CN106280590B - A kind of Flameproofness type super hydrophobic coating and preparation method thereof - Google Patents
A kind of Flameproofness type super hydrophobic coating and preparation method thereof Download PDFInfo
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- CN106280590B CN106280590B CN201610811883.3A CN201610811883A CN106280590B CN 106280590 B CN106280590 B CN 106280590B CN 201610811883 A CN201610811883 A CN 201610811883A CN 106280590 B CN106280590 B CN 106280590B
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- 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
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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Abstract
The invention discloses a kind of Flameproofness type super hydrophobic coatings and preparation method thereof, and by 1 10 parts of inorganic nanoparticles, 0.01 1 parts of silicon fluorides, 1 10 parts of low-melting alloy powder, 0.01 1 parts of auxiliary agents, 0.1 2 parts of pigment powders, which are scattered in 100 500 parts of hydrofluoroethers, to be prepared.Has many advantages, such as equipment and simple for process, operation is simple, designability and of low cost, and has industrial-scale production foreground.The Flameproofness type super hydrophobic coating that the present invention prepares can be applied to various soft or hard substrates and obtain super hydrophobic surface, which does not have ignition point, non-environmental-pollution to be conducive to mass transit, and construction environment requires low, safe class height.
Description
Technical field
The invention belongs to coating preparation field, more particularly to a kind of Flameproofness type super hydrophobic coating and preparation method thereof.
Background technology
Continually developing and utilizing with super hydrophobic material technology has developed the preparation of following super hydrophobic surface in recent years
Technology：Wet method/reactive ion etching, coining, mechanical processing, laser ablation, chemical/electrochemical oxidation, chemical/electrochemical are heavy
Product, sol-gel, hydrothermal synthesis, thermal spraying etc..However, expensive instrument and equipment and harsh process conditions make these systems
Standby super-hydrophobic coat/thin film technique is difficult to carry out scale industrial production, and there is the risk for being easier to be destroyed.In order to solve this
The super hydrophobic coating of preparation is uniformly sprayed the skill that super-hydrophobic coat is formed in substrate surface by sprayed coating film method by a little problems
Art has been developed to as a kind of method of the novel super-hydrophobic film layer of structure, and has obtained relatively broad application.
However, it is inflammable to be all made of ethyl alcohol, isopropanol, petroleum hydrocarbon, acetone etc. with regard to used super hydrophobic coating at present
The organic solvent of type is used as dispersant or lytic agent so that super hydrophobic coating exist during preparation, production, transport etc. compared with
Big security risk has greatly limited to large-scale production, construction environment and the bulk transport of super-hydrophobic coat.Secondly, super thin
Often contain some flammable particles, such as carbon nanotube, organic powder in water coating additive, can also make super hydrophobic coating
There is security risk in practical applications.So it is to overcome its flammable weight to develop a kind of Flameproofness type super hydrophobic coating
It works, is to become the key factor for improving super hydrophobic coating grade safe to use.
Invention content
The purpose of the invention is to overcome the flammability problems of above-mentioned coating of the existing technology, provide a kind of anti-
Combustion type super hydrophobic coating and preparation method thereof, so that improving safe class in production, transport and work progress.The technology is set
It is standby and simple for process, operation it is simple, of low cost, be easy to industrial-scale production.
The technical scheme is that：A kind of Flameproofness type super hydrophobic coating, raw material is in parts by weight：Inorganic nanoparticles 1-
10 parts, 0.01-1 parts of silicon fluoride, 1-10 parts of low-melting alloy powder or organic resin powder, 0.01-1 parts of auxiliary agent, pigment powder 0.1-2
Part, 100-500 parts of hydrofluoroether.
The hydrofluoroether includes appointing in hexafluoro propyl ether, hexafluoro butyl ether, nona-fluoro butyl group methyl ether, ring fluorine ether, ring fluroxene
A kind of or several mixture.
The inorganic micro-nano granules include titanium dioxide, silica, zinc oxide, calcium oxide, clay powder, sludge
Any one of powder, mica powder, silicon powder, glass microballoon, flyash or the powder for appointing several compoundings to obtain, grain size 10nm-
20μm。
The silicon fluoride end group includes any one of ethyoxyl, methoxyl group, isopropyl or chloro.
The low-melting alloy powder includes any one of Sn-Pb, Sn-Bi, Sn-Zn, Sn-In series low-temperature alloy powder
Or appoint several mixtures, grain size is 1-20 μm.
The auxiliary agent includes dispersant, anti-settling agent and rosin, and weight ratio is dispersant：Anti-settling agent：Rosin=1：1：1,
Wherein, anti-settling agent can be one kind in bentonite and aerosil
The pigment includes any one of rust red, titanium dioxide, carbon black, permanent violet.
The organic resin point includes polypropylene, polyethylene, organosilicon, fluororesin, and grain size is at 1-20 μm.
The preparation method of the Flameproofness type super hydrophobic coating, includes the following steps：Inorganic micro-nano granules are added to
In hydrofluoroether solvent, after room temperature mechanical stirs evenly again through ultrasonic disperse, then low-melting alloy powder or organic tree are added according to the ratio
Cosmetics, auxiliary agent and pigment powder, continue to be stirred to react, silicon fluoride are finally added dropwise, be stirred at room temperature, that is, obtain evenly dispersed anti-flaming
Type super hydrophobic coating.
The application method of the Flameproofness type super hydrophobic coating in use, coating carries out after being vigorously stirred uniformly, then sprays
Or brush in soft or hard substrate surface, it finally dries again, that is, obtains the super-hydrophobic coat with anti-flammability.
Advantageous effect：
(1) Flameproofness type super hydrophobic coating of the present invention, the raw material used are inorganic or alloy powder, are not present
Combustion problem, although the auxiliary agent and silicon fluoride of addition are organic matter, content is few, and forms chemical knot with powder after addition
It closes, is coated on powder surface, surplus is also dispersed in coating, not will produce combustion problem.So the Flameproofness type of the present invention
Super hydrophobic coating does not burn in igniting or close kindling material, and spraying is not burnt when being atomized, and the coating of formation is also with fire-retardant.
(2) after the inorganic micro-nano powder film forming in coating, micro-nano coarse structure can be effectively built, it is super thin to obtain
Water surface.
(3) the alloy powder fusing point in coating is 100-200 DEG C, after coating film forming, in one timing of this temperature range processing
Between after, you can fusing, good bonding effect can be played to nano particle.Meanwhile on the one hand addition rosin can prevent alloyed powder
On the one hand the oxidation of melt can also reduce the surface tension of alloy melt, increase the wetability of melt and inorganic particle, further
Improve adhesive effect of the alloyed powder to inorganic particle.
(4) addition of auxiliary agent not only effectively increases the dispersion effect of coating, prevents the sedimentation of bulky grain, while also carrying
The high intensity of coating.
(5) hydrofluoroether is chlorofluorocarbons, the substitute of hydrogen fluorohydrocarbon class compound, low to the damage capability of earth's ozone layer, greatly
Gas residence time section, and ODP is zero, safety and low toxicity, it is non-corrosive, non-ignitable, do not generate flue dust, be easy to store and transport, often quilt
As refrigerant and cleaning agent, surface tension and heat of evaporation are low, are good organic solvent, highly volatile.The present invention is with hydrogen fluorine
Ether is solvent, not only effectively increases the performance of coating and coating, also eliminates the flammability problems of conventional coating, has been expanded super
The application range of hydrophobic coating and its environmental demand is reduced, safety etc. is effectively increased in production, transport and work progress
Grade.
(6) coating of coating preparation of the present invention has good anti-flammability, is remarkably improved the anti-flaming effect of substrate,
Also adjustable color obtains different decorative effects.
(7) the method for the present invention device therefor and simple for process, operation is simple and of low cost, and reaction condition is mild, energy consumption
It is small, it is at low cost, it is reproducible, it is suitable for mass producing.The soft or hard substrate of coating can be used.
Description of the drawings：
The water contact angle and roll angle of coating in Fig. 1 substrate of glass.
The water contact angle and roll angle of coating in Fig. 2 metallic substrates.
The water contact angle and roll angle of coating in Fig. 3 construction material substrates.
The water contact angle and roll angle of coating on Fig. 4 flexible subserates.
The anti-flaming experiment of Fig. 5 type inflammables super hydrophobic coatings (A) and Flameproofness type super hydrophobic coating (B).
Water contact angles and roll angle of Fig. 6 after the coating sprayed in 200 DEG C of substrates is cooled to room temperature.
Specific implementation mode：
A kind of Flameproofness type super hydrophobic coating and preparation method thereof, the Flameproofness type super hydrophobic coating is in igniting or close to kindling material
When do not burn, when spraying atomization, does not burn, and the coating of formation also has anti-flammability, is by a certain percentage, by inorganic micro-nano
Grain, silicon fluoride, low-melting alloy powder, auxiliary agent and pigment powder are scattered in hydrofluoroether and are prepared, in parts by weight：It is inorganic to receive
1-10 parts of rice grain, 0.01-1 parts of silicon fluoride, 1-10 parts of low-melting alloy powder, 0.01-1 parts of auxiliary agent, 0.1-2 parts of pigment powder,
100-500 parts of hydrofluoroether can be brushed or be sprayed in various soft or hard substrates, then can get the super-hydrophobic painting of flame retardant type through low-temperature setting
Layer.
The hydrofluoroether can be in hexafluoro propyl ether, hexafluoro butyl ether, nona-fluoro butyl group methyl ether, ring fluorine ether, ring fluroxene
Any one or two kinds of or more mixed solvents.
The inorganic micro-nano granules are that grain size is 10-200nm or 1-20 μm of titanium dioxide, silica, oxidation
The powders any one or more ofs such as zinc, calcium oxide, clay powder, sludge powder, mica powder, silicon powder, glass microballoon, flyash
The powder that grain compounding obtains.
The silicon fluoride end group is any one of ethyoxyl, methoxyl group, isopropyl or chloro.
The soft or hard substrate includes any one in glass, copper, aluminium, stainless steel, exterior wall tile, timber, paper, cloth.
The low-melting alloy powder refers to the serial low temperature such as Sn-Pb, Sn-Bi, Sn-Zn, Sn-In that grain size is 1-20 μm
The mixture of one or more of alloyed powder.
The auxiliary agent includes dispersant, anti-settling agent and rosin (increasing wetability when alloyed powder fusing), weight ratio
For dispersant：Anti-settling agent：Rosin=1：1：1, wherein anti-settling agent can be one kind in bentonite and aerosil.
The pigment includes any one of rust red, titanium dioxide, carbon black, permanent violet.
The preparation method includes the following steps：Inorganic micro-nano granules are added in hydrofluoroether solvent, through ultrasound
After disperseing 10-60min and room temperature mechanical stirring 10-60min, then alloyed powder, auxiliary agent and pigment are added according to the ratio, continue to stir
Silicon fluoride is finally added dropwise in 30-60min, and 24-72h is stirred at room temperature, you can obtains evenly dispersed Flameproofness type super hydrophobic coating.
The alloyed powder is also replaced by polypropylene, polyethylene, organosilicon, fluororesin equidimension at 1-20 μm or so
Powder, concentration are identical as alloyed powder.
In use, coating need to carry out being vigorously stirred 5-10min, then sprays or brush in substrate surface, finally in 100-200
DEG C baking oven in place 30-60min, you can obtain with anti-flammability super-hydrophobic coat.
Embodiment 1
By the titanium dioxide nano-particle that 0.1g grain sizes are 100-200nm and the fly ash grain that 0.1g grain sizes are 1-20 μm
It is added in 10g nona-fluoro butyl group methyl ether solvents, ultrasonic disperse 10min, subsequent mechanical agitation 60min, it is 1- to add 0.1g grain sizes
20 μm of Sn-Pb alloys, 1mg mixed aids (dispersant, anti-settling agent and the rosin of equal portions) and 10mg rust red, continues to stir
30min is eventually adding 1mg silicon fluorides and continues stirring/fluorination for 24 hours, by the coating even application in substrate of glass and at 100 DEG C
Dry 30min obtains super-hydrophobic coat in baking oven, and water contact angle is 164.2 °, and roll angle is 2.7 ° (Fig. 1).
Embodiment 2
The aerosil that 0.5g grain sizes are 10-100nm is added in 50g nona-fluoro butyl group methyl ether solvents, ultrasonic disperse
30min, subsequent mechanical agitation 30min add Sn-Zn alloys, 10mg mixed aids and 50mg titaniums that 1g grain sizes are 1-20 μm
White powder continues to stir 60min, is eventually adding 5mg silicon fluorides, continues mechanical agitation/fluorination 36h, by the super hydrophobic coating of acquisition,
Even application in metal (copper, aluminium, stainless steel etc.) substrate and in 200 DEG C of baking ovens dry 60min obtain super-hydrophobic coat,
Water contact angle is 159.7 °, and roll angle is 2.5 ° (Fig. 2).
Embodiment 3
50g hexafluoros are added in the nano zine oxide that 0.5g grain sizes are 10-50nm and the sludge powder that 0.5g grain sizes are 10-20 μm
In butyl ether solvent, ultrasonic disperse 60min, subsequent mechanical agitation 60min add the equal mass mixings that 0.5g grain sizes are 1-20 μm
Sn-Zn and Sn-Bi alloys and 100mg mixed aids and 200mg carbon blacks, continue to stir 60min, be eventually adding 10mg fluorine
Silane continues mechanical agitation/fluorination 72h, by the coating even application of acquisition in construction material substrate and in 200 DEG C of baking ovens
Dry 60min obtains super-hydrophobic coat, and water contact angle is 153.3 °, and roll angle is 3.6 ° (Fig. 3).
Embodiment 4
Nine fluorine of 50g is added in the titanium dioxide that 0.5g grain sizes are 100-200nm and the silicon powder that 0.5g grain sizes are 1-10 μm
In butyl methyl ether solvent, ultrasonic disperse 60min, subsequent mechanical agitation 60min add poly- third that 0.1g grain sizes are 10-20 μm
Alkene powder, 10mg mixed aids and 10mg titanium dioxides continue to stir 60min, are eventually adding 5mg silicon fluorides, continue mechanical agitation/
Be fluorinated 72h, by the coating even application of acquisition on flexible subserate and in 100 DEG C of baking ovens dry 30min obtain super-hydrophobic coat,
Its water contact angle is 156.4 °, and roll angle is 4.2 ° (Fig. 4).
Embodiment 5
By the type inflammable for substituting nona-fluoro butyl group methyl ether with absolute ethyl alcohol of anti-burning coating material and same formula in above-described embodiment 2
Coating is put in draught cupboard simultaneously, is lighted to it with open fire flame, the results showed that using absolute ethyl alcohol as organic solvent
Type inflammable coating is easily ignited (Fig. 5 A), and Flameproofness type super hydrophobic coating prepared by the method for the present invention does not have ignition point, in open fire
Sustained ignition 3-5min under flame, in addition to partial solvent volatilizees, do not burn significantly sign, removes flame, and coating appearance does not have
There is significant change (Fig. 5 B), super-hydrophobic coat can still be obtained by being sprayed at substrate surface.
Embodiment 6
Metallic copper is placed in 200 DEG C of high temperature ovens after its temperature stabilization, then immediately will be anti-described in above-described embodiment 2
Combustion type super hydrophobic coating uniformly sprays on its surface not to be occurred firing sign in substrate surface, spraying process, waits for metal
Copper obtains super-hydrophobic coat after being cooled to room temperature, water contact angle is 156.4 °, and roll angle is 2.9 ° (Fig. 6).
Claims (8)
1. a kind of Flameproofness type super hydrophobic coating, which is characterized in that raw material is in parts by weight：Inorganic micro-nano granules 1-10 parts, fluorine
0.01-1 parts of silane, 1-10 parts of low-melting alloy powder, 0.01-1 parts of auxiliary agent, 0.1-2 parts of pigment powder, 100-500 parts of hydrofluoroether；
The low-melting alloy powder includes any one of Sn-Pb, Sn-Bi, Sn-Zn, Sn-In series low-temperature alloy powder or appoints several
Mixture, grain size be 1-20 μm.
2. Flameproofness type super hydrophobic coating as described in claim 1, which is characterized in that the hydrofluoroether include hexafluoro propyl ether,
Any one of hexafluoro butyl ether, nona-fluoro butyl group methyl ether, ring fluorine ether, ring fluroxene appoint several mixtures.
3. Flameproofness type super hydrophobic coating as described in claim 1, which is characterized in that the inorganic micro-nano granules include two
In titanium oxide, silica, zinc oxide, calcium oxide, clay powder, sludge powder, mica powder, silicon powder, glass microballoon, flyash
Powder that is any or appointing several compoundings to obtain, grain size is 10nm-20 μm.
4. Flameproofness type super hydrophobic coating as described in claim 1, which is characterized in that the silicon fluoride end group includes ethoxy
Any one of base, methoxyl group, isopropyl or chloro.
5. Flameproofness type super hydrophobic coating as described in claim 1, which is characterized in that the auxiliary agent includes dispersant, anti-settling
Agent and rosin, weight ratio are dispersant：Anti-settling agent：Rosin=1：1：1, wherein anti-settling agent is bentonite or aerosil.
6. Flameproofness type super hydrophobic coating as described in claim 1, which is characterized in that the pigment includes rust red, titanium white
Any one of powder, carbon black, permanent violet.
7. the preparation method of any Flameproofness type super hydrophobic coating of claim 1~6, which is characterized in that including following step
Suddenly：Inorganic micro-nano granules are added in hydrofluoroether solvent, after through ultrasonic disperse, room temperature mechanical stirs evenly again, then according to the ratio
Low-melting alloy powder, auxiliary agent and pigment powder are added, continues to be stirred to react, silicon fluoride is finally added dropwise, be stirred at room temperature, that is, is obtained equal
The Flameproofness type super hydrophobic coating of even dispersion.
8. the application method of any Flameproofness type super hydrophobic coating of claim 1~6, which is characterized in that in use, coating
It carries out after being vigorously stirred uniformly, then sprays or brush in soft or hard substrate surface, finally dry again, that is, obtain super with anti-flammability
Hydrophobic coating.
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| CN108329835B (en) * | 2018-03-22 | 2020-02-11 | 河南科技学院 | Low-melting-point metal alloy modified super-hydrophobic material and preparation method and application thereof |
| CN109096804A (en) * | 2018-08-10 | 2018-12-28 | 中国科学技术大学 | A kind of method that wear-resisting type super-hydrophobic coat arranges substrate |
| CN113698839B (en) * | 2021-08-30 | 2023-02-28 | 浙江理工大学 | Environment-friendly organic super-hydrophobic composite coating without VOC (volatile organic compound) emission and preparation method thereof |
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| CN105419450A (en) * | 2015-11-30 | 2016-03-23 | 东南大学 | Highly-wear-resistant super-hydrophobic composite coating and preparation method thereof |
| CN105567067A (en) * | 2016-02-05 | 2016-05-11 | 东南大学 | Organic and inorganic hybrid waterproof paint and preparation method thereof |
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| CN105419450A (en) * | 2015-11-30 | 2016-03-23 | 东南大学 | Highly-wear-resistant super-hydrophobic composite coating and preparation method thereof |
| CN105567067A (en) * | 2016-02-05 | 2016-05-11 | 东南大学 | Organic and inorganic hybrid waterproof paint and preparation method thereof |
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| 低熔点合金;武希哲等;《稀有金属材料与工程》;19841231(第1期);第53-56页 * |
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