CN116023846A - Carbon nanotube-containing static conductive paint and preparation method thereof - Google Patents
Carbon nanotube-containing static conductive paint and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 83
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 83
- 239000003973 paint Substances 0.000 title claims abstract description 38
- 230000003068 static effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 89
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 65
- 229920000570 polyether Polymers 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 58
- 239000000539 dimer Substances 0.000 claims abstract description 51
- -1 modified phenolic amine Chemical class 0.000 claims abstract description 45
- KOJYENXGDXRGDK-ZUGARUELSA-N 9(Z),11(E),13(E)-Octadecatrienoic Acid methyl ester Chemical compound CCCC\C=C\C=C\C=C/CCCCCCCC(=O)OC KOJYENXGDXRGDK-ZUGARUELSA-N 0.000 claims abstract description 30
- 239000004952 Polyamide Substances 0.000 claims abstract description 27
- 229920002647 polyamide Polymers 0.000 claims abstract description 27
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 25
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 18
- YTLQFZVCLXFFRK-UHFFFAOYSA-N bendazol Chemical compound N=1C2=CC=CC=C2NC=1CC1=CC=CC=C1 YTLQFZVCLXFFRK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 14
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 116
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 45
- 238000001816 cooling Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000010306 acid treatment Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 24
- 150000004658 ketimines Chemical class 0.000 claims description 21
- 229920005862 polyol Polymers 0.000 claims description 20
- 150000003077 polyols Chemical class 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000012300 argon atmosphere Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000003828 vacuum filtration Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 229960001124 trientine Drugs 0.000 claims description 8
- 239000002383 tung oil Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001431 2-methylbenzaldehyde Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 40
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon nanotube-containing static conductive coating and a preparation method thereof, and relates to the technical field of coatings. The carbon nanotube-containing static conductive paint prepared by the invention is prepared by mixing a component A and a component B; the component A comprises modified phenolic amine, dimer acid polyamide and ureido polyether amine; the component B comprises epoxy resin, modified carbon nano tubes, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator; the modified phenolic amine is prepared by adding methyl eleostearate and phenol and then reacting with phenolic amine, so that the flexibility and heat resistance of a paint film are improved, the modified carbon nano tube is prepared by reacting an acid-treated carbon nano tube with benzyl benzimidazole, the modified carbon nano tube can be uniformly dispersed in a component B, and after the component A and the component B are blended, the modified carbon nano tube is connected in a crosslinked structure of the component A to form a conductive path, so that the conductivity of the paint is enhanced.
Description
Technical Field
The invention relates to the technical field of paint, in particular to a carbon nanotube-containing static conductive paint and a preparation method thereof.
Background
The epoxy paint has strong adhesive force, good chemical resistance, corrosion resistance, water resistance, thermal stability and electrical insulation, and is widely used in the aspects of building, chemical industry, automobiles, ships, electrical insulation and the like.
The curing agent of the common epoxy paint is polyamide or phenolic amine, wherein the polyamide contains free aliphatic polyamine, and reacts with carbon dioxide in the air to produce salt in cold weather or in high humidity, so that a paint film is fogged, the interlayer adhesive force is affected, and the phenolic amine has poor flexibility due to short molecular chains. Therefore, the invention researches and prepares the carbon nanotube-containing static conductive paint with excellent flexibility, heat resistance and strong adhesive force.
Disclosure of Invention
The invention aims to provide a carbon nanotube-containing static conductive coating and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the carbon-containing nanotube static conductive paint is prepared by mixing a component A and a component B; the component A comprises modified phenolic amine, dimer acid polyamide and ureido polyether amine; the component B comprises epoxy resin, modified carbon nano tubes, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator.
Preferably, the modified phenolic amine is prepared by adding methyl eleostearate and phenol and then reacting with phenolic amine.
Preferably, the dimer acid polyamide is prepared by reacting dimer acid with ethylenediamine; the ureido polyether amine is prepared from polyoxypropylene ether dihydric alcohol, isophorone diisocyanate and ketimine as raw materials.
Preferably, the modified carbon nanotubes are prepared by reacting acid-treated carbon nanotubes with benzyl benzimidazole.
Preferably, the preparation method of the carbon nanotube-containing static conductive paint comprises the following specific steps:
(1) Mixing methyl eleostearate, phenol and concentrated sulfuric acid according to a mass ratio of 3:1:0.02-3:1.2:0.04, heating to 60-70 ℃, and reacting for 2-3 h to obtain a methyl eleostearate addition product; mixing eleostearic acid methyl ester addition product, triethylene tetramine and formaldehyde according to the mass ratio of 1:0.6:3-1:0.8:5, heating to 75-85 ℃, reacting for 2-4 h, heating to 100-110 ℃, continuing to react for 1-2 h, and vacuum dehydrating to obtain modified phenolic amine;
(2) Vacuumizing polyether polyol at 110 ℃ for 2-3 hours, cooling to 65-75 ℃, adding isophorone diisocyanate with the mass 1.5-2 times of the polyether polyol and stannous octoate with the mass 0.001 times of the polyether polyol under argon atmosphere, continuing to react for 3-5 hours, cooling to room temperature, adding ketimine with the mass 2-3 times of the polyether polyol, heating to 40-60 ℃, reacting for 3-5 hours, adding deionized water with the mass 0.3-0.5 time of the polyether polyol, heating to 75-85 ℃, hydrolyzing for 4-6 hours, and finally performing reduced pressure distillation to obtain ureido polyether amine;
(3) Mixing modified phenolic amine, dimer acid polyamide and ureido polyether amine according to the mass ratio of 1:1:1-2:1:2, heating to 50-70 ℃ at 200-400 rpm, and stirring for reacting for 3-5 h to obtain a component A;
(4) Mixing the carbon nano tube subjected to acid treatment with benzyl benzimidazole according to a mass ratio of 1:20-1:50, heating to 60-80 ℃, and performing ultrasonic dispersion for 8-12 min at 60-80 kHz to obtain a modified carbon nano tube;
(5) Mixing epoxy resin, modified carbon nano tubes, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator according to a mass ratio of 10:2:20:10:1.5-14:4:24:12:1.7, and stirring and dispersing for 2-4 hours at 500-700 rpm to prepare a component B;
(6) Mixing the component A and the component B according to the mass ratio of 1:4-1:8, stirring and dispersing for 2-4 hours at 500-700 rpm, then heating to 50-60 ℃ and preserving heat for 3-6 hours to prepare the carbon nanotube-containing static conductive paint.
Preferably, in the step (1): the preparation method of methyl eleostearate comprises the following steps: mixing methanol, tung oil and concentrated sulfuric acid according to a mass ratio of 2:2:0.05-2:4:0.08, heating to 50-60 ℃, reacting for 5-8 h, standing for layering, and cooling to room temperature to obtain methyl eleostearate.
Preferably, in the step (2): the preparation method of the ketimine comprises the following steps: and (2) mixing diethylenetriamine, methyl isobutyl ketone and toluene according to a mass ratio of 1:2:0.6-1:4:0.6, heating to 100-110 ℃ in an argon atmosphere, reacting for 8-10 h, and removing reaction water to obtain ketimine.
Preferably, in the step (3): the preparation method of the dimer acid polyamide comprises the following steps: placing dimer acid into a four-neck flask, adding phosphoric acid with the mass of 0.01-0.02 times of that of the dimer acid, heating to 140 ℃, dropwise adding ethylenediamine with the mass of 0.09 times of that of the dimer acid for 30min, stirring at 1500rpm for reaction for 1h, heating to 240 ℃ for continuous stirring for reaction for 3h, vacuumizing to 10Pa for reaction for 30min, and cooling to 160 ℃ to obtain dimer acid polyamide.
Preferably, in the step (4): the preparation method of the acid-treated carbon nano tube comprises the following steps: mixing the carbon nano tube with nitric acid solution with the concentration of 15-25% according to the mass ratio of 1:18-1:20, performing ultrasonic dispersion for 8-12 min at 20-40 kHz, heating to 70-80 ℃, performing reflux reaction for 3-6 h, filtering, washing with deionized water for 5-8 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment.
Preferably, in the step (4): the preparation method of the benzyl benzimidazole comprises the following steps: mixing 2-aminobenzimidazole, 3-methylbenzaldehyde, zinc chloride and absolute methanol according to the mass ratio of 1:1:0.5:30-1.5:1.3:0.8:45, heating to 60-80 ℃ at 50-100 rpm, stirring for reaction for 10-12 h, cooling to room temperature and performing rotary evaporation to obtain yellow solid, dissolving the yellow solid by using ethyl acetate, performing column chromatography by using 300-400 meshes of silica gel, performing rotary evaporation again, and finally obtaining the benzyl benzimidazole, wherein the volume ratio of petroleum ether to ethyl acetate in the eluent is 5:1.
Compared with the prior art, the invention has the following beneficial effects:
the carbon nanotube-containing static conductive paint prepared by the invention is prepared by mixing a component A and a component B; the component A comprises modified phenolic amine, dimer acid polyamide and ureido polyether amine; the component B comprises epoxy resin, modified carbon nano tubes, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator;
the modified phenolic amine is prepared by adding methyl eleostearate and phenol and then reacting with phenolic amine, so that not only is a fatty chain introduced into the phenolic amine to enhance the heat resistance of the epoxy resin, but also the molecular chain of the phenolic amine is lengthened, and the flexibility of the coating after film formation is enhanced; the ureido polyether amine is prepared from polyoxypropylene ether dihydric alcohol, isophorone diisocyanate and ketimine as raw materials, and a urea bond structure is introduced into the polyether amine, so that the flexibility and the heat resistance are further improved; the modified phenolic amine, the dimer acid polyamide and the ureido polyether amine are mixed to form a first component with a cross-linked structure as a curing agent of the coating, so that free aliphatic polyamine in the coating is reduced, a paint film is prevented from fogging, and interlayer adhesive force is enhanced;
the modified carbon nano tube is prepared by reacting an acid-treated carbon nano tube with benzyl benzimidazole; pi electrons on the imidazole ring and the outer wall of the carbon nano tube form pi-pi interaction force, so that the modified carbon nano tube can be uniformly dispersed in the component B while the surface structure of the carbon nano tube is not damaged; after the component A and the component B are blended, the modified carbon nano tube is connected in a cross-linked structure of the component A to form a conductive path, so that the conductivity of the coating is enhanced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the test method of each index of the antistatic breathable fabric manufactured in the following examples is as follows:
flexibility: the carbon nanotube-containing static conductive paint prepared in the examples and the comparative examples is subjected to flexibility test by referring to GB/T1731;
heat resistance: the carbon nanotube-containing static conductive paint prepared in the example and the comparative example is coated on the surface of the same material, the dosage is the same, the thickness is the same, and after the same drying time, the heat resistance test is carried out for 120 hours at 450 ℃ by referring to GB/T1735;
adhesion force: the carbon nanotube-containing conductive paint prepared in examples and comparative examples was subjected to adhesion test with reference to GB 5210.
Conductivity: the carbon nanotube-containing static conductive paint prepared in the examples and the comparative examples is respectively coated on plastic substrates of the same specification and the same material, the coating thickness is 0.5mm, and after the conductive paint on the surface of the plastic substrate is dried, the resistivity of the plastic substrate without the conductive paint and the carbon nanotube-containing static conductive paint are respectively tested.
Example 1
(1) Mixing methanol, tung oil and concentrated sulfuric acid according to a mass ratio of 2:2:0.05, heating to 50 ℃, reacting for 5 hours, standing for layering, and cooling to room temperature to obtain methyl eleostearate; mixing methyl eleostearate, phenol and concentrated sulfuric acid according to a mass ratio of 3:1:0.02, heating to 60 ℃, and reacting for 2 hours to obtain a methyl eleostearate addition product; mixing eleostearic acid methyl ester addition product, triethylene tetramine and formaldehyde according to the mass ratio of 1:0.6:3, heating to 75 ℃, reacting for 2 hours, heating to 100 ℃, continuing to react for 1 hour, and vacuum dehydrating to obtain modified phenolic amine;
(2) The preparation method comprises the steps of mixing diethylenetriamine, methyl isobutyl ketone and toluene according to a mass ratio of 1:2:0.6, heating to 100 ℃ under an argon atmosphere, and removing reaction water after reacting for 8 hours to prepare ketimine; vacuumizing polyether polyol at 110 ℃ for 2 hours, cooling to 65 ℃, adding isophorone diisocyanate with the mass 1.5 times of the polyether polyol and stannous octoate with the mass 0.001 times of the polyether polyol under argon atmosphere, continuing to react for 3 hours, cooling to room temperature, adding ketimine with the mass 2 times of the polyether polyol, heating to 40 ℃, reacting for 3 hours, adding deionized water with the mass 0.3 times of the polyether polyol, heating to 75 ℃, hydrolyzing for 4-6 hours, and finally performing reduced pressure distillation to obtain ureido polyether amine;
(3) Placing dimer acid into a four-neck flask, adding phosphoric acid with the mass of 0.01 times of that of the dimer acid, heating to 140 ℃, dropwise adding ethylenediamine with the mass of 0.09 times of that of the dimer acid for 30min, stirring at 1500rpm for reaction for 1h, heating to 240 ℃, continuously stirring for reaction for 3h, vacuumizing to 10Pa for reaction for 30min, and cooling to 160 ℃ to obtain dimer acid polyamide; mixing modified phenolic amine, dimer acid polyamide and ureido polyether amine according to the mass ratio of 1:1:1, heating to 50 ℃ at 200rpm, and stirring for 3 hours to prepare a component A;
(4) Mixing the carbon nano tube with 15% nitric acid solution according to a mass ratio of 1:18, performing ultrasonic dispersion for 8min at 20kHz, heating to 70 ℃, performing reflux reaction for 3h, filtering, washing with deionized water for 5 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube with 15% nitric acid solution according to a mass ratio of 1:18, performing ultrasonic dispersion for 8min at 20kHz, heating to 70 ℃, performing reflux reaction for 3h, filtering, washing with deionized water for 5 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube subjected to acid treatment with benzyl benzimidazole according to the mass ratio of 1:20, heating to 60 ℃, and performing ultrasonic dispersion for 8min at 60kHz to obtain a modified carbon nano tube;
(5) Mixing epoxy resin, modified carbon nano tubes, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator according to a mass ratio of 10:2:20:10:1.5, and stirring and dispersing for 2 hours at 500rpm to prepare a component B;
(6) Mixing the component A and the component B according to the mass ratio of 1:4, stirring and dispersing for 2 hours at 500rpm, then heating to 50 ℃ and preserving heat for 3 hours to prepare the carbon nanotube-containing static conductive paint.
Example 2
(1) Mixing methanol, tung oil and concentrated sulfuric acid according to a mass ratio of 2:3:0.06, heating to 55 ℃, reacting for 6 hours, standing for layering, and cooling to room temperature to obtain methyl eleostearate; mixing methyl eleostearate, phenol and concentrated sulfuric acid according to a mass ratio of 3:1.1:0.03, heating to 65 ℃, and reacting for 2.5h to obtain a methyl eleostearate addition product; mixing eleostearic acid methyl ester addition product, triethylene tetramine and formaldehyde according to the mass ratio of 1:0.7:4, heating to 80 ℃, reacting for 3 hours, heating to 15 ℃, continuing to react for 1-2 hours, and carrying out vacuum dehydration to obtain modified phenolic amine;
(2) The preparation method comprises the steps of mixing diethylenetriamine, methyl isobutyl ketone and toluene according to a mass ratio of 1:3:0.6, heating to 15 ℃ under an argon atmosphere, and removing reaction water after reacting for 9 hours to prepare ketimine; vacuumizing polyether glycol at 110 ℃ for 2.5 hours, cooling to 70 ℃, adding isophorone diisocyanate with the mass 1.75 times of the polyether glycol and stannous octoate with the mass 0.001 times of the polyether glycol under argon atmosphere, continuing to react for 4 hours, cooling to room temperature, adding ketimine with the mass 2.5 times of the polyether glycol, heating to 50 ℃, reacting for 4 hours, adding deionized water with the mass 0.4 times of the polyether glycol, heating to 80 ℃, hydrolyzing for 5 hours, and finally performing reduced pressure distillation to obtain ureido polyether amine;
(3) Placing dimer acid into a four-neck flask, adding phosphoric acid with the mass of 0.015 times of that of the dimer acid, heating to 140 ℃, dropwise adding ethylenediamine with the mass of 0.09 times of that of the dimer acid for 30min, stirring at 1500rpm for reaction for 1h, heating to 240 ℃, continuously stirring for reaction for 3h, finally vacuumizing to 10Pa for reaction for 30min, and cooling to 160 ℃ to obtain dimer acid polyamide; mixing modified phenolic amine, dimer acid polyamide and ureido polyether amine according to the mass ratio of 1.5:1:1.5, heating to 60 ℃ at 300rpm, and stirring for reacting for 4 hours to obtain a component A;
(4) Mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube subjected to acid treatment with benzyl benzimidazole according to a mass ratio of 1:40, heating to 70 ℃, and performing ultrasonic dispersion for 10min at 70kHz to obtain a modified carbon nano tube;
(5) Mixing epoxy resin, modified carbon nano tube, dimethylbenzene, propylene glycol methyl ether and epoxy accelerator according to a mass ratio of 123:22:11:1.6, and stirring and dispersing for 3 hours at 600rpm to obtain a component B;
(6) Mixing the component A and the component B according to the mass ratio of 1:6, stirring and dispersing for 3 hours at 600rpm, then heating to 55 ℃ and preserving heat for 4 hours to prepare the carbon nanotube-containing static conductive paint.
Example 3
(1) Mixing methanol, tung oil and concentrated sulfuric acid according to a mass ratio of 2:4:0.08, heating to 60 ℃, reacting for 8 hours, standing for layering, and cooling to room temperature to obtain methyl eleostearate; mixing methyl eleostearate, phenol and concentrated sulfuric acid according to a mass ratio of 3:1.2:0.04, heating to 70 ℃, and reacting for 3 hours to obtain a methyl eleostearate addition product; mixing eleostearic acid methyl ester adduct, triethylene tetramine and formaldehyde according to the mass ratio of 1:0.8:5, heating to 85 ℃, reacting for 4 hours, heating to 110 ℃, continuing to react for 2 hours, and carrying out vacuum dehydration to obtain modified phenolic amine;
(2) The preparation method comprises the steps of mixing diethylenetriamine, methyl isobutyl ketone and toluene according to a mass ratio of 1:4:0.6, heating to 110 ℃ under an argon atmosphere, and removing reaction water after reacting for 10 hours to prepare ketimine; vacuumizing polyether polyol at 110 ℃ for 3 hours, cooling to 75 ℃, adding isophorone diisocyanate with 2 times of the mass of the polyether polyol and stannous octoate with 0.001 time of the mass of the polyether polyol under argon atmosphere, continuing to react for 5 hours, cooling to room temperature, adding ketimine with 3 times of the mass of the polyether polyol, heating to 60 ℃, reacting for 5 hours, adding deionized water with 0.5 time of the mass of the polyether polyol, heating to 85 ℃, hydrolyzing for 6 hours, and finally distilling under reduced pressure to obtain ureido polyether amine;
(3) Placing dimer acid into a four-neck flask, adding phosphoric acid with the mass of 0.02 times of that of the dimer acid, heating to 140 ℃, dropwise adding ethylenediamine with the mass of 0.09 times of that of the dimer acid for 30min, stirring at 1500rpm for reaction for 1h, heating to 240 ℃, continuously stirring for reaction for 3h, vacuumizing to 10Pa for reaction for 30min, and cooling to 160 ℃ to obtain dimer acid polyamide; mixing modified phenolic amine, dimer acid polyamide and ureido polyether amine according to the mass ratio of 2:1:2, heating to 70 ℃ at 400rpm, and stirring for reacting for 5 hours to obtain a component A;
(4) Mixing the carbon nano tube with 25% nitric acid solution according to the mass ratio of 1:20, performing ultrasonic dispersion for 12min at 40kHz, heating to 80 ℃, performing reflux reaction for 6h, filtering, washing with deionized water for 8 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube with 25% nitric acid solution according to the mass ratio of 1:20, performing ultrasonic dispersion for 12min at 40kHz, heating to 80 ℃, performing reflux reaction for 6h, filtering, washing with deionized water for 8 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube subjected to acid treatment with benzyl benzimidazole according to a mass ratio of 1:50, heating to 80 ℃, and performing ultrasonic dispersion for 12min at 80kHz to obtain a modified carbon nano tube;
(5) Mixing epoxy resin, modified carbon nano tubes, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator according to a mass ratio of 14:4:24:12:1.7, and stirring and dispersing for 4 hours at 700rpm to prepare a component B;
(6) Mixing the component A and the component B according to the mass ratio of 1:8, stirring and dispersing for 4 hours at 700rpm, then heating to 60 ℃ and preserving heat for 6 hours to prepare the carbon nanotube-containing static conductive paint.
Comparative example 1
(1) The preparation method comprises the steps of mixing diethylenetriamine, methyl isobutyl ketone and toluene according to a mass ratio of 1:3:0.6, heating to 15 ℃ under an argon atmosphere, and removing reaction water after reacting for 9 hours to prepare ketimine; vacuumizing polyether glycol at 110 ℃ for 2.5 hours, cooling to 70 ℃, adding isophorone diisocyanate with the mass 1.75 times of the polyether glycol and stannous octoate with the mass 0.001 times of the polyether glycol under argon atmosphere, continuing to react for 4 hours, cooling to room temperature, adding ketimine with the mass 2.5 times of the polyether glycol, heating to 50 ℃, reacting for 4 hours, adding deionized water with the mass 0.4 times of the polyether glycol, heating to 80 ℃, hydrolyzing for 5 hours, and finally performing reduced pressure distillation to obtain ureido polyether amine;
(2) Placing dimer acid into a four-neck flask, adding phosphoric acid with the mass of 0.015 times of that of the dimer acid, heating to 140 ℃, dropwise adding ethylenediamine with the mass of 0.09 times of that of the dimer acid for 30min, stirring at 1500rpm for reaction for 1h, heating to 240 ℃, continuously stirring for reaction for 3h, finally vacuumizing to 10Pa for reaction for 30min, and cooling to 160 ℃ to obtain dimer acid polyamide; mixing phenolic aldehyde amine, dimer acid polyamide and ureido polyether amine according to the mass ratio of 1.5:1:1.5, heating to 60 ℃ at 300rpm, and stirring for reacting for 4 hours to obtain a component A;
(3) Mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube subjected to acid treatment with benzyl benzimidazole according to a mass ratio of 1:40, heating to 70 ℃, and performing ultrasonic dispersion for 10min at 70kHz to obtain a modified carbon nano tube;
(4) Mixing epoxy resin, modified carbon nano tube, dimethylbenzene, propylene glycol methyl ether and epoxy accelerator according to a mass ratio of 123:22:11:1.6, and stirring and dispersing for 3 hours at 600rpm to obtain a component B;
(5) Mixing the component A and the component B according to the mass ratio of 1:6, stirring and dispersing for 3 hours at 600rpm, then heating to 55 ℃ and preserving heat for 4 hours to prepare the carbon nanotube-containing static conductive paint.
Comparative example 2
(1) Mixing methanol, tung oil and concentrated sulfuric acid according to a mass ratio of 2:3:0.06, heating to 55 ℃, reacting for 6 hours, standing for layering, and cooling to room temperature to obtain methyl eleostearate; mixing methyl eleostearate, phenol and concentrated sulfuric acid according to a mass ratio of 3:1.1:0.03, heating to 65 ℃, and reacting for 2.5h to obtain a methyl eleostearate addition product; mixing eleostearic acid methyl ester addition product, triethylene tetramine and formaldehyde according to the mass ratio of 1:0.7:4, heating to 80 ℃, reacting for 3 hours, heating to 15 ℃, continuing to react for 1-2 hours, and carrying out vacuum dehydration to obtain modified phenolic amine;
(2) Placing dimer acid into a four-neck flask, adding phosphoric acid with the mass of 0.015 times of that of the dimer acid, heating to 140 ℃, dropwise adding ethylenediamine with the mass of 0.09 times of that of the dimer acid for 30min, stirring at 1500rpm for reaction for 1h, heating to 240 ℃, continuously stirring for reaction for 3h, finally vacuumizing to 10Pa for reaction for 30min, and cooling to 160 ℃ to obtain dimer acid polyamide; mixing modified phenolic amine and dimer acid polyamide according to the mass ratio of 1.5:1, heating to 60 ℃ at 300rpm, and stirring for reacting for 4 hours to obtain a component A;
(3) Mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube subjected to acid treatment with benzyl benzimidazole according to a mass ratio of 1:40, heating to 70 ℃, and performing ultrasonic dispersion for 10min at 70kHz to obtain a modified carbon nano tube;
(4) Mixing epoxy resin, modified carbon nano tube, dimethylbenzene, propylene glycol methyl ether and epoxy accelerator according to a mass ratio of 123:22:11:1.6, and stirring and dispersing for 3 hours at 600rpm to obtain a component B;
(5) Mixing the component A and the component B according to the mass ratio of 1:6, stirring and dispersing for 3 hours at 600rpm, then heating to 55 ℃ and preserving heat for 4 hours to prepare the carbon nanotube-containing static conductive paint.
Comparative example 3
(1) Mixing methanol, tung oil and concentrated sulfuric acid according to a mass ratio of 2:3:0.06, heating to 55 ℃, reacting for 6 hours, standing for layering, and cooling to room temperature to obtain methyl eleostearate; mixing methyl eleostearate, phenol and concentrated sulfuric acid according to a mass ratio of 3:1.1:0.03, heating to 65 ℃, and reacting for 2.5h to obtain a methyl eleostearate addition product; mixing eleostearic acid methyl ester addition product, triethylene tetramine and formaldehyde according to the mass ratio of 1:0.7:4, heating to 80 ℃, reacting for 3 hours, heating to 15 ℃, continuing to react for 1-2 hours, and carrying out vacuum dehydration to obtain modified phenolic amine;
(2) The preparation method comprises the steps of mixing diethylenetriamine, methyl isobutyl ketone and toluene according to a mass ratio of 1:3:0.6, heating to 15 ℃ under an argon atmosphere, and removing reaction water after reacting for 9 hours to prepare ketimine; vacuumizing polyether glycol at 110 ℃ for 2.5 hours, cooling to 70 ℃, adding isophorone diisocyanate with the mass 1.75 times of the polyether glycol and stannous octoate with the mass 0.001 times of the polyether glycol under argon atmosphere, continuing to react for 4 hours, cooling to room temperature, adding ketimine with the mass 2.5 times of the polyether glycol, heating to 50 ℃, reacting for 4 hours, adding deionized water with the mass 0.4 times of the polyether glycol, heating to 80 ℃, hydrolyzing for 5 hours, and finally performing reduced pressure distillation to obtain ureido polyether amine;
(3) Mixing modified phenolic amine and ureido polyether amine according to the mass ratio of 1:1, heating to 60 ℃ at 300rpm, and stirring for reacting for 4 hours to obtain a component A;
(4) Mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube subjected to acid treatment with benzyl benzimidazole according to a mass ratio of 1:40, heating to 70 ℃, and performing ultrasonic dispersion for 10min at 70kHz to obtain a modified carbon nano tube;
(5) Mixing epoxy resin, modified carbon nano tube, dimethylbenzene, propylene glycol methyl ether and epoxy accelerator according to a mass ratio of 123:22:11:1.6, and stirring and dispersing for 3 hours at 600rpm to obtain a component B;
(6) Mixing the component A and the component B according to the mass ratio of 1:6, stirring and dispersing for 3 hours at 600rpm, then heating to 55 ℃ and preserving heat for 4 hours to prepare the carbon nanotube-containing static conductive paint.
Comparative example 4
(1) Mixing methanol, tung oil and concentrated sulfuric acid according to a mass ratio of 2:3:0.06, heating to 55 ℃, reacting for 6 hours, standing for layering, and cooling to room temperature to obtain methyl eleostearate; mixing methyl eleostearate, phenol and concentrated sulfuric acid according to a mass ratio of 3:1.1:0.03, heating to 65 ℃, and reacting for 2.5h to obtain a methyl eleostearate addition product; mixing eleostearic acid methyl ester addition product, triethylene tetramine and formaldehyde according to the mass ratio of 1:0.7:4, heating to 80 ℃, reacting for 3 hours, heating to 15 ℃, continuing to react for 1-2 hours, and carrying out vacuum dehydration to obtain modified phenolic amine;
(2) The preparation method comprises the steps of mixing diethylenetriamine, methyl isobutyl ketone and toluene according to a mass ratio of 1:3:0.6, heating to 15 ℃ under an argon atmosphere, and removing reaction water after reacting for 9 hours to prepare ketimine; vacuumizing polyether glycol at 110 ℃ for 2.5 hours, cooling to 70 ℃, adding isophorone diisocyanate with the mass 1.75 times of the polyether glycol and stannous octoate with the mass 0.001 times of the polyether glycol under argon atmosphere, continuing to react for 4 hours, cooling to room temperature, adding ketimine with the mass 2.5 times of the polyether glycol, heating to 50 ℃, reacting for 4 hours, adding deionized water with the mass 0.4 times of the polyether glycol, heating to 80 ℃, hydrolyzing for 5 hours, and finally performing reduced pressure distillation to obtain ureido polyether amine;
(3) Placing dimer acid into a four-neck flask, adding phosphoric acid with the mass of 0.015 times of that of the dimer acid, heating to 140 ℃, dropwise adding ethylenediamine with the mass of 0.09 times of that of the dimer acid for 30min, stirring at 1500rpm for reaction for 1h, heating to 240 ℃, continuously stirring for reaction for 3h, finally vacuumizing to 10Pa for reaction for 30min, and cooling to 160 ℃ to obtain dimer acid polyamide; mixing modified phenolic amine, dimer acid polyamide and ureido polyether amine according to the mass ratio of 1.5:1:1.5, heating to 60 ℃ at 300rpm, and stirring for reacting for 4 hours to obtain a component A;
(4) Mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment; mixing the carbon nano tube with a nitric acid solution with the concentration of 20% according to the mass ratio of 1:19, performing ultrasonic dispersion for 10min at 30kHz, heating to 75 ℃, performing reflux reaction for 4h, filtering, washing with deionized water for 6 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment;
(5) Mixing epoxy resin, an acid-treated carbon nano tube, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator according to a mass ratio of 123:22:11:1.6, and stirring and dispersing for 3 hours at 600rpm to prepare a component B;
(6) Mixing the component A and the component B according to the mass ratio of 1:6, stirring and dispersing for 3 hours at 600rpm, then heating to 55 ℃ and preserving heat for 4 hours to prepare the carbon nanotube-containing static conductive paint.
Effect example
The following table 1 gives the results of performance analysis of carbon nanotube-containing static conductive coatings employing examples 1 to 3 of the present invention and comparative examples 1 to 4: the resistivity of the plastic substrate without the carbon nanotube-containing static conductive coating is 1.35 multiplied by 10 -10
| Flexibility mm | Heat resistance | Adhesive force (MPa) | Resistivity (Ω cm) | |
| Example 1 | 1.0 | No change | 12 | 9.6×10 -10 |
| Example 2 | 0.8 | No change | 13 | 8.9×10 -10 |
| Example 3 | 1.1 | No change | 11 | 9.7×10 -10 |
| Comparative example 1 | 0.6 | Softening of the coating | 9 | 8.7×10 -10 |
| Comparative example 2 | 0.6 | Softening of the coating | 8 | 9.2×10 -10 |
| Comparative example 3 | 0.5 | Softening of the coating | 9 | 9.0×10 -10 |
| Comparative example 4 | 0.9 | No change | 11 | 6.35×10 -10 |
As is evident from comparison of the experimental data of examples and comparative examples in Table 1, the carbon nanotube-containing electrostatic conductive coatings prepared in examples 1, 2 and 3 are superior in flexibility, heat resistance, adhesion and conductivity.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The carbon-containing nanotube static conductive coating is characterized in that the carbon-containing nanotube static conductive coating is prepared by mixing a component A and a component B; the component A comprises modified phenolic amine, dimer acid polyamide and ureido polyether amine; the component B comprises epoxy resin, modified carbon nano tubes, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator.
2. The carbon nanotube-containing static conductive coating of claim 1, wherein the modified phenolic amine is prepared by adding methyl eleostearate and phenol and then reacting with phenolic amine.
3. The carbon nanotube-containing electrostatic conductive coating of claim 1, wherein the dimer acid polyamide is prepared by reacting dimer acid with ethylenediamine; the ureido polyether amine is prepared from polyoxypropylene ether dihydric alcohol, isophorone diisocyanate and ketimine as raw materials.
4. The electrostatic conductive paint for carbon nanotubes of claim 1, wherein the modified carbon nanotubes are prepared by reacting acid-treated carbon nanotubes with benzyl benzimidazole.
5. The preparation method of the carbon nanotube-containing static conductive paint is characterized by comprising the following specific steps of:
(1) Mixing methyl eleostearate, phenol and concentrated sulfuric acid according to a mass ratio of 3:1:0.02-3:1.2:0.04, heating to 60-70 ℃, and reacting for 2-3 h to obtain a methyl eleostearate addition product; mixing eleostearic acid methyl ester addition product, triethylene tetramine and formaldehyde according to the mass ratio of 1:0.6:3-1:0.8:5, heating to 75-85 ℃, reacting for 2-4 h, heating to 100-110 ℃, continuing to react for 1-2 h, and vacuum dehydrating to obtain modified phenolic amine;
(2) Vacuumizing polyether polyol at 110 ℃ for 2-3 hours, cooling to 65-75 ℃, adding isophorone diisocyanate with the mass 1.5-2 times of the polyether polyol and stannous octoate with the mass 0.001 times of the polyether polyol under argon atmosphere, continuing to react for 3-5 hours, cooling to room temperature, adding ketimine with the mass 2-3 times of the polyether polyol, heating to 40-60 ℃, reacting for 3-5 hours, adding deionized water with the mass 0.3-0.5 time of the polyether polyol, heating to 75-85 ℃, hydrolyzing for 4-6 hours, and finally performing reduced pressure distillation to obtain ureido polyether amine;
(3) Mixing modified phenolic amine, dimer acid polyamide and ureido polyether amine according to the mass ratio of 1:1:1-2:1:2, heating to 50-70 ℃ at 200-400 rpm, and stirring for reacting for 3-5 h to obtain a component A;
(4) Mixing the carbon nano tube subjected to acid treatment with benzyl benzimidazole according to a mass ratio of 1:20-1:50, heating to 60-80 ℃, and performing ultrasonic dispersion for 8-12 min at 60-80 kHz to obtain a modified carbon nano tube;
(5) Mixing epoxy resin, modified carbon nano tubes, dimethylbenzene, propylene glycol methyl ether and an epoxy accelerator according to a mass ratio of 10:2:20:10:1.5-14:4:24:12:1.7, and stirring and dispersing for 2-4 hours at 500-700 rpm to prepare a component B;
(6) Mixing the component A and the component B according to the mass ratio of 1:4-1:8, stirring and dispersing for 2-4 hours at 500-700 rpm, then heating to 50-60 ℃ and preserving heat for 3-6 hours to prepare the carbon nanotube-containing static conductive paint.
6. The method for preparing an electrostatic conductive paint containing carbon nanotubes according to claim 5, wherein in the step (1): the preparation method of methyl eleostearate comprises the following steps: mixing methanol, tung oil and concentrated sulfuric acid according to a mass ratio of 2:2:0.05-2:4:0.08, heating to 50-60 ℃, reacting for 5-8 h, standing for layering, and cooling to room temperature to obtain methyl eleostearate.
7. The method for preparing an electrostatic conductive paint containing carbon nanotubes according to claim 5, wherein in the step (2): the preparation method of the ketimine comprises the following steps: and (2) mixing diethylenetriamine, methyl isobutyl ketone and toluene according to a mass ratio of 1:2:0.6-1:4:0.6, heating to 100-110 ℃ in an argon atmosphere, reacting for 8-10 h, and removing reaction water to obtain ketimine.
8. The method for preparing an electrostatic conductive paint containing carbon nanotubes according to claim 5, wherein in the step (3): the preparation method of the dimer acid polyamide comprises the following steps: placing dimer acid into a four-neck flask, adding phosphoric acid with the mass of 0.01-0.02 times of that of the dimer acid, heating to 140 ℃, dropwise adding ethylenediamine with the mass of 0.09 times of that of the dimer acid for 30min, stirring at 1500rpm for reaction for 1h, heating to 240 ℃ for continuous stirring for reaction for 3h, vacuumizing to 10Pa for reaction for 30min, and cooling to 160 ℃ to obtain dimer acid polyamide.
9. The method for preparing an electrostatic conductive paint containing carbon nanotubes according to claim 5, wherein in the step (4): the preparation method of the acid-treated carbon nano tube comprises the following steps: mixing the carbon nano tube with nitric acid solution with the concentration of 15-25% according to the mass ratio of 1:18-1:20, performing ultrasonic dispersion for 8-12 min at 20-40 kHz, heating to 70-80 ℃, performing reflux reaction for 3-6 h, filtering, washing with deionized water for 5-8 times, performing vacuum filtration, and finally drying at 110 ℃ for 6h to obtain the carbon nano tube subjected to acid treatment.
10. The method for preparing an electrostatic conductive paint containing carbon nanotubes according to claim 5, wherein in the step (4): the preparation method of the benzyl benzimidazole comprises the following steps: mixing 2-aminobenzimidazole, 3-methylbenzaldehyde, zinc chloride and absolute methanol according to the mass ratio of 1:1:0.5:30-1.5:1.3:0.8:45, heating to 60-80 ℃ at 50-100 rpm, stirring for reaction for 10-12 h, cooling to room temperature and performing rotary evaporation to obtain yellow solid, dissolving the yellow solid by using ethyl acetate, performing column chromatography by using 300-400 meshes of silica gel, performing rotary evaporation again, and finally obtaining the benzyl benzimidazole, wherein the volume ratio of petroleum ether to ethyl acetate in the eluent is 5:1.
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