CN108192493B - Preparation method of graphene and carbon nanotube reinforced anticorrosive bulletproof paint - Google Patents
Preparation method of graphene and carbon nanotube reinforced anticorrosive bulletproof paint Download PDFInfo
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- CN108192493B CN108192493B CN201810003455.7A CN201810003455A CN108192493B CN 108192493 B CN108192493 B CN 108192493B CN 201810003455 A CN201810003455 A CN 201810003455A CN 108192493 B CN108192493 B CN 108192493B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a preparation method of graphene and carbon nanotube reinforced anticorrosive bulletproof paint, which comprises the following steps: heating the first and second components separately prepared to 50 ℃, using a high pressure spray apparatus, according to a ratio of 1: 1 volume ratio, setting the pressure of a main machine of the device at 70kg/cm2 and the temperature at 50 ℃, and performing spray coating to form a film. The invention has the beneficial effects that: the anticorrosive bulletproof paint prepared by the preparation method has the advantages of good corrosion resistance, high impact resistance, environmental protection and quick drying.
Description
Technical Field
The invention relates to the field of preparation of anticorrosive bulletproof coatings, in particular to a preparation method of a graphene and carbon nanotube reinforced anticorrosive bulletproof coating.
Background
Graphene (Graphene) is a honeycomb-shaped planar thin film formed by carbon atoms in an sp2 hybridization mode, is a two-dimensional material with the thickness of only one atomic layer, is also a novel nano material which is the thinnest, the greatest strength and the strongest electric and heat conducting performance and is discovered at present, is the king of new materials, and scientists predict that Graphene will completely change the technology into 21 century. Due to excellent physical and chemical properties of graphene, the graphene has wide application in the field of coatings, for example, the electric conductivity, heat conductivity, wear resistance, corrosion resistance and other properties of the coatings can be enhanced; the carbon nano tube is used as a one-dimensional nano material, has light weight, perfect connection of a hexagonal structure and a plurality of abnormal mechanical, electrical and chemical properties.
At present, elastomers widely applied in the coating are polyurethane and polyurea, but the pure polyurethane or polyurea coating cannot meet the explosion-proof and bulletproof requirements in the market, and the polyurethane and polyurea coating has poor ageing resistance and corrosion resistance, so that the application of the polyurethane and polyurea coating is limited.
The paint has the solid content of not 100 percent, is long in time consumption in the drying process, is possibly accompanied with the release of toxic solvent in the drying process, does not meet the requirements of environmental protection and energy saving, and can not effectively prevent the attack of shrapnel and even bullets in the explosion process.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene and carbon nanotube reinforced anticorrosive bulletproof coating, and aims to solve the problems of poor anticorrosive performance, low impact resistance, environmental pollution, incapability of quick drying and the like in the prior art. The coating of the invention is a bi-component coating, and the specific preparation method comprises the following steps:
a preparation method of graphene and carbon nanotube reinforced anticorrosive bulletproof paint comprises the following steps:
step 1, preparing a first component:
adding 0.01-10 parts of graphene, 0.01-3 parts of dispersing agent, 0.01-10 parts of carbon nano tube and 20-40 parts of polyol into a reaction kettle, continuously stirring, heating to 90-120 ℃, and vacuumizing for 0.5-4 hours for later use;
1B, cooling the solution in the step A to 40-70 ℃, adding 40-60 parts of isocyanate and 0.1-15 parts of silicone oil, continuously stirring for 0.5-2h, then heating to 75-95 ℃, reacting for 1-5h, and then measuring the NCO content, wherein the NCO content is 10-30%;
step 2, preparing a second component:
adding 10-50 parts of chain extender into a reaction kettle, adding 0.01-5 parts of graphene, 0.01-5 parts of dispersing agent and 0.01-5 parts of carbon nano tube, stirring for 0.5-2h, uniformly dispersing, and vacuumizing;
2B, adding 20-40 parts of amine-terminated polyether, 5-20 parts of polyether polyol, 1-10 parts of pigment, 1-10 parts of silicone oil and other trace auxiliaries into the solution A in sequence, stirring for 0.5-2h, and vacuumizing simultaneously
Step 3, preparing a membrane:
heating the A component and the B component to 50 ℃, and spraying the components by using a high-pressure spraying device according to the proportion of 1: 1 volume ratio, the pressure of a main machine is set to be 70kg/cm2, the temperature is 50 ℃, and the spraying film formation is carried out.
In the first component preparation:
the graphene can be one or more of graphene oxide, reduced graphene oxide, physical graphene, multilayer graphene, modified graphene and the like.
The carbon nano tube can be one or more of a single-wall carbon nano tube, a multi-wall carbon nano tube, a modified carbon nano tube and the like.
The dispersant can be one or more of BYK210, a silane coupling agent, sodium taurocholate, Tween 80 and the like.
The polyalcohol is one or more of polycaprolactone diol PCL, polycarbonate diol PCDL, polypropylene glycol PPG and polytetrahydrofuran diol PTMEG.
The isocyanate may be one or more of isophorone diisocyanate (IPDI), xylylene isocyanate (XDI), cyclohexanedimethylene diisocyanate (HXDI), 4, -dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI).
In the preparation of the second component:
adding 10-50 parts of chain extender into a reaction kettle, adding 0.01-5 parts of graphene, 0.01-5 parts of dispersing agent and 0.01-5 parts of carbon nano tube, stirring for 0.5-2h, uniformly dispersing, and vacuumizing;
2B, sequentially adding 20-40 parts of amine-terminated polyether, 5-20 parts of polyether polyol, 1-10 parts of pigment, 1-10 parts of silicone oil and other trace auxiliaries into the solution A, stirring for 0.5-2h, and vacuumizing at the same time;
the chain extender is one or more of 1, 6-hexanediamine, isophorone diamine, dimethyl-sulfur-based toluene diamine and diethyl toluene diamine.
The amino-terminated polyether can be one or more of D400, D2000, T5000, T-403, D-230 and D3000.
The polyether polyol can be one or more of polyoxypropylene diol, polytetrahydrofuran diol and tetrahydrofuran-propylene oxide copolymerized diol.
The invention has the beneficial effects that: the anticorrosive bulletproof paint prepared by the preparation method has the advantages of good anticorrosive performance, high impact resistance, environmental protection and quick drying.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The first embodiment is as follows:
preparation of a first component: adding 30 parts of polypropylene glycol PPG, 5 parts of graphene, 8 parts of carbon nano tube and 5 parts of dispersant BYK210 into a reaction kettle at one time, continuously stirring, heating to 110 ℃, vacuumizing for 2h, then cooling to 55 ℃, then adding 45 parts of MDI and 7 parts of silicone oil, stirring uniformly, heating to 85 ℃, reacting for 1.5h, and cooling to room temperature to obtain a first component;
preparation of a second component: adding 40 parts of chain extender diethyl toluene diamine into a reaction kettle, adding 1 part of graphene, 1 part of dispersing agent and 3 parts of carbon nano tubes, stirring for 1 hour, uniformly dispersing, and vacuumizing; then sequentially adding 20 parts of amino-terminated polyether D2000, 10 parts of T5000, 15 parts of polytetrahydrofuran glycol, 3 parts of pigment, 5 parts of silicone oil and other trace auxiliaries, stirring for 1 hour, and vacuumizing at the same time to obtain a second component;
the construction method comprises the following steps:
heating the first component and the second component to 50 ℃, using a high-pressure spraying device, according to the weight ratio of 1: 1 volume ratio, the pressure of a main machine is set to be 70kg/cm2, the temperature is 50 ℃, and the spraying film formation is carried out. The physical property and the salt spray resistance are tested according to GB/T2423.17 after being placed for 7 days under the specified condition of GB 9278.
The anticorrosive bulletproof coating prepared by the method has 100 percent of solid content, does not contain solvent after 10 seconds of drying, does not need heating, and can effectively prevent the attack of explosion shrapnel and even bullets when being coated on a substrate.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of graphene and carbon nanotube reinforced anticorrosive bulletproof paint is characterized by comprising the following steps:
step 1, preparing a first component:
adding 0.01-10 parts of graphene, 0.01-3 parts of dispersing agent, 0.01-10 parts of carbon nano tube and 20-40 parts of polyol into a reaction kettle, continuously stirring, heating to 90-120 ℃, and vacuumizing for 0.5-4 hours for later use;
1B, cooling the solution in the step 1A to 40-70 ℃, adding 40-60 parts of isocyanate and 0.1-15 parts of silicone oil, continuously stirring for 0.5-2h, then heating to 75-95 ℃, reacting for 1-5h, and then measuring the NCO content, wherein the NCO content is 10-30%;
step 2, preparing a second component:
adding 10-50 parts of chain extender into a reaction kettle, adding 0.01-5 parts of graphene, 0.01-5 parts of dispersant and 0.01-5 parts of carbon nano tube, stirring for 0.5-2h, uniformly dispersing, and vacuumizing;
2B, sequentially adding 20-40 parts of amine-terminated polyether, 5-20 parts of polyether polyol, 1-10 parts of pigment, 1-10 parts of silicone oil and other trace auxiliaries into the solution 2A, stirring for 0.5-2h, and vacuumizing at the same time;
step 3, preparing a membrane:
heating the first and second components to 50 ℃, using a high pressure spray apparatus, in the ratio of 1: 1 volume ratio, the pressure of a main machine of the device is set to be 70kg/cm2, the temperature is 50 ℃, and the spraying film formation is carried out.
2. The method according to claim 1, wherein in step 1A, the graphene is one or more of graphene oxide, reduced graphene oxide, physical graphene, multilayer graphene, modified graphene, and the like.
3. The method according to claim 1, wherein in step 1A, the carbon nanotubes are one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, modified carbon nanotubes, and the like.
4. The method according to claim 1, wherein in step 1A, the dispersant is one or more of BYK210, a silane coupling agent, sodium taurocholate, tween 80, and the like.
5. The method according to claim 1, wherein in step 1A, the polyol is one or more selected from polycaprolactone diol PCL, polycarbonate diol PCDL, polypropylene glycol PPG, and polytetrahydrofuran diol PTMEG.
6. The method of claim 1, wherein in step 1A, the isocyanate is one or more of isophorone diisocyanate (IPDI), xylylene isocyanate (XDI), cyclohexanedimethylene diisocyanate (HXDI), 4' -dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), and diphenylmethane diisocyanate (MDI).
7. The method according to claim 1, wherein in step 2A, the chain extender is one or more selected from the group consisting of 1, 6-hexanediamine, isophoronediamine, diamine, dimethylthiotoluenediamine, and diethyltoluenediamine.
8. The method according to claim 1, wherein in step 2B, the amino-terminated polyether is one or more selected from D400, D2000, T5000, T-403, D-230 and D3000.
9. The method according to claim 1, wherein in step 2B, the polyether polyol is one or more selected from polyoxypropylene glycol, polytetrahydrofuran glycol and tetrahydrofuran-oxypropylene copolyol.
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| CN109369873A (en) * | 2018-08-24 | 2019-02-22 | 东莞市加伏新材料研究院有限公司 | A kind of function slurry and its preparation method and application |
| CN109517514B (en) * | 2018-10-22 | 2021-02-05 | 天津昌海新材料科技发展有限公司 | Graphene modified puncture-resistant heavy-duty anticorrosive spraying material and preparation method thereof |
| CN110791186A (en) * | 2019-11-18 | 2020-02-14 | 中国建材检验认证集团厦门宏业有限公司 | Weather-proof bulletproof paint and preparation method thereof |
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