 50~100 parts of water, then with it is described
The mother liquor in mass ratio 1 of steel structure fireproofing anti-corrosion function integrative paint:4~5 ratio mixing, is produced.
The aqueous epoxy resins are Ar555 epoxy resin, H228A epoxy resin, E44 epoxy emulsions, E51 epoxies breast
Liquid, E20 epoxy emulsions.
The waterborne curing agent is Aq419 or H228B or W651 or W650.
Beneficial effects of the present invention compared with prior art.
Steel structure fireproofing anti-corrosion function integrative paint that the present invention is provided and preparation method thereof, stone is prepared using hydro-thermal method
Benzoic acid functionalization graphene is generated after black alkene, an one-step functional of going forward side by side as Nano filling, is combined into aqueous epoxy resins
Steel structure fireproofing anti-corrosion function Integrative Coating material, preparation process environmental protection, energy consumption low the characteristics of small with amount of filler；Should
Filler has the characteristics of specific surface area is big, barrier property is strong, electric conductivity is excellent, by means of uniqueness in aqueous epoxy resins
Skin effect can reach good dispersion effect.Filler has fine compatibility with aqueous epoxy resins in the preparation method, enters
And increase the crosslink density of coating, so as to improve the heat rejection and corrosion resistance of epoxy resin to the full extent, reach and more manage
The fire retardant, anticorrosive effect thought, so that the barrier for overcoming generally existing in current water-repellent preservation coating is poor and the anti-corrosion cycle is short
Shortcoming, with preferable application prospect and practical significance.
Brief description of the drawings
Fig. 1 is benzoic acid functionalization graphene mechanism figure.
Fig. 2 is anticorrosion with coat mechanism ideal structure figure of the present invention.
Embodiment
The present invention is further described with reference to specific embodiment.
The present embodiment provides a kind of steel structure fireproofing anti-corrosion function integrative paint, by benzoic acid functionalization graphene, water
Property epoxy resin, waterborne curing agent and water are compound is made；The benzoic acid functionalization graphene is main by graphene and to amino
Benzoic acid is made；The aqueous epoxy resins are E51 epoxy emulsions；The waterborne curing agent is Aq419.
Fig. 1, Fig. 2 are referred to, the present embodiment also provides a kind of preparation side of steel structure fireproofing anti-corrosion function integrative paint
Method, comprises the following steps.
Step 1, the addition 1.2g graphite under the conditions of ice-water bath（The mesh of crystalline flake graphite 325）With 2g NaNO3；Pour into 50ml cold
Hide（0℃）Dense H2SO4And stir 60min under conditions of rotor speed is 350 turns/min；Add 4g KMnO4And stir 4h；So
The temperature of reaction system is simultaneously risen to 35 DEG C by recession fall ice water-bath, continues to stir 60min at this temperature；Then it is slowly added to
300 ml deionized waters, then heat to 98 DEG C and stir 30min；It is slowly added to preheating（60℃）200ml deionized waters are simultaneously stirred
Mix；Then hydrogen peroxide is added dropwise into solution until no bubble is produced；Stand until being layered and pouring out supernatant liquor, lower floor is molten
Liquid is washed to neutrality with distillation, and graphene oxide is made.
Step 2, the solution that graphene oxide is made into 1mg/ml with deionized water, and every gram of graphene oxide need plus
Enter 20ml hydrazine hydrates；The graphene oxide solution for adding hydrazine hydrate is poured into three-necked flask and reaction system is warming up to 98
DEG C, persistently stir 4h at 98 DEG C；Pour out solution to be washed till after neutrality with distilled water and ethanol, filtration drying（80℃）, stone is made
Black alkene.
Step 3,0.96g p-aminobenzoic acid, 0.28g sodium hydroxides and 0.526g natrium nitrosums be added to reaction vessel
In, 80ml distilled water is then added, 6ml concentration is slowly added at 0 DEG C and is 20% HCl, and stirs 45min, the color of solution
Become light yellow；The graphene of 0.3g by ultrasound is added in pale yellow solution and stirs 4h at 0 DEG C, the pH of solution is adjusted
Be worth for 2~3 and with dialysis membrane dialyse 3 times, products therefrom washes neutrality with ethanol and organic solvent DMF, produces benzoic acid function
Graphite alkene（BFG）.
Step 4, step 4, take 10 parts of benzoic acid functionalization graphenes as filler by weight, be added to 100 parts of water
In the mixed liquor of 100 parts of E51 epoxy emulsions, dispersed with stirring 1h produces the mother of steel structure fireproofing anti-corrosion function integrative paint
Liquid.
Step 5, take by weight after 30 parts of Aq419 are well mixed with 100 parts of water, then it is anti-with the steel structure fireproofing
The mother liquor in mass ratio 1 of rotten function integration coating:4 ratio mixing, is produced.
Steel structure fireproofing anti-corrosion function integrative paint manufactured in the present embodiment, is coated in through pre- place by air spray finishing
On the metal substrate of reason, control thickness is in 30~200 μm, drying at room temperature solidification, you can obtain clear coat.The Metal Substrate
The preprocessing process of plate is：Sandblasting or grinding process, are removed water with absolute ethyl alcohol, and acetone deoils, and are dried.
Graphene is a kind of tightly packed carbonaceous new material into individual layer bi-dimensional cellular shape lattice structure of carbon atom, with height
The characteristics such as the big and excellent electric conductivity of intensity, specific surface area, make the cathode reaction in corrosion process be transferred to coating and air circle
Carried out on face, slow down the generation of electrochemical corrosion reaction.It the method overcome the resistance of generally existing in current water-repellent preservation coating
Every the short shortcoming of property difference and anti-corrosion cycle, the heat rejection and antiseptic property of aqueous coating are substantially increased.In addition, graphene is in itself
Easily reunite, be not readily dissolved in water and poor with the compatibility of epoxy resin.This method is by the benzene first generated after graphene functionalized
Acid functionalization graphene is soluble in water, and this material has certain chemical polarity, can have relatively with epoxy resin-base
Preferable compatibility, and then increase the crosslink density of coating, it will have more preferable application prospect and reality as anticorrosion material
Meaning.
Claims (3)
1. a kind of preparation method of steel structure fireproofing anti-corrosion function integrative paint, it is characterised in that comprise the following steps：
Step 1, addition 0.5~3g325 mesh graphite and 1~3g NaNO under the conditions of ice-water bath3；Pour into 20~50ml cold at 0 DEG C
The dense H hidden2SO4And stir 30~60min under conditions of rotor speed is 350 turns/min；Add 2~5g KMnO4And stir 2
~4h；Then remove ice-water bath and the temperature of reaction system risen to 30~50 DEG C, at this temperature continue stir 30~
60min；Then 150~300 ml deionized waters are slowly added to, 98 DEG C is then heated to and stirs 15~30min；It is slowly added to
100~200ml deionized waters of 60 DEG C of preheatings are simultaneously stirred；Then hydrogen peroxide is added dropwise into solution until no bubble is produced；It is quiet
Put up to being layered and pouring out supernatant liquor, lower floor's solution is washed to neutrality with distillation, graphene oxide is made；
Step 2, the solution that graphene oxide is made into 1~2mg/ml with deionized water, and every gram of graphene oxide need plus
Enter 10~20ml hydrazine hydrates；The graphene oxide solution for adding hydrazine hydrate is poured into three-necked flask and reaction system is warming up to
98 DEG C, 2~4h is persistently stirred at 98 DEG C；Pour out solution to be washed till after neutrality with distilled water and ethanol, filtered under the conditions of 80 DEG C
Dry, graphene is made；
Step 3,0.96g p-aminobenzoic acid, 0.28g sodium hydroxides and 0.526g natrium nitrosums be added in reaction vessel,
Then 80ml distilled water is added, 6ml concentration is slowly added at 0~5 DEG C and is 20% HCl, and stirs 45min, the color of solution
Become light yellow；The graphene of 0.2~0.5g by ultrasound is added in pale yellow solution 4h, regulation are stirred at 0~5 DEG C
The pH value of solution is 2~3 and filtered that products therefrom washes neutrality with ethanol and organic solvent DMF, produces benzoic acid function fossil
Black alkene；
Step 4, take 3~10 parts of benzoic acid functionalization graphenes by weight as filler, be added to 50~100 parts of water and
In the mixed liquor of 100~200 parts of aqueous epoxy resins, 0.5~1h of dispersed with stirring produces the integration of steel structure fireproofing anti-corrosion function
The mother liquor of coating；
Step 5, take by weight after 25~50 parts of waterborne curing agents are well mixed with 50~100 parts of water, then with the steel knot
The mother liquor in mass ratio 1 of structure fire retardant anticorrosion function integration coating:4~5 ratio mixing, is produced.
2. the preparation method of steel structure fireproofing anti-corrosion function integrative paint as claimed in claim 1, it is characterised in that described
Aqueous epoxy resins are Ar555 epoxy resin, H228A epoxy resin, E44 epoxy emulsions, E51 epoxy emulsions or E20 epoxies breast
Liquid.
3. the preparation method of steel structure fireproofing anti-corrosion function integrative paint as claimed in claim 1, it is characterised in that described
Waterborne curing agent is one kind in Aq419 or H228B.
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| CN105838195B (en) * | 2016-05-13 | 2018-12-14 | 江苏科技大学 | A kind of water corrosion-resistant epoxy paint and preparation method thereof containing graphene oxide |
| CN106189680A (en) * | 2016-07-04 | 2016-12-07 | 沈阳化工大学 | A kind of building fire-resisting coating material and preparation method thereof |
| CN106497311A (en) * | 2016-09-29 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of Graphene fire-resisting coating material |
| CN109666259B (en) * | 2017-10-16 | 2022-05-27 | 山东欧铂新材料有限公司 | Preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid |
| CN107722830B (en) * | 2017-10-24 | 2019-09-17 | 长春顺风新材料有限公司 | A kind of preparation method of weatherability Environment-friendlyanti-corrosive anti-corrosive paint |
| CN108531045B (en) * | 2018-05-23 | 2020-06-23 | 上海理工大学 | Graphene-modified waterborne epoxy resin coating and preparation method and application thereof |
| CN108948852B (en) * | 2018-05-24 | 2021-06-22 | 安徽强盛交通设备制造有限公司 | Paint composite additive for reducing vehicle paint spraying cost |
| CN109294317B (en) * | 2018-07-31 | 2021-06-18 | 信和新材料股份有限公司 | Preparation method of bifunctional ligand dispersed graphene for coating |
| CN109370368B (en) * | 2018-09-06 | 2021-02-12 | 沈阳化工大学 | Preparation method of steel structure water-based paint |
| CN109486361B (en) * | 2018-12-14 | 2021-03-16 | 沈阳顺风实业集团有限公司 | Preparation method of water-based anticorrosion and fireproof integrated coating |
| CN111117431B (en) * | 2020-01-08 | 2021-04-27 | 沈阳市津浩科技有限公司 | Water-based epoxy flame-retardant coating and preparation method thereof |
| CN112709132B (en) * | 2020-12-31 | 2023-02-28 | 南通福伦利新材料有限公司 | Preparation and spraying method of normal-temperature asphalt stress absorption film for heavy corrosion prevention of steel bridge deck/steel base surface |
| CN113637379A (en) * | 2021-09-24 | 2021-11-12 | 肇庆市海特复合材料技术研究院 | Fireproof anticorrosive paint and preparation method thereof |
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| CN102862976A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Method for preparing functionalized graphene and composite material of functionalized graphene |
| CN102977742B (en) * | 2012-12-19 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | A kind of electrically conducting coating |
| CN104445155B (en) * | 2013-09-17 | 2016-03-23 | 中国科学院大连化学物理研究所 | Grapheme material of a kind of carboxyl-functional and preparation method thereof |
| CN104327619A (en) * | 2014-11-05 | 2015-02-04 | 北京化工大学 | Water-based intumescent profiled steel structure fire-resistant paint and preparation method thereof |
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Application publication date: 20160309 Assignee: Shenyang Jinhao Technology Co.,Ltd. Assignor: SHENYANG SHUNFENG INDUSTRIAL GROUP Co.,Ltd. Contract record no.: X2023210000129 Denomination of invention: A fire-resistant and anti-corrosion integrated coating for steel structures and its preparation method Granted publication date: 20170811 License type: Common License Record date: 20230921 |