CN109517470B - Water-based ultrathin fireproof coating and preparation method thereof - Google Patents
Water-based ultrathin fireproof coating and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract 16
- 239000011248 coating agent Substances 0.000 title claims abstract 11
- 238000000576 coating method Methods 0.000 title claims abstract 11
- 238000002360 preparation method Methods 0.000 title claims abstract 3
- 239000002109 single walled nanotube Substances 0.000 claims abstract 27
- 238000003756 stirring Methods 0.000 claims abstract 15
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract 5
- 150000001412 amines Chemical class 0.000 claims abstract 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract 5
- 239000010452 phosphate Substances 0.000 claims abstract 5
- 239000011159 matrix material Substances 0.000 claims abstract 4
- 238000002156 mixing Methods 0.000 claims abstract 4
- 239000002994 raw material Substances 0.000 claims abstract 4
- 239000005995 Aluminium silicate Substances 0.000 claims abstract 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract 3
- 229920000877 Melamine resin Polymers 0.000 claims abstract 3
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract 3
- 239000012752 auxiliary agent Substances 0.000 claims abstract 3
- 239000001913 cellulose Substances 0.000 claims abstract 3
- 229920002678 cellulose Polymers 0.000 claims abstract 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000012065 filter cake Substances 0.000 claims 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 6
- 238000000967 suction filtration Methods 0.000 claims 6
- 238000005406 washing Methods 0.000 claims 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims 4
- 239000003431 cross linking reagent Substances 0.000 claims 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims 4
- 238000001914 filtration Methods 0.000 claims 4
- 239000000243 solution Substances 0.000 claims 4
- 238000000034 method Methods 0.000 claims 3
- CCMKPCBRNXKTKV-UHFFFAOYSA-N 1-hydroxy-5-sulfanylidenepyrrolidin-2-one Chemical compound ON1C(=O)CCC1=S CCMKPCBRNXKTKV-UHFFFAOYSA-N 0.000 claims 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims 2
- MSWDKRMGRFOUHD-UHFFFAOYSA-N 2-aminoethyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCCN MSWDKRMGRFOUHD-UHFFFAOYSA-N 0.000 claims 2
- GGPAGKBQJNEPCZ-UHFFFAOYSA-N 2-aminoethyl dimethyl phosphate Chemical compound COP(=O)(OC)OCCN GGPAGKBQJNEPCZ-UHFFFAOYSA-N 0.000 claims 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims 2
- QBNZQTCUABQLNJ-UHFFFAOYSA-N 3-aminopropyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCCCN QBNZQTCUABQLNJ-UHFFFAOYSA-N 0.000 claims 2
- RDXVLFWRGQLRMT-UHFFFAOYSA-N 3-aminopropyl dimethyl phosphate Chemical compound P(=O)(OC)(OC)OCCCN RDXVLFWRGQLRMT-UHFFFAOYSA-N 0.000 claims 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 239000000839 emulsion Substances 0.000 claims 2
- 239000003063 flame retardant Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 230000007935 neutral effect Effects 0.000 claims 2
- 235000006408 oxalic acid Nutrition 0.000 claims 2
- 238000010992 reflux Methods 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 claims 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 239000003755 preservative agent Substances 0.000 claims 1
- 239000002562 thickening agent Substances 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- 239000000080 wetting agent Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 239000002041 carbon nanotube Substances 0.000 abstract 1
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
Classifications
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- 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
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a water-based ultrathin fireproof coating, which comprises the following raw material components in parts by weight: 20-25 parts of an aqueous film-forming matrix, 4-10 parts of calcium sulfate, 5-15 parts of kaolin, 3.5-5 parts of phosphorus-nitrogen doped single-walled carbon nanotubes, 10-20 parts of ammonium polyphosphate, 3-7 parts of pentaerythritol, 2-6 parts of melamine, 1-3 parts of cellulose, 10-18 parts of water and 1-2 parts of an auxiliary agent; the preparation method comprises the following steps: step 1, firstly carboxylating a single-walled carbon nanotube, and then combining carboxyl on the surface of the carbon nanotube with amine alkyl phosphate through an amide bond to obtain a phosphorus-nitrogen doped single-walled carbon nanotube; and 2, mixing the raw material components, and uniformly stirring to obtain the water-based ultrathin fireproof coating. The invention provides a water-based ultrathin fireproof coating based on a phosphorus-nitrogen doped single-walled carbon nanotube, which has the characteristics of green, high-efficiency flame retardance, good adhesion with a substrate, good weather resistance and antibacterial property.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based ultrathin fireproof coating based on a phosphorus-nitrogen doped single-walled carbon nanotube.
Background
The steel structure is very practical in the building engineering, not only can shorten the building engineering construction cycle, can also improve building stability. The steel material has good heat resistance but poor fire resistance, so that blue brittleness is caused at 250 ℃, and the strength is basically lost at 650 ℃. In case of fire, a great loss occurs. Therefore, the research on the fireproof coating for the steel structure is significant. In general, the fire-retardant coating with a thick coating layer has better fire-retardant properties than thin coatings. However, under certain fire-proof requirements, the thick-coating type coating is gradually replaced by the ultra-thin type fire-proof coating due to the defects of high cost, long construction period, lack of decoration and the like. The currently used ultra-thin steel structure fire-retardant coating can be classified into a non-expansion type and an expansion type. The intumescent steel structure fireproof coating gradually becomes the mainstream because of the better fireproof performance, and can be divided into the following parts according to the dispersion matrix: water-based and solvent-based. The water-based ultrathin fireproof coating has better fireproof performance and decorative performance, and is environment-friendly, so that the water-based ultrathin fireproof coating draws more and more attention of people.
Patent CN102675992B discloses an intumescent water-based facing fire retardant coating, which comprises raw materials of styrene-acrylic emulsion, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide, aluminum hydroxide, zinc borate, chlorinated paraffin, antiseptic bactericide, dispersant, film forming aid, cellulose ether, hydroxyl silicone oil and water; the intumescent water-based facing fireproof coating provided by the invention does not crack, bubble or fall off after being soaked in water for 72 hours, and the fire-resistant time is 40 min. The fire retardant coating has a short fire-resistant time due to the lack of strength and durability of the expanded carbon generated in a fire. Patent CN102417789B discloses a bromine carbon polyurethane steel structure fireproof paint and a preparation method thereof, the fireproof paint is composed of a component A and a component B, wherein the component A is composed of modified brominated epoxy resin, dimethyl silicone oil, a catalyst dibutyltin dilaurate, a flame retardant and an auxiliary agent, the component B is a modified TDI curing agent, and the fire-resistant time is 64 min. However, the fireproof coating contains halogen elements, which easily causes environmental pollution.
At present, there are studies showing that: the nano carbon material is added into the fireproof coating, so that the strength and the expansion rate of a carbonized layer of the fireproof coating after being ignited can be improved, the temperature rise rate of the back of the coating is reduced, and the cracking resistance of the coating is enhanced. Moreover, the nano carbon material particles have large specific surface, especially the super-large length-diameter ratio of the carbon nano tubes, can play a role in strengthening and toughening the coating, can obviously improve the mechanical property of the coating, can also have strong interface acting force with the substrate, and improve the bonding strength. However, the nano carbon material is extremely easy to agglomerate and is not easy to disperse when in use, the fire resistance of the fire-proof material is directly influenced, and the fire resistance of the prepared fire-proof coating is limited.
Disclosure of Invention
The invention aims to provide a water-based ultrathin fireproof coating based on a phosphorus-nitrogen doped single-walled carbon nanotube aiming at the technical problem that the fireproof performance of the existing fireproof coating needs to be improved.
The invention provides a water-based ultrathin fireproof coating which comprises the following raw material components in parts by weight: 20-25 parts of an aqueous film-forming matrix, 4-10 parts of calcium sulfate, 5-15 parts of kaolin, 3.5-5 parts of phosphorus-nitrogen doped single-walled carbon nanotubes, 10-20 parts of ammonium polyphosphate, 3-7 parts of pentaerythritol, 2-6 parts of melamine, 1-3 parts of cellulose, 10-18 parts of water and 1-2 parts of an auxiliary agent. Wherein the structural formula of the phosphorus-nitrogen doped single-walled carbon nanotube is as follows:
in the formula, R is alkyl, and x ranges from 1 to 4. Preferably, R is methyl or ethyl, and x has the value of 1 or 2.
The aqueous film-forming substrate is vinyl acetate-ethylene copolymer emulsion or pure acrylic emulsion.
The auxiliary agent comprises a film forming auxiliary agent, a defoaming agent, a wetting dispersant, a thickening agent, an antifreezing agent and a preservative.
The preparation method of the water-based ultrathin fireproof coating comprises the following steps:
s1, preparing the phosphorus-nitrogen doped single-walled carbon nanotube: firstly, carboxylating a single-walled carbon nanotube, and then combining carboxyl on the surface of the carbon nanotube with amine alkyl phosphate through an amide bond to obtain a phosphorus-nitrogen doped single-walled carbon nanotube;
s2, firstly adding water into a reaction container, stirring, sequentially adding an auxiliary agent, calcium sulfate, kaolin, a phosphorus-nitrogen doped single-walled carbon nanotube, ammonium polyphosphate, pentaerythritol, melamine and cellulose, stirring uniformly, then adding a water-based film-forming matrix, and stirring uniformly to obtain the water-based ultrathin fireproof coating.
Preferably, the operation of step S1 is as follows:
s11, dispersing 6 parts by weight of single-walled carbon nanotubes in water, adding 1 part by weight of hydrobromic acid, stirring at a high speed for 24 hours, then adding 20 parts by weight of oxalic acid, continuing stirring for 8 hours, carrying out suction filtration, and washing to obtain preliminary carboxylated single-walled carbon nanotubes; at this time, the carboxyl group content is still less, and in order to further increase the number of carboxyl groups on the carbon nanotube, steps S12 and S13 are performed;
s12, dispersing the preliminary carboxylated single-walled carbon nanotubes in toluene, adding 2, 2-azobisisobutyronitrile with the weight equal to that of the carboxylated single-walled carbon nanotubes, keeping the temperature at 75 ℃ under the protection of argon, stirring for 4 hours, carrying out suction filtration while the mixture is hot, washing filter cakes with hot toluene, and obtaining the filter cakes, namely the carboxylated single-walled carbon nanotubes containing cyano;
s13, dispersing the carboxylated single-walled carbon nanotube containing the cyano group in methanol, adjusting the pH value to 10, stirring at the constant temperature of 60 ℃, carrying out reflux reaction for 2 days, adjusting the pH value to be neutral, carrying out suction filtration, washing and drying a filter cake to obtain the carboxylated single-walled carbon nanotube; the carboxyl content is higher, which is beneficial to introducing more nitrogen and phosphorus in the subsequent step S14; the buffer solution for adjusting pH can be one of sodium hydroxide, hydrochloric acid, sodium hydrogen phosphate and triethanolamine;
s14, dispersing the carboxylated single-walled carbon nanotubes in the cross-linking agent solution, filtering after 30min, mixing the filter cake with amine alkyl phosphate according to the weight ratio of 1:50, stirring and reacting at 40 ℃ for 2 days, and filtering to obtain the filter cake, namely the phosphorus-nitrogen doped single-walled carbon nanotubes.
Preferably, the crosslinking agent solution is an aqueous solution of one of N-hydroxysuccinimide, N-hydroxythiosuccinimide, (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) amide or N, N' -dicyclohexylcarbodiimide, and the concentration is 0.4 mol/L. The cross-linking agent is used for activating carboxyl on the surface of the single-walled carbon nanotube. Since the crosslinker and the carboxyl group readily form an intermediate which is then replaced by the amine alkyl phosphate to form an amide bond. In the absence of the activation of the cross-linking agent, it is difficult to directly react the carboxylated single-walled carbon nanotubes with the amine alkyl phosphate.
Preferably, the aminoalkyl phosphate is one or a combination of two of aminoethyl dimethyl phosphate, aminoethyl diethyl phosphate, aminopropyl dimethyl phosphate and aminopropyl diethyl phosphate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the phosphorus-nitrogen doped single-walled carbon nanotube is added into the fireproof coating, and simultaneously contains a nano carbon material, nitrogen and phosphorus, the carbon nanotube and the phosphorus-nitrogen act synergistically to serve as a flame retardant, so that the flame retardant property of the fireproof coating is remarkably improved, the fire-resistant time is as long as 180 minutes, and the fireproof coating is green, environment-friendly and efficient.
(2) Compared with the carbon nano tube, the phosphorus-nitrogen doped single-walled carbon nano tube has improved dispersion performance, is not easy to agglomerate when preparing the fireproof coating and has good dispersion; through simple mixing and stirring, the phosphorus-nitrogen doped single-walled carbon nanotube can be uniformly mixed with other components, the contact surface is large, and the fireproof coating with excellent performance is obtained.
(3) The single-walled carbon nanotube can generate mechanical damage to bacterial cell membranes, so that cells are broken and damaged, and bacteria die, so that the fireproof coating does not need other auxiliary agents and has bacteriostasis; the coating can play an indoor purification role when being coated in a large steel structure building with dense population.
(4) The single-walled carbon nanotube has the length-diameter ratio far exceeding that of other nano materials, and after being uniformly mixed, the single-walled carbon nanotube is beneficial to improving the toughness and the wear resistance of a coating, and the fireproof coating with excellent mechanical property is obtained.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is described in further detail below to enable those skilled in the art to practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
The preparation method of the water-based ultrathin fireproof coating comprises the following steps:
s1, preparing the phosphorus-nitrogen doped single-walled carbon nanotube: s11, ultrasonically dispersing 6 parts by weight of single-walled carbon nanotubes in water to obtain a suspension, adding 1 part by weight of hydrobromic acid, stirring for 24 hours by intense magnetic force, adding 20 parts by weight of oxalic acid into the suspension, continuing stirring for 8 hours, performing suction filtration, and washing a filter cake, wherein the filter cake is the preliminary carboxylated single-walled carbon nanotube; s12, adding 100 parts by weight of toluene and 10 parts by weight of preliminary carboxylated single-walled carbon nanotubes into a four-neck flask provided with a speed-regulating stirrer, a reflux pipe, a thermometer and an air inlet and outlet pipe, uniformly dispersing, then adding 10 parts by weight of 2, 2-azobisisobutyronitrile, continuously stirring for 4 hours at a constant temperature of 75 ℃ under the protection of argon gas, then carrying out suction filtration while hot, washing a filter cake with hot toluene, and obtaining the filter cake which is the carboxylated single-walled carbon nanotubes containing cyano groups; s13, dispersing the carboxylated single-walled carbon nanotube containing the cyano in methanol, adjusting the pH to 10 by using 0.1mol/L sodium hydroxide, stirring at a constant temperature of 60 ℃, refluxing for two days, adjusting the pH to be neutral, performing suction filtration, washing and drying a filter cake to obtain the carboxylated single-walled carbon nanotube; s14, dispersing 1 part by weight of carboxylated single-walled carbon nanotubes in 0.4mol/L N-hydroxy sulphosuccinimido solution, filtering after 30 minutes, mixing a filter cake with 50 parts by weight of aminoethyl dimethyl phosphate, stirring for two days at a constant temperature of 40 ℃, and filtering to obtain the filter cake, namely the phosphorus-nitrogen doped single-walled carbon nanotubes.
S2, adding 18 parts by weight of water into a reaction container, adding 2 parts by weight of an auxiliary agent, 4 parts by weight of calcium sulfate, 15 parts by weight of kaolin, 3.5 parts by weight of phosphorus-nitrogen doped single-walled carbon nanotube, 20 parts by weight of ammonium polyphosphate, 7 parts by weight of pentaerythritol, 6 parts by weight of melamine and 1 part by weight of modified hydroxyethyl cellulose while stirring and dispersing uniformly, adding 25 parts by weight of pure acrylic emulsion into the stirred mixture, and stirring uniformly to obtain the water-based ultrathin fireproof coating. Wherein the auxiliary agent is a film-forming auxiliary agent alcohol ester twelve, a defoaming agent, a wetting dispersant, a thickening agent and a preservative.
Example 2
The preparation method of the water-based ultrathin fireproof coating comprises the following steps:
s1, preparing the phosphorus-nitrogen doped single-walled carbon nanotube:
steps S11, S12, S13 are the same as in example 1; s14, dispersing 1 part by weight of carboxylated single-walled carbon nanotubes in 0.4mol/L (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) amide solution, filtering after 30 minutes, mixing a filter cake with aminopropyl diethyl phosphate according to the weight ratio of 1:50, stirring for two days at the constant temperature of 40 ℃, and filtering to obtain the filter cake, namely the phosphorus-nitrogen doped single-walled carbon nanotubes.
S2, adding 15 parts by weight of water into a reaction container, adding 1 part by weight of an auxiliary agent, 6 parts by weight of calcium sulfate, 10 parts by weight of kaolin, 5 parts by weight of phosphorus-nitrogen doped single-walled carbon nanotube, 10 parts by weight of ammonium polyphosphate, 5 parts by weight of pentaerythritol, 4 parts by weight of melamine and 3 parts by weight of modified hydroxyethyl cellulose while dispersing uniformly, adding 20 parts by weight of vinyl acetate-ethylene copolymer emulsion into the stirred mixture, and stirring uniformly to obtain the aqueous ultrathin fireproof coating. Wherein the auxiliary agent is alcohol ester twelve, a defoaming agent, a wetting dispersant, a thickening agent, an antifreezing agent and a preservative.
Example 3
The preparation method of the water-based ultrathin fireproof coating comprises the following steps:
s1, preparing the phosphorus-nitrogen doped single-walled carbon nanotube:
steps S11, S12, S13 are the same as in example 1; s14, dispersing 1 part by weight of carboxylated single-walled carbon nanotubes in 0.4mol/L N, N' -dicyclohexylcarbodiimide solution, filtering after 30 minutes, mixing a filter cake with amine alkyl phosphate according to the weight ratio of 1:50, wherein the amine alkyl phosphate is a mixture of diethyl aminoethyl phosphate and aminopropyl dimethyl phosphate according to the weight ratio of 1:1, stirring for two days at constant temperature of 40 ℃, and filtering to obtain the filter cake, namely the phosphorus-nitrogen doped single-walled carbon nanotubes.
S2, adding 10 parts by weight of water into a reaction container, adding 1.5 parts by weight of an auxiliary agent, 10 parts by weight of calcium sulfate, 5 parts by weight of kaolin, 4 parts by weight of phosphorus-nitrogen doped single-walled carbon nanotube, 15 parts by weight of ammonium polyphosphate, 3 parts by weight of pentaerythritol, 2 parts by weight of melamine and 2 parts by weight of modified hydroxyethyl cellulose while dispersing uniformly, adding 25 parts by weight of pure acrylic emulsion into the stirred mixture, and stirring uniformly to obtain the water-based ultrathin fireproof coating. Wherein the auxiliary agent is a film-forming auxiliary agent alcohol ester twelve, a defoaming agent, a wetting dispersant, a thickening agent, an antifreezing agent and a preservative.
The fire-retardant coatings prepared in examples 1-3 above were subjected to fire performance tests, and the results are shown in Table 1. It can be seen that the fire retardant coating prepared by the invention has improved water resistance, oil resistance, impact resistance, flexibility and fire resistance, particularly the fire resistance time is 188 minutes, the fire resistance time is obviously longer than that of the existing fire retardant coating, and the flame retardant effect is obviously improved.
TABLE 1 test results of fire resistance
In conclusion, the invention provides the water-based ultrathin fireproof coating based on the phosphorus-nitrogen doped single-walled carbon nanotube, which has the advantages of good adhesion with a substrate, good weather resistance, good flame retardant effect and antibacterial property.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. It is therefore intended that the invention not be limited to the exact details and illustrations contained herein, but fall within the scope and range of equivalents of the claims.
Claims (6)
1. The water-based ultrathin fireproof coating is characterized by comprising the following raw material components in parts by weight: 20-25 parts of an aqueous film-forming matrix, 4-10 parts of calcium sulfate, 5-15 parts of kaolin, 3.5-5 parts of phosphorus-nitrogen doped single-walled carbon nanotubes, 10-20 parts of ammonium polyphosphate, 3-7 parts of pentaerythritol, 2-6 parts of melamine, 1-3 parts of cellulose, 10-18 parts of water and 1-2 parts of an auxiliary agent; the aqueous film-forming matrix is vinyl acetate-ethylene copolymer emulsion or pure acrylic emulsion; the structural formula of the phosphorus-nitrogen doped single-walled carbon nanotube is as follows:
in the formula, R is alkyl, and x ranges from 1 to 4;
the preparation method of the phosphorus-nitrogen doped single-walled carbon nanotube comprises the following steps:
s11, dispersing 6 parts by weight of single-walled carbon nanotubes in water, adding 1 part by weight of hydrobromic acid, stirring at a high speed for 24 hours, then adding 20 parts by weight of oxalic acid, continuing stirring for 8 hours, carrying out suction filtration, and washing a filter cake, wherein the filter cake is the primary carboxylated single-walled carbon nanotube;
s12, dispersing the preliminary carboxylated single-walled carbon nanotubes in toluene, adding 2, 2-azobisisobutyronitrile with the weight equal to that of the carboxylated single-walled carbon nanotubes, keeping the temperature at 75 ℃ under the protection of argon, stirring for 4 hours, carrying out suction filtration while the mixture is hot, washing filter cakes with hot toluene, and obtaining the filter cakes, namely the carboxylated single-walled carbon nanotubes containing cyano;
s13, dispersing the carboxylated single-walled carbon nanotube containing the cyano group in methanol, adjusting the pH value to 10, stirring at the constant temperature of 60 ℃, carrying out reflux reaction for 2 days, adjusting the pH value to be neutral, carrying out suction filtration, washing and drying a filter cake to obtain the carboxylated single-walled carbon nanotube;
s14, dispersing the carboxylated single-walled carbon nanotubes in a cross-linking agent solution, filtering after 30min, mixing a filter cake with amine alkyl phosphate according to the weight ratio of 1:50, stirring at 40 ℃ for reaction for 2 days, and filtering to obtain a filter cake, namely the phosphorus-nitrogen doped single-walled carbon nanotubes;
the cross-linking agent solution is one of N-hydroxysuccinimide, N-hydroxythiosuccinimide, (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) amide or N, N' -dicyclohexylcarbodiimide aqueous solution;
the amine alkyl phosphate is one or a combination of two of aminoethyl dimethyl phosphate, aminoethyl diethyl phosphate, aminopropyl dimethyl phosphate and aminopropyl diethyl phosphate.
2. The aqueous ultrathin fireproof coating of claim 1, wherein R is methyl or ethyl and x has the value of 1 or 2.
3. The aqueous ultra-thin fire retardant coating of claim 1, wherein the adjuvants comprise film forming aids, defoamers, wetting and dispersing agents, thickeners, anti-freezing agents, preservatives.
4. A method for preparing the water-based ultra-thin fire-retardant coating according to any one of claims 1 to 3, which comprises the following steps:
s1, preparing the phosphorus-nitrogen doped single-walled carbon nanotube, which comprises the following steps:
s11, dispersing 6 parts by weight of single-walled carbon nanotubes in water, adding 1 part by weight of hydrobromic acid, stirring at a high speed for 24 hours, then adding 20 parts by weight of oxalic acid, continuing stirring for 8 hours, carrying out suction filtration, and washing a filter cake, wherein the filter cake is the primary carboxylated single-walled carbon nanotube;
s12, dispersing the preliminary carboxylated single-walled carbon nanotubes in toluene, adding 2, 2-azobisisobutyronitrile with the weight equal to that of the carboxylated single-walled carbon nanotubes, keeping the temperature at 75 ℃ under the protection of argon, stirring for 4 hours, carrying out suction filtration while the mixture is hot, washing filter cakes with hot toluene, and obtaining the filter cakes, namely the carboxylated single-walled carbon nanotubes containing cyano;
s13, dispersing the carboxylated single-walled carbon nanotube containing the cyano group in methanol, adjusting the pH value to 10, stirring at the constant temperature of 60 ℃, carrying out reflux reaction for 2 days, adjusting the pH value to be neutral, carrying out suction filtration, washing and drying a filter cake to obtain the carboxylated single-walled carbon nanotube;
s14, dispersing the carboxylated single-walled carbon nanotubes in a cross-linking agent solution, filtering after 30min, mixing a filter cake with amine alkyl phosphate according to the weight ratio of 1:50, stirring at 40 ℃ for reaction for 2 days, and filtering to obtain a filter cake, namely the phosphorus-nitrogen doped single-walled carbon nanotubes; the cross-linking agent solution is one of N-hydroxysuccinimide, N-hydroxy thiosuccinimide, (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) amide or N, N' -dicyclohexylcarbodiimide aqueous solution;
and S2, mixing the raw material components, and uniformly stirring to obtain the water-based ultrathin fireproof coating.
5. The method for preparing the water-based ultrathin fireproof paint of claim 4, wherein the amine alkyl phosphate is one or a combination of two of aminoethyl dimethyl phosphate, aminoethyl diethyl phosphate, aminopropyl dimethyl phosphate and aminopropyl diethyl phosphate.
6. The method for preparing the water-based ultrathin fireproof coating of claim 4, wherein the step S2 is specifically: firstly, adding water into a reaction container, stirring, sequentially adding an auxiliary agent, calcium sulfate, kaolin, a phosphorus-nitrogen doped single-walled carbon nanotube, ammonium polyphosphate, pentaerythritol, melamine and cellulose, uniformly stirring, then adding a water-based film-forming matrix, and uniformly stirring to obtain the water-based ultrathin fireproof coating.
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