CN111423797A - Water-based static conductive polyurea coating and preparation method thereof - Google Patents

Water-based static conductive polyurea coating and preparation method thereof Download PDF

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CN111423797A
CN111423797A CN201910022604.9A CN201910022604A CN111423797A CN 111423797 A CN111423797 A CN 111423797A CN 201910022604 A CN201910022604 A CN 201910022604A CN 111423797 A CN111423797 A CN 111423797A
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conductive
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diisocyanate
polyoxyethylene ether
powder
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孔凡厚
张宇
吴井龙
滕赟
王佳妮
王新
张学龙
宋丽凤
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Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
Sinochem Shenyang Advanced Materials Technology Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
Sinochem Shenyang Advanced Materials Technology Co Ltd
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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
    • C09D175/02—Polyureas
    • 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
    • C09D5/24—Electrically-conducting paints
    • 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
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    • C09D7/65—Additives macromolecular
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention relates to the technical field of composite materials, and particularly relates to a water-based static conductive polyurea coating and a preparation method thereof. The coating is a component I containing polyisocyanate and a component II serving as a curing agent; wherein, the component one comprises 10 to 50 portions of polyisocyanate, 0.1 to 10 portions of dispersant, 2 to 25 portions of emulsifier and 2 to 30 portions of conductive powder according to 100 portions of weight; the second component is alkaline solution or metal salt solution with the concentration of 10-80 wt%; the mass ratio of the first component to the second component is 1:1-20: 1. The aqueous static conductive polyurea coating realizes the static conductive function of the aqueous polyurea coating, uses the conductive powder matched with the aqueous polyurea, selects and determines proper dispersant and emulsifier, ensures that the matched conductive powder is uniformly distributed in the aqueous polyurea-based coating, can effectively prevent static aggregation, can release the aggregated static brought by foreign objects through conduction dissipation, and has the function of preventing static sparks.

Description

Water-based static conductive polyurea coating and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to a water-based static conductive polyurea coating and a preparation method thereof.
Background
Polyurea technology is a significant technological advance beyond high solids coatings, waterborne coatings, powder coatings. The polyurea has wide prospect as a high-solid-content environment-friendly and green functional material in the application of the surfaces of structures such as metal, concrete and the like. Compared with a polyurethane system, the polyurea system has the greatest characteristics of fast reaction, energy conservation and high efficiency. However, the current polyurea technology is mainly based on solvent-type or solvent-free elastomers, and a small number of patents report water-based polyurea-based coatings, and no water-based electrostatic conductive polyurea-based coating is disclosed in the patent at present.
The current waterborne static conductive coating is mainly prepared into a film substance by modified waterborne epoxy resin, waterborne polyurethane resin and the like. The conductive powder is used as an external conductive filler, has certain conductivity in coatings such as epoxy resin, polyurethane and the like, and can meet the requirements of static conductive parts, but no patent reports exist at present that a conductive powder product is added in a water-based polyurea coating. For example, patent publication No. CN108165076A discloses that the inventive aqueous nano antistatic epoxy floor paint has the characteristics of good compatibility among components, small addition amount of conductive filler, and the like, and patent publication No. CN104893538B discloses that the aqueous polyurethane resin and the sulfonated graphene/PEDOT composite are used for preparing the aqueous antistatic coating, and the inventive aqueous antistatic coating has the defects of low solid content, poor wear resistance, low temperature resistance, low hardness, poor acid resistance, poor alkali resistance, poor conductivity, poor solvent resistance, poor flame retardance, and the like.
Meanwhile, the application of the publication No. CN108586688A discloses an organic-inorganic hybrid composite material and a preparation method thereof, and the obtained aqueous polyurea-based organic-inorganic hybrid material has the defects of poor mechanical property, poor impact toughness, low hardness and the like due to poor effect of an interface dispersant. It can be seen that whether the conductive powder can be sufficiently and uniformly dispersed in the aqueous polyurea-based coating is the key to determine the conductivity of the conductive powder.
Disclosure of Invention
The invention aims to provide a water-based static conductive polyurea coating and a preparation method thereof aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a water-based static conductive polyurea coating is characterized in that the coating comprises a first component containing polyisocyanate and a second component serving as a curing agent; wherein, the component one comprises 10 to 50 portions of polyisocyanate, 0.1 to 10 portions of dispersant, 2 to 25 portions of emulsifier and 2 to 30 portions of conductive powder according to 100 portions of weight; the second component is alkaline solution or metal salt solution with the concentration of 10-80 wt%; the mass ratio of the first component to the second component is 1:1-20: 1.
Preferably, the mass ratio of the first component to the second component is 1:1-5: 1.
Preferably, the first component comprises, by weight, 100 parts of 35-50 parts of polyisocyanate, 5-10 parts of dispersant, 10-20 parts of emulsifier and 2-15 parts of conductive powder.
The curing agent of the second component is preferably an alkaline solution or a metal salt solution with a concentration of 40 to 70 wt%.
The polyisocyanate is 2,4(6) -toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, lysine diisocyanate, polymethylene polyphenyl polyisocyanate, liquefied MDI, TDI dimer, TDI trimer, TDI-TMP adduct, HDI dimer, HDI trimer, HDI diisocyanate, and the like, HDI biuret, IPDI trimer, TDI-HDI mixed polymer, HDI-IPDI mixed polymer, triphenylmethane triisocyanate, dimethyl triphenylmethane tetraisocyanate, thiophosphoric acid tri (4-phenyl isocyanate) and one or more of heptaisocyanate;
the dispersant is one or a mixture of more of Taiwan Zhongya 5040, Japan Nopodaceae 5027, dispersant AD-25, calcium stearate, BYK-163, BYK-2055, Digao 760W dispersant, Digao wetting dispersant 670, OROTAN 731A, Demodex FX365, Demodex FA620, Luborun Solsperse, Disasbrolone AQ-320, Clariana A4075, Clariana A4100, subfamily DA-01 and Youtoyt-5040;
the emulsifier is one or a mixture of more of nonylphenol polyoxyethylene ether NP series, agricultural emulsion No. 100 and the like, octylphenol polyoxyethylene ether emulsifier OP series, phosphooctyl No. 10 (sec-octylphenol polyoxyethylene ether), tributylphenol polyoxyethylene ether (C4H9) - -O (EO) nH, alkylphenol polyoxyethylene ether emulsifier No. 11, lauryl polyoxyethylene ether, isooctyl polyoxyethylene ether Igepal CA, octadecyl polyoxyethylene ether, isotridecyl alcohol polyoxyethylene ether, phenethyl phenol polyoxyethylene ether, fatty amine (also called alkylamine) polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate SOPA-II (270), phenol formaldehyde condensate sodium sulfonate dispersant HN and desugarized lignin sodium sulfonate M-9;
the conductive powder is one or a mixture of more of conductive metal powder, iron powder, aluminum powder, zinc powder, copper powder, silver-coated copper powder, nickel powder, conductive mica powder, conductive titanium dioxide, zinc oxide, conductive graphite, conductive carbon black, conductive carbon fiber, conductive graphene, conductive carbon nanotube, indium tin oxide, high-molecular conductive material POM and high-molecular polyaniline;
the alkaline solution or the metal salt solution is one or more of phosphate, chlorate, molysite, polyaluminium salt, polyammonium salt, silicate, carbonate, hydroxide, borate and sulfate of one or more of lithium, beryllium, sodium, magnesium, aluminum, magnesium, potassium, calcium, iron, copper, lead, zinc, nickel, manganese, cadmium, mercury, germanium, antimony, tellurium and polonium.
Preferably, the polyisocyanate is one or more of 2,4(6) -toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, TDI trimer, HDI-IPDI mixed polymer and triphenylmethane triisocyanate;
the dispersant is one or more of BYK-163, dikaohu dispersant 670, Droju FA620, Luborun Solsperse, Kelaien A4075, and subfamily DA-01;
the emulsifier is one or more of laurinol polyoxyethylene ether, octadecanol polyoxyethylene ether, phenethyl phenol polyoxyethylene ether, fatty amine (also called alkylamine) polyoxyethylene ether, phenol formaldehyde condensate sodium sulfonate dispersant HN and desugarized sodium lignosulfonate M-9;
the conductive powder is one or more of aluminum powder, silver powder, conductive mica powder, conductive titanium dioxide, conductive carbon black, conductive carbon fiber and conductive graphene.
A preparation method of water-based static conductive polyurea coating,
(1) mixing 10-50 parts of polyisocyanate, 0.1-10 parts of dispersant and 2-25 parts of emulsifier according to the parts by weight, fully and uniformly stirring, and adding 2-30 parts of conductive powder into a polyisocyanate mixture to be fully dispersed and mixed to serve as a component I;
(2) dissolving an alkaline compound or metal salt in 100 parts of water, and adjusting the concentration of the solution to 10-80% by mass as a second component;
(3) and (2) fully mixing the obtained component I and the component II in parts by mass (mixing at present) at the present time, wherein the mass ratio of the component I to the component II is 1:1-20:1, and curing at room temperature for 24 hours to obtain the waterborne static conductive polyurea coating.
The detection of the aqueous electrostatic conductive polyurea coating prepared according to the method shows that the material has high solid content, good wear resistance and good conductivity (surface resistance 10)5-108) The coating has the characteristics of high strength, high temperature resistance, corrosion resistance, good mechanical property and the like, and can be applied to the fields of petrochemical static conductive and anticorrosive coatings, wear-resistant static conductive terraces, engineering machinery, aerospace and the like.
The invention has the advantages that:
the aqueous static conductive polyurea coating realizes the static conductive function of the aqueous polyurea coating, uses the conductive powder matched with the aqueous polyurea, selects and determines proper dispersant and emulsifier, ensures that the matched conductive powder is uniformly distributed in the aqueous polyurea-based coating, can effectively prevent static aggregation, can release the aggregated static brought by foreign objects through conduction dissipation, and has the function of preventing static sparks. Meanwhile, the mechanical properties (such as impact toughness and hardness) and the corrosion resistance (acid resistance, alkali resistance, salt resistance and solvent resistance) of the aqueous polyurea-based coating are relatively improved. Compared with the solid content of the waterborne epoxy resin and waterborne polyurethane static conductive coating, the coating has the defects of high solid content, strong wear resistance, high temperature resistance, high hardness, strong acid resistance, strong alkali resistance, strong conductivity, high solvent resistance, strong flame retardance and the like.
Drawings
FIG. 1 is an electron microscope photograph of the coating obtained in control group 2.
FIG. 2 is an electron microscope photograph of the coating obtained in example 12 of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
Example 1
According to the weight portion, 30 portions of polymeric diphenylmethane diisocyanate are added into a container A, a dispersing agent AD-255 portions are added dropwise, 3 portions of emulsifier octyl phenol polyoxyethylene ether emulsifier OP series are added dropwise, the mixture is fully and uniformly stirred, 10 portions of conductive powder iron powder are added, and the mixture is fully mixed to form a first component; dissolving 40 parts of sodium dihydrogen phosphate in water in a container B, and adjusting the concentration of the solution to 25% to obtain a second component; and (3) adding 50 parts of the first component into the container C at room temperature, slowly adding 50 parts of the second component while stirring, fully mixing the two components (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 2
Adding 20 parts by weight of triphenylmethane triisocyanate into a container A, dropwise adding 6702 parts by weight of dispersant dikaohumiron dispersant, dropwise adding 7 parts by weight of emulsifier octadecanol-based polyoxyethylene ether, fully and uniformly stirring, adding 14 parts by weight of conductive powder silver powder, and fully mixing to obtain a first component; dissolving 35 parts of ferric chloride powder in water in a container B, and adjusting the concentration of the solution to be 30% to be a second component; and adding 66.7 parts of the first component into the container C, slowly adding 33.3 parts of the second component under the stirring state, fully mixing the first component and the second component (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 3
Adding 40 parts by weight of trimethyl-1, 6-hexamethylene diisocyanate into a container A, dropwise adding 8 parts by weight of dispersant Lubrium Solsperse, dropwise adding 4 parts by weight of emulsifier phosphaxane No. 10 (sec-octyl phenol polyoxyethylene ether), fully stirring uniformly, adding 20 parts by weight of conductive mica powder, and fully mixing to obtain a first component; dissolving 20 parts of calcium hydroxide powder in water in a container B, and adjusting the concentration of the solution to be 20% to be a second component; and adding 75 parts of the first component into the container C, slowly adding 25 parts of the second component under the stirring state, fully mixing the two components (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 4
Adding 30 parts by weight of polymethylene polyphenyl polyisocyanate into a container A, dropwise adding a dispersant, namely a modesty FX 3650.5 parts, dropwise adding 24 parts by weight of emulsifier laurinol polyoxyethylene ether, fully and uniformly stirring, adding 5 parts by weight of conductive titanium dioxide, and fully mixing to obtain a first component; dissolving 30 parts of sodium silicate powder in water in a container B, and adjusting the concentration of the solution to 27% to be a second component; and adding 50 parts of the first component into the container C, slowly adding 20 parts of the second component under the stirring state, fully mixing the two components (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 5
According to the weight portion, 30 portions of HDI biuret by weight are added into a container A, 10 portions of emulsifier isooctyl polyoxyethylene ether Igepal CA are added in a dropwise manner, and the mixture is fully stirred uniformly, 15 portions of zinc oxide are added and fully mixed to form a first component; dissolving 20 parts of potassium sulfate powder in water in a container B, and adjusting the concentration of the solution to 50% to be a second component; and (3) adding 80 parts of the first component into the container C, slowly adding 20 parts of the second component under the stirring state, fully mixing the first component and the second component (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 6
According to the weight parts, 10 parts of thiophosphoric acid tris (4-phenyl isocyanate) in a container A are added with BYK-1638 parts of dispersing agent dropwise, and added with M-913 parts of emulsifier desugared sodium lignosulfonate dropwise, and the mixture is fully stirred uniformly, and added with 4 parts of conductive carbon nano tubes and fully mixed to form a first component; dissolving 30 parts of sodium carbonate powder in water in a container B, and adjusting the concentration of the solution to be 20% to be a second component; and (3) adding 83.3 parts of the first component into the container C, slowly adding 16.7 parts of the second component under the stirring state, fully mixing the first component and the second component (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 7
According to the weight parts, 40 parts of mixed polymer of thiophosphoric acid tris (4-phenyl isocyanate) and HDI-IPDI is added into a container A, the proportion of the thiophosphoric acid tris (4-phenyl isocyanate) and the HDI-IPDI is 1:1, dispersant BYK-20555 parts and emulsifier isotridecanol polyoxyethylene ether 6 parts are added dropwise, the mixture is fully and uniformly stirred, and conductive graphene 4 parts is added and fully mixed to form a first component; dissolving 20 parts of aluminum borate powder in water in a container B, and adjusting the concentration of the solution to 40% to be a second component; and adding 87.5 parts of the first component into the container C, slowly adding 12.5 parts of the second component under the stirring state, fully mixing the first component and the second component (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 8
According to parts by weight, 35 parts of mixed polymer of dimethyl biphenyl diisocyanate, lysine diisocyanate and HDI-IPDI in a container A, wherein the ratio of the mass of the mixed polymer to the mass of the HDI-IPDI is 1:1, dripping 40750.2 parts of dispersant Kelaien A, dripping 100 # 8 parts of emulsifier agricultural emulsion, fully and uniformly stirring, adding 7 parts of indium tin oxide, and fully mixing to obtain a first component; dissolving 18 parts of copper phosphate powder in water in a container B, and adjusting the concentration of the solution to be 34% to be a second component; and (3) adding 89 parts of the first component into the container C, slowly adding 11 parts of the second component under the stirring state, fully mixing the first component and the second component (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 9
Adding 30 parts by weight of p-phenylene diisocyanate, polymethylene polyphenyl polyisocyanate and TDI dimer into a container A according to the weight part ratio of 1: 2, dripping 1 part of dispersant calcium stearate, dripping 4 parts of emulsifier octyl phenol polyoxyethylene ether emulsifier OP series, fully and uniformly stirring, adding 10 parts of high-molecular conductive material POM, and fully mixing to obtain a first component; dissolving 25 parts of magnesium chloride powder in water in a container B, and adjusting the concentration of the solution to 45% to be a second component; and adding 85 parts of the first component into the container C, slowly adding 15 parts of the second component under the stirring state, fully mixing the first component and the second component (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 10
Adding 20 parts by weight of 2,4(6) -toluene diisocyanate, dimethyl diphenyl diisocyanate and IPDI trimer into a container A according to the weight part ratio of 1: 3: 2, dripping dispersant BYK-20554 parts, dripping emulsifier fatty amine (also called alkylamine) polyoxyethylene ether 6 parts, fully and uniformly stirring, adding conductive titanium dioxide 16 parts, and fully mixing to obtain a first component; dissolving 30 parts of sodium hydroxide powder in water in a container B, and adjusting the concentration of the solution to 50% to be a second component; and (3) adding 70 parts of the first component into the container C, slowly adding 30 parts of the second component under the stirring state, fully mixing the first component and the second component (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 11
Adding 40 parts by weight of tetramethyl m-xylylene diisocyanate, polymethylene polyphenyl polyisocyanate and IPDI trimer into a container A according to the weight parts, wherein the ratio of the tetramethyl m-xylylene diisocyanate to the polymethylene polyphenyl polyisocyanate to the IPDI trimer is 3: 1: 2, dripping 8 parts of emulsifier alkylphenol polyoxyethylene ether emulsifier No. 11 into the dispersant Kelaien A40752 parts, fully and uniformly stirring, adding 25 parts of nickel powder, and fully mixing to obtain a first component; dissolving 12 parts of calcium borate powder in water in a container B, and adjusting the concentration of the solution to be 60% to be a second component; and adding 60 parts of the first component into the container C, slowly adding 40 parts of the second component under the stirring state, fully mixing the two components (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
Example 12
Adding 40 parts by weight of tetramethyl m-xylylene diisocyanate, norbornane diisocyanate and IPDI trimer into a container A according to the parts by weight, wherein the ratio of the tetramethyl m-xylylene diisocyanate to the norbornane diisocyanate to the IPDI trimer is 1: 6: 2 dripping 6708 parts of dispersant dikaohumizing dispersant, dripping emulsifying agent tributyl phenol polyoxyethylene ether (C)4H9)--O(EO)nH14, fully and uniformly stirring, adding 5 parts of high-molecular polyaniline, and fully mixing to obtain a first component; dissolving 14 parts of sodium sulfate powder in water in a container B, and adjusting the concentration of the solution to 70% to be a second component; and adding 50 parts of the first component into the container C, slowly adding 50 parts of the second component under the stirring state, fully mixing the first component and the second component (mixing at present), brushing, and curing at room temperature for 24 hours to prepare the water-based static conductive polyurea coating.
The invention compares a comparison group 1 (the publication number is CN108165076A discloses the invention aqueous nanometer antistatic epoxy floor paint) with a comparison group 2 (the publication number is CN108586688A discloses the organic-inorganic hybrid composite material and the polyurea-based organic-inorganic hybrid material obtained by the preparation method), and the invention uses the above 1-12 practical examples to cure for 12h at room temperature, and detects the mechanical property of the composite material after 7 days of maintenance. The bending property test of the material is carried out according to the standard GB/T93412008, and the tensile property test of the material is carried out according to the standard GB/T1040-2006, and the results are shown in the table (Table 1).
TABLE 1
Figure BDA0001941313780000061
The data in table 1 are compared, and the detection shows that the novel material has the characteristics of high strength, high modulus, good mechanical property and the like. The flexural modulus, flexural strength, flexural stress at a predetermined deflection, flexural stress at break, tensile strain at break, tensile strength, tensile strain at tensile strength and tensile yield stress of the aqueous electrostatic conductive polyurea coating in examples 1, 3, 5, 7, 9 and 11 were all superior to those of the control group 1 and 2, and the comparative group 2.
Comparing the coatings of the control group 1 and the control group 2, the coating of the invention of the 12 specific examples is cured for 12 hours at room temperature, and after the coating is maintained for 7 days, the temperature resistance, the hardness, the solvent resistance, the impact toughness and the like of the composite material are detected. Respectively testing the hardness performance of the material by using a standard GB/T6739-1996; testing the solvent resistance and acid and alkali resistance of the material by using a standard GB/T9274-1988; tests for testing the static conductive performance of the coating by using the standard GB50515-2010 static conductive (anti) ground design specification and the like, wherein the standard value range of the surface resistance of the static conductive coating is 105-109Ohm, results are shown in the table below (table 2).
TABLE 2
Figure BDA0001941313780000062
Compared with the control group 1 and the control group 2, the detection shows that the waterborne static conductive polyurea coating in the inventive material of the embodiment 2, the embodiment 4, the embodiment 6, the embodiment 8, the embodiment 10 and the embodiment 12 has the characteristics of high temperature resistance, high hardness, corrosion resistance, high reaction rate, good static conductive performance and the like. The data in Table 2 show that the temperature resistance, hardness, solvent resistance, acid resistance, alkali resistance, impact toughness and the like of the aqueous static conductive polyurea coating are all larger than those of the control group. Epoxy control group 1 had a surface resistance of 107-108Ohm meterAnd the surface resistance value of the water-based electrostatic conductive polyurea coating ranges from 105-108Ohm, the resistance is more stable.
The invention selects and determines proper dispersant and emulsifier, and 2-30% of conductive powder is efficiently dispersed in the aqueous polyurea coating system, such as the coating surface resistance value range of 105-108 ohm in the embodiments 2,4, 6, 8, 10 and 12, which realizes the static conductive function of the aqueous polyurea coating; meanwhile, the bending modulus, the bending strength, the bending stress at a specified deflection, the bending stress at break, the tensile strain at tensile strength and the tensile yield stress of the aqueous electrostatic conductive polyurea coating in example 1, example 3, example 5, example 7, example 9 and example 11 are all superior to those of the control group 1 and the control group 2. The temperature resistance, hardness, solvent resistance, acid resistance, alkali resistance, impact toughness and the like of the aqueous electrostatic conductive polyurea coating in the embodiment 2, the embodiment 4, the embodiment 6, the embodiment 8, the embodiment 10 and the embodiment 12 are all larger than those of the control group. Observing an electron microscope picture (figure 1) of a control group 2 and an electron microscope picture (figure 2) of a test example 12, wherein the figure 1 shows that an organic component is separated from an inorganic component, and the figure 2 shows that the organic component and the inorganic component have larger lapping degree and are in a 'bone-meat connection' state, so that the matched conductive powder is uniformly distributed in the aqueous polyurea-based coating, has less vacancy, can effectively prevent electrostatic aggregation, can release aggregated static brought by a foreign object through conduction dissipation, has the function of preventing electrostatic sparks, and simultaneously improves the density of the coating to achieve the corrosion resistance.

Claims (5)

1. The water-based static conductive polyurea coating is characterized in that: the coating is a component I containing polyisocyanate and a component II serving as a curing agent; wherein, the component one comprises 10 to 50 portions of polyisocyanate, 0.1 to 10 portions of dispersant, 2 to 25 portions of emulsifier and 2 to 30 portions of conductive powder according to 100 portions of weight; the second component is alkaline solution or metal salt solution with the concentration of 10-80 wt%; the mass ratio of the first component to the second component is 1:1-20: 1.
2. The aqueous electrostatic conductive polyurea coating according to claim 1, wherein: the emulsifier is polyoxyethylene ether or sodium sulfonate, and the mass ratio of the component I to the component II is 1:1-5: 1.
3. The aqueous electrostatic conductive polyurea coating according to claim 1 or 2, wherein:
the polyisocyanate is 2,4(6) -toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, lysine diisocyanate, polymethylene polyphenyl polyisocyanate, liquefied MDI, TDI dimer, TDI trimer, TDI-TMP adduct, HDI dimer, HDI trimer, HDI diisocyanate, and the like, HDI biuret, IPDI trimer, TDI-HDI mixed polymer, HDI-IPDI mixed polymer, triphenylmethane triisocyanate, dimethyl triphenylmethane tetraisocyanate, thiophosphoric acid tri (4-phenyl isocyanate) and one or more of heptaisocyanate;
the dispersant is one or a mixture of more of Taiwan Zhongya 5040, Japan Nopodaceae 5027, dispersant AD-25, calcium stearate, BYK-163, BYK-2055, Digao 760W dispersant, Digao wetting dispersant 670, OROTAN 731A, Demodex FX365, Demodex FA620, Luborun Solsperse, Disasbrolone AQ-320, Clariana A4075, Clariana A4100, subfamily DA-01 and Youtoyt-5040;
the emulsifier is one or a mixture of more of nonylphenol polyoxyethylene ether NP series, agricultural emulsion No. 100 and the like, octylphenol polyoxyethylene ether emulsifier OP series, phosphooctyl No. 10 (sec-octylphenol polyoxyethylene ether), tributylphenol polyoxyethylene ether (C4H9) - -O (EO) nH, alkylphenol polyoxyethylene ether emulsifier No. 11, lauryl polyoxyethylene ether, isooctyl polyoxyethylene ether Igepal CA, octadecyl polyoxyethylene ether, isotridecyl alcohol polyoxyethylene ether, phenethyl phenol polyoxyethylene ether, fatty amine (also called alkylamine) polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate SOPA-II (270), phenol formaldehyde condensate sodium sulfonate dispersant HN and desugarized lignin sodium sulfonate M-9;
the conductive powder is one or a mixture of more of conductive metal powder, iron powder, aluminum powder, zinc powder, copper powder, silver-coated copper powder, nickel powder, conductive mica powder, conductive titanium dioxide, zinc oxide, conductive graphite, conductive carbon black, conductive carbon fiber, conductive graphene, conductive carbon nanotube, indium tin oxide, high-molecular conductive material POM and high-molecular polyaniline;
the alkaline solution or the metal salt solution is one or more of phosphate, chlorate, molysite, polyaluminium salt, polyammonium salt, silicate, carbonate, hydroxide, borate and sulfate of one or more of lithium, beryllium, sodium, magnesium, aluminum, magnesium, potassium, calcium, iron, copper, lead, zinc, nickel, manganese, cadmium, mercury, germanium, antimony, tellurium and polonium.
4. The aqueous electrostatic conductive polyurea coating of claim 3, wherein:
the polyisocyanate is one or more of 2,4(6) -toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, TDI trimer, HDI-IPDI mixed polymer and triphenylmethane triisocyanate;
the dispersant is one or more of BYK-163, dikaohu dispersant 670, Droju FA620, Luborun Solsperse, Kelaien A4075, and subfamily DA-01;
the emulsifier is one or more of laurinol polyoxyethylene ether, octadecanol polyoxyethylene ether, phenethyl phenol polyoxyethylene ether, fatty amine (also called alkylamine) polyoxyethylene ether, phenol formaldehyde condensate sodium sulfonate dispersant HN and desugarized sodium lignosulfonate M-9;
the conductive powder is one or more of aluminum powder, silver powder, conductive mica powder, conductive titanium dioxide, conductive carbon black, conductive carbon fiber and conductive graphene;
the alkaline solution or metal salt solution is lithium, beryllium, sodium, magnesium, potassium, calcium, germanium, antimony, tellurium, polonium phosphate, chlorate, silicate, carbonate, sulfate.
5. A method for preparing the aqueous static conductive polyurea coating according to claim 1, which is characterized in that:
(1) mixing 10-50 parts of polyisocyanate, 0.1-10 parts of dispersant and 2-25 parts of emulsifier according to the parts by weight, fully and uniformly stirring, and adding 2-30 parts of conductive powder into a polyisocyanate mixture to be fully dispersed and mixed to serve as a component I;
(2) dissolving an alkaline compound or metal salt in 100 parts of water, and adjusting the concentration of the solution to 10-80% by mass as a second component;
(3) and (2) fully mixing the obtained component I and the component II according to the mass part ratio of 1:1-20:1, and curing at room temperature for 24 hours to obtain the waterborne static conductive polyurea coating.
CN201910022604.9A 2019-01-10 2019-01-10 Water-based static conductive polyurea coating and preparation method thereof Pending CN111423797A (en)

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Application publication date: 20200717