CN115968065A - Electric heating slurry and preparation method thereof - Google Patents
Electric heating slurry and preparation method thereof Download PDFInfo
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- CN115968065A CN115968065A CN202310041202.XA CN202310041202A CN115968065A CN 115968065 A CN115968065 A CN 115968065A CN 202310041202 A CN202310041202 A CN 202310041202A CN 115968065 A CN115968065 A CN 115968065A
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- 238000005485 electric heating Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000007613 slurry method Methods 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 142
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 81
- 239000000843 powder Substances 0.000 claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 239000007822 coupling agent Substances 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 19
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- 238000000227 grinding Methods 0.000 claims description 39
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- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 2
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 2
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- -1 amine salt Chemical class 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
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- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 10
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Landscapes
- Conductive Materials (AREA)
Abstract
The invention discloses an electric heating slurry and a preparation method thereof, and relates to the technical field of slurries. The invention provides an electric heating slurry which comprises the following components in parts by weight: 10-30 parts of a first binding phase, 15-40 parts of a second binding phase, 0.2-2 parts of a coupling agent, 3-15 parts of a dispersing agent, 0.2-2 parts of a leveling agent, 10-30 parts of graphene powder and 20-45 parts of spherical graphite powder; the first binding phase is a mixture of a thermosetting resin and a latent curing agent, and the weight ratio of the thermosetting resin to the latent curing agent is that the thermosetting resin: latent curative =100: (2-20); the second binding phase is a mixture of thermoplastic resin and a solvent, and the weight percentage of the thermoplastic resin in the second binding phase is 10-40%. According to the electric heating slurry prepared by the invention, the graphene is matched with the spherical graphite to form a conductive network with a synergistic effect, so that the solid content of the electric heating slurry is increased, and the resistance and film forming defects of the slurry after solidification are reduced.
Description
Technical Field
The invention relates to the technical field of slurry, in particular to electric heating slurry and a preparation method thereof.
Background
The electrothermal slurry is a viscous fluid formed by uniformly mixing and dispersing conductive filler, a binding phase, a solvent, an auxiliary agent and the like, and can form a film layer with an electrothermal conversion function on a base material through drying and curing in the process modes of screen printing, gravure printing, blade coating, coating and the like. The traditional conductive filler comprises metal powder such as silver, copper, nickel and the like. Among them, silver powder has a problem of high cost although it is excellent in conductivity and stable in chemical properties. Copper powder and nickel powder have good conductivity but poor oxidation resistance. Meanwhile, the problems of large density and high unit dosage of the electrothermal slurry prepared from the metal powder generally exist. The electrothermal carbon paste has good comprehensive performance, stable resistance after curing and high cost performance, and has been developed and applied to a certain extent at present.
The graphene is a novel two-dimensional carbon nano material consisting of single-layer carbon atoms, has excellent performances of electric conduction, heat conduction, corrosion resistance, light weight and the like, and has the room-temperature carrier mobility of 15000cm 2 V.s, thermal conductivity as high as 5300W/(m.K), theoretical electric conductivity as high as 10 8 S/m, can generate far infrared light with the wavelength of 6-16 mu m after being electrified and heated, has the wavelength similar to the wavelength of infrared light emitted by a human body, can be better absorbed by the human body to generate a physical therapy health-care effect, and is ideal carbon conductive filler. The graphene can be matched with other carbon-based conductive fillers such as carbon nanotubes, conductive carbon black, graphite and the like to form a point-line-plane space synergistic effect, so that the conductivity of the electric heating slurry is enhanced. For example, chinese patent CN 108305704A discloses a highly conductive carbon slurry in which graphene and conductive carbon black are used as conductive fillers and aqueous resin is used as a binder, chinese patent CN 104517664B discloses a carbon-based electrothermal slurry based on graphene clusters, which uses graphene clusters or a combination of graphene clusters and other carbon materials as conductive fillers, and chinese patent CN 107682943B discloses a multifunctional graphene electrothermal slurry, which uses physically-modified or chemically-modified graphene as conductive fillers. To be provided withThe electrothermal slurry prepared above all showed good conductivity. However, the graphene, the conductive carbon black and the carbon nanotube have large specific surface area and oil absorption, poor dispersibility, and low solid content of the prepared electric heating slurry, which causes a problem of slow curing speed. Meanwhile, the shrinkage degree of the film layer is large during curing, the film forming property is poor, the risk of causing the penetration of a dry film, pinholes and even cracking is caused, and potential safety hazards such as ignition, burning and the like are caused by local hot spots generated after power-on heating, so that the method becomes an important reason for limiting the practical large-scale use of the electrothermal slurry. The graphite has relatively low specific surface area and good dispersibility, but the expanded graphite and the flake graphite which are widely used at present are flaky powder. When the slurry is cured, the slurry tends to be arranged in the direction of the substrate in parallel and flatly, so that the volatilization of a solvent in the film layer is hindered, the curing speed and the curing completeness of the electrothermal slurry are influenced, and the expected performance is difficult to show.
In conclusion, the application of graphene in the electric heating slurry is further realized, the dispersion effect and the solid content of the slurry are improved, the film forming defect is reduced, the curing efficiency of the slurry is improved, and the key problem to be solved in the field of the electric heating slurry is solved urgently.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide the electric heating slurry and the preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: an electric heating slurry comprises the following components in parts by weight: 10-30 parts of a first binder phase, 15-40 parts of a second binder phase, 0.2-2 parts of a coupling agent, 3-15 parts of a dispersing agent, 0.2-2 parts of a leveling agent, 10-30 parts of graphene powder and 20-45 parts of spherical graphite powder; the first binding phase is a mixture of a thermosetting resin and a latent curing agent, and the weight ratio of the thermosetting resin to the latent curing agent is that the thermosetting resin: latent curative =100: (2-20); the second binding phase is a mixture of thermoplastic resin and a solvent, and the weight percentage of the thermoplastic resin in the second binding phase is 10-40%.
The first binding phase is a mixture of thermosetting resin and a latent curing agent, the thermosetting resin is chemically crosslinked by the curing agent to form a rigid net structure, and the composite material has the advantages of high strength, aging resistance, high dimensional stability, strong adhesive force and the like, and can be used as a basic material for forming an electrothermal slurry film layer. The latent curing agent can form a single-component system with normal-temperature storage stability with thermosetting resin, and the latent curing agent can quickly react to achieve the purpose of crosslinking and curing when being heated. The second binding phase is prepared by uniformly dissolving thermoplastic resin in a solvent. The thermoplastic resin is a linear polymer or a polymer with a small amount of branched chains, has good flexibility, and can effectively improve the brittleness of the thermosetting resin generated by crosslinking and curing. The thermoplastic resin is dissolved in the solvent to form stable fluid with certain viscosity, which is beneficial to leveling the slurry and improving the film forming effect.
The spherical graphite powder used in the invention is dispersed among the flaky graphene powder in a slurry system, plays a role in blocking the agglomeration of the graphene powder, and constructs a conductive network with a synergistic effect with the graphene powder, so that the slurry has better conductivity and film forming quality.
Preferably, the electrothermal slurry comprises the following components in parts by weight: 15-25 parts of first binder phase, 18-35 parts of second binder phase, 0.5-1.5 parts of coupling agent, 5-10 parts of dispersing agent, 0.5-1.5 parts of flatting agent, 15-25 parts of graphene powder and 25-38 parts of spherical graphite powder.
Preferably, the graphene powder is a mixture of graphene powder a and graphene powder B, and the weight ratio of graphene powder a to graphene powder B is graphene powder a: graphene powder B = (2-8): 1; wherein the number of layers of the graphene powder A is 10-30, the average sheet diameter of the graphene powder A is 8-20 mu m, the number of layers of the graphene powder B is 3-10, and the average sheet diameter of the graphene powder B is 0.5-3 mu m; the average grain diameter of the spherical graphite powder is 4-15 μm.
Through a great deal of research, the inventor finds that the matching of graphene powder with different sheet diameters can fill gaps with small sheet diameters, and a conductive network is formed better. When the particle size of the spherical graphite powder is smaller than 4 μm, the agglomeration tendency of the graphene powder cannot be effectively blocked, and the conductivity and the film forming quality of the slurry after curing are poor. When the particle size of the spherical graphite powder is larger than 15 μm, the ordered stacking of graphene sheets in the slurry curing process is excessively hindered, the compactness of a film layer is damaged, and the conductivity and the film forming quality of the slurry are also not facilitated.
More preferably, the weight ratio of the graphene powder a to the graphene powder B is graphene powder a: graphene powder B = (3.5-6): 1.
through a great deal of research, the inventors find that when the weight ratio of the graphene powder a to the graphene powder B is within the above range, the prepared electrothermal slurry has better performance.
Preferably, the electrothermal slurry is at least one of the following (a) to (g):
(a) The thermosetting resin is liquid epoxy resin; preferably, the liquid epoxy resin is at least one of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, brominated bisphenol a epoxy resin, bisphenol F epoxy resin and novolac epoxy resin;
(b) The latent curing agent is an imidazole curing agent; preferably, the imidazole curing agent is at least one of 2-ethyl-4-methylimidazole (2E 4 MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E 4 MZ-CN), 2-undecylimidazole (C11Z), 1-cyanoethyl-2-undecylimidazole (C11Z-CN), 1-cyanoethyl-2-undecylimidazole trimellitate (C11Z-CNs), 1-benzyl-2-phenylimidazole (1B 2 PZ);
(c) The thermoplastic resin is at least one of saturated polyester resin, saturated polyurethane resin, polyacrylic resin, polyvinyl butyral and ethylene-vinyl acetate copolymer;
(d) The solvent is at least one of ketone solvent, ether solvent and ester solvent;
(e) The coupling agent is at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconate coupling agent and bimetallic coupling agent;
(f) The dispersant is at least one of amine salt type dispersant, block copolymer type dispersant, acrylate type dispersant, hyperbranched polyester type dispersant and polycarboxylic acid ester type dispersant;
(g) The leveling agent is at least one of an organic silicon type leveling agent, an acrylic acid type leveling agent and a fluorocarbon type leveling agent.
Preferably, the electrothermal slurry is at least one of the following (a) to (f):
(a) The liquid epoxy resin is at least one of bisphenol A epoxy resin E44, bisphenol A epoxy resin E51, hydrogenated bisphenol A epoxy resin 1510, bisphenol F epoxy resin 862, novolac epoxy resin F44 and novolac epoxy resin F51;
(b) The thermoplastic resin is saturated polyester resin, and the relative molecular weight is 15000-35000;
(c) The solvent is at least one of cyclohexanone, diisobutyl ketone, isophorone, ethylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate and DBE
(d) The coupling agent is at least one of a silane coupling agent KH171, a silane coupling agent KH550, a silane coupling agent KH560, a silane coupling agent KH570, a silane coupling agent KH792, a titanate coupling agent KR-TTS, a titanate coupling agent KR-38S and an aluminate coupling agent LD-B-1;
(e) The dispersant is at least one of DISPERBYK-110, DISPERBYK-163, DISPERBYK-180, TEGO Dispers 610 and TEGO Dispers 671;
(f) The leveling agent is at least one of BYK-306, BYK-333, BYK-358N, EFKA-3740 and EFKA-3777.
In addition, the invention provides a preparation method of the electric heating slurry, which comprises the following steps:
(1) Preparing a first binding phase; weighing thermosetting resin and latent curing agent according to the weight part ratio, and uniformly mixing to obtain a first bonding phase;
(2) Preparing a second binder phase; weighing thermoplastic resin and a solvent according to the weight percentage, heating for dissolving, and cooling to obtain a second binding phase;
(3) Weighing a first bonding phase, a second bonding phase, a coupling agent, a dispersing agent and a flatting agent according to the weight part ratio, and uniformly mixing to obtain a slurry matrix;
(4) And mixing and grinding the slurry matrix, the graphene powder and the spherical graphite powder, filtering and defoaming in vacuum to obtain the electrothermal slurry.
Preferably, in the step (1), the rotation speed of mixing is 500-1500rpm, and the mixing time is 0.5-2h; in the step (2), the heating temperature is 50-90 ℃, the heating time is 3-8h, and the temperature is cooled to the room temperature; in the step (3), the mixing speed is 500-1500rpm, and the mixing time is 0.5-2h.
Preferably, in the step (4), grinding is performed twice, and the first grinding is performed by mixing and grinding the slurry matrix and the graphene powder to obtain a mixture; the second grinding is to mix and grind the mixture and the spherical graphite powder; filtering with 50-200 mesh gauze; preferably, the rotation speed of the first grinding is 2000-3000rpm, the time of the first grinding is 3-6h, the rotation speed of the second grinding is 1500-2500rpm, and the time of the first grinding is 1-2.5h.
Further, the invention provides application of the electrothermal slurry in the field.
Compared with the prior art, the invention has the beneficial effects that: (1) According to the electric heating slurry prepared by the invention, the graphene and the spherical graphite are matched to form a conductive network with a synergistic effect, the spherical graphite blocks the agglomeration tendency of the graphene, the conductive filler is easy to disperse in the slurry matrix, the solid content of the electric heating slurry is improved, and the resistance and film forming defects of the slurry after solidification are reduced. Meanwhile, the spherical graphite provides more volatilization channels for the solvent, so that the blockage of the flaky powder to the volatilization of the solvent is reduced, and the curing efficiency of the slurry is greatly improved. (2) The method has simple and convenient operation steps, does not need complex process flow, improves the stability of the product, and is suitable for industrial mass production.
Detailed Description
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available unless otherwise specified.
The materials used in the examples and comparative examples are now described below, but are not limited to these materials:
graphene powder A1: the number of layers is 10-30, and the average sheet diameter is 12 mu m;
graphene powder B1: the number of layers is 3-10, and the average sheet diameter is 1.5 mu m;
spherical graphite powder 1: the average particle size is 5 μm;
spherical graphite powder 2: the average particle size is 10 μm;
spherical graphite powder 3: the average particle size is 15 μm;
spherical graphite powder 4: the average particle size was 2.5 μm;
spherical graphite powder 5: the average particle size was 17 μm;
examples 1 to 8 and comparative examples 1 to 3
Example 1
The invention relates to an electric heating paste, and a preparation method of the electric heating paste comprises the following steps:
(1) Preparing a first binding phase; weighing thermosetting resin (100 parts, bisphenol A type epoxy resin E51) and latent curing agent (10 parts, imidazole curing agent 2E4 MZ) according to the weight part ratio, and uniformly mixing to obtain a first binding phase; the mixing speed is 800rpm, and the mixing time is 1h; thermosetting resin: latent curative =100:10;
(2) Preparing a second binder phase; weighing thermoplastic resin (25% of saturated polyester resin, relative molecular weight 22000) and solvent (25% of cyclohexanone and 50% of ethylene glycol butyl ether acetate) according to weight percentage, heating for dissolving, and cooling to obtain a second binding phase; heating at 60 deg.C for 5h, and cooling to room temperature;
(3) Weighing a first binding phase (20 parts), a second binding phase (20 parts), a coupling agent (0.5 part of a silane coupling agent KH560, 0.3 part of a titanate coupling agent KR-TTS), a dispersing agent (7 parts of a dispersant DISPERBYK-180) and a flatting agent (1 part of a flatting agent BYK-306) according to the weight part ratio, and uniformly mixing to obtain a slurry matrix; the mixing speed is 1200rpm, and the mixing time is 1h;
(4) Mixing and grinding the slurry substrate prepared in the step (3), graphene powder (13.5 parts of graphene powder A1 and 3.2 parts of graphene powder B1) and spherical graphite powder (34.5 parts of spherical graphite powder 1) in two times, wherein the first grinding is to mix and grind the slurry substrate and the graphene powder, the first grinding speed is 2500rpm, and the first grinding time is 5 hours to obtain a mixture; the second grinding is to mix and grind the mixture and the spherical graphite powder, the rotation speed of the second grinding is 1800rpm, and the time of the first grinding is 1.5h; filtering by adopting a gauze with 150 meshes, and obtaining the electric heating slurry after vacuum defoamation.
Example 2
The invention relates to an electric heating paste, and a preparation method of the electric heating paste comprises the following steps:
(1) Preparing a first binding phase; weighing thermosetting resin (30 parts of hydrogenated bisphenol A epoxy resin 1510 and 70 parts of bisphenol F epoxy resin 862) and a latent curing agent (5 parts of imidazole curing agent 2E4 MZ-CN) according to the weight part ratio, and uniformly mixing to obtain a first bonding phase; the mixing speed is 700rpm, and the mixing time is 1h; thermosetting resin: latent curing agent =100:5;
(2) Preparing a second binder phase; weighing thermoplastic resin (22% of saturated polyester resin relative molecular weight 30000) and solvent (36% of isophorone and 42% of dipropylene glycol methyl ether) according to weight percentage, heating for dissolving, and cooling to obtain a second binding phase; heating at 80 deg.C for 4h, and cooling to room temperature;
(3) Weighing 18 parts of a first bonding phase, 25 parts of a second bonding phase, 0.7 part of a silane coupling agent KH570, 0.3 part of an aluminate coupling agent LD-B-1, 8 parts of a dispersant DISPERBYK-110 and 0.5 part of a leveling agent BYK-358N according to the weight parts, and uniformly mixing to obtain a slurry matrix; the mixing speed is 1000rpm, and the mixing time is 1h;
(4) Mixing and grinding the slurry substrate prepared in the step (3), graphene powder (16 parts of graphene powder A1 and 3 parts of graphene powder B1) and spherical graphite powder (28.5 parts of spherical graphite powder 1) in two times, wherein the first grinding is to mix and grind the slurry substrate and the graphene powder, the first grinding rotation speed is 2300rpm, and the first grinding time is 4.5 hours to obtain a mixture; the second grinding is to mix and grind the mixture and the spherical graphite powder, the rotation speed of the second grinding is 2000rpm, and the time of the first grinding is 2 hours; filtering by adopting a gauze with 150 meshes, and obtaining the electric heating slurry after vacuum defoaming.
Example 3
The invention relates to an electric heating paste, and a preparation method of the electric heating paste comprises the following steps:
(1) Preparing a first binder phase; weighing thermosetting resin (80 parts of bisphenol A epoxy resin E51 and 20 parts of novolac epoxy resin F51) and latent curing agent (7 parts of imidazole curing agent 1B2 PZ) according to the weight part ratio, and uniformly mixing to obtain a first bonding phase; the mixing speed is 1000rpm, and the mixing time is 1.5h; thermosetting resin: latent curing agent =100:7;
(2) Preparing a second binder phase; weighing thermoplastic resin (27% relative molecular weight 18000 of saturated polyester resin) and solvent (32% diethylene glycol ethyl ether acetate and 41% DBE) by weight percentage, heating for dissolving, and cooling to obtain a second binder phase; heating at 80 deg.C for 6h, and cooling to room temperature;
(3) Weighing a first bonding phase (20 parts), a second bonding phase (26 parts), a coupling agent (1 part of a silane coupling agent KH 171), a dispersing agent (6 parts of a TEGO Dispers 671), a leveling agent (0.7 part of EFKA-3740 and 0.5 part of EFKA-3777) according to the weight part ratio, and uniformly mixing to obtain a slurry matrix; the mixing speed is 1000rpm, and the mixing time is 1.5h;
(4) Mixing and grinding the slurry substrate prepared in the step (3), graphene powder (14.2 parts of graphene powder A1 and 3.7 parts of graphene powder B1) and spherical graphite powder (27.9 parts of spherical graphite powder 1) in two times, wherein the first grinding is to mix and grind the slurry substrate and the graphene powder, the first grinding rotation speed is 2700rpm, and the first grinding time is 5.5 hours to obtain a mixture; the second grinding is to mix and grind the mixture and the spherical graphite powder, the rotation speed of the second grinding is 1800rpm, and the time of the first grinding is 1.5h; filtering by adopting a gauze with 150 meshes, and obtaining the electric heating slurry after vacuum defoaming.
Example 4
Compared with the example 1, only the selection of the spherical graphite powder in the step (4) is different, 34.5 parts of the spherical graphite powder 2 is selected in the example 4, and the rest components, the parts by weight and the preparation method are completely the same as those in the example 1.
Example 5
Compared with the example 1, only the selection of the spherical graphite powder in the step (4) is different, 34.5 parts of the spherical graphite powder 3 is selected in the example 5, and the rest components, the parts by weight and the preparation method are completely the same as those in the example 1.
Example 6
Compared with the example 1, the selection of the weight parts of the graphene powder in the step (4) is different, the selection of the example 6 is 12 parts of the graphene powder A1,4.7 parts of the graphene powder B1, and the rest components, the weight parts and the preparation method are completely the same as those of the example 1.
Example 7
Compared with the embodiment 1, the selection of the weight parts of the graphene powder in the step (4) is different, the embodiment 7 selects 14.7 parts of the graphene powder A1 and 2 parts of the graphene powder B1, and the rest components, the weight parts and the preparation method are completely the same as those of the embodiment 1.
Example 8
Compared with the example 1, the selection of the weight parts of the graphene powder in the step (4) is different, the selection of the example 8 is 14 parts of the graphene powder A1, and the selection of the example 8 is 2.7 parts of the graphene powder B1, and the rest components, the weight parts and the preparation method are completely the same as those of the example 1.
Comparative example 1
Compared with the embodiment 1, only in the step (4), 30 parts of conductive carbon black with the particle size of 30nm and 4.5 parts of carbon nano tube powder with the length range of 5-20 mu m are selected to replace the spherical graphite powder, and in the preparation step of the comparative example, 11 parts of cyclohexanone and 22 parts of ethylene glycol butyl ether acetate are additionally added to adjust the viscosity so as to adapt to the printing process. The rest components, the parts by weight and the preparation method are completely the same as the example 1.
Comparative example 2
Compared with the example 1, only the selection of the spherical graphite powder in the step (4) is different, 34.5 parts of the spherical graphite powder 4 is selected in the example 4, and the rest components, the parts by weight and the preparation method are completely the same as those in the example 1.
Comparative example 3
Compared with the example 1, only the selection of the spherical graphite powder in the step (4) is different, 34.5 parts of the spherical graphite powder 5 is selected in the example 4, and the rest components, the parts by weight and the preparation method are completely the same as those in the example 1.
Performance testing
The testing process comprises the following steps: the electrothermal slurries prepared in examples and comparative examples were separately sampled and printed as 10cm x 10cm-sized films using a 100-mesh screen having a thickness of 25 μm. And respectively testing the viscosity, the curing efficiency, the solid content, the adhesive force and the film forming quality. The detection method comprises the following steps:
viscosity: this was measured by Brookfield viscometer under CPA-51Z spindle, 100rpm,25 ℃.
Curing efficiency: the curing temperature is set according to the specification, and the sheet resistance of the sizing agent is changed under different curing time. The sheet resistance of the electric heating pastes were measured at curing times of 15min, 30min, 45min, and 60min, respectively, and the curing temperatures of examples 1-2, examples 4-8, and comparative examples 1-3 were defined as 120 ℃ and the curing temperature of example 3 was defined as 130 ℃ depending on the solvent system. The square resistance value is measured by a four-probe tester.
Solid content: obtained by calculating the ratio of the weight of the dry film after curing at 150 ℃ for 90min to the weight of the wet film before curing;
adhesion force: testing is carried out according to GB/T9286-2021 'test for drawing squares of colored paint and varnish';
film forming quality: and (4) observing whether the film layer has film forming defects such as cracks, air permeability, pinholes and the like after the slurry is cured by using a backlight source and a microscope to represent.
The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the graphene/spherical graphite composite electric heating slurry provided by the invention has the advantages of low resistance, moderate viscosity, high adhesive force and the like, achieves lower sheet resistance at 15min, has no various defects on a cured film layer, and has the characteristics of high curing speed and high film-forming quality. Compared with the existing carbon-based electric heating slurry, the graphene/spherical graphite composite electric heating slurry has obvious advantages in self performance and process adaptability, can effectively prevent local hot spots of a film layer, and has important significance in improving the safety and quality of an electric heating product.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The electric heating slurry is characterized by comprising the following components in parts by weight: 10-30 parts of a first binding phase, 15-40 parts of a second binding phase, 0.2-2 parts of a coupling agent, 3-15 parts of a dispersing agent, 0.2-2 parts of a leveling agent, 10-30 parts of graphene powder and 20-45 parts of spherical graphite powder; the first binding phase is a mixture of thermosetting resin and a latent curing agent, and the weight ratio of the thermosetting resin to the latent curing agent is that the thermosetting resin: latent curing agent =100: (2-20); the second binding phase is a mixture of thermoplastic resin and a solvent, and the weight percentage of the thermoplastic resin in the second binding phase is 10-40%.
2. The electrothermal slurry of claim 1, comprising the following components in parts by weight: 15-25 parts of first binder phase, 18-35 parts of second binder phase, 0.5-1.5 parts of coupling agent, 5-10 parts of dispersing agent, 0.5-1.5 parts of flatting agent, 15-25 parts of graphene powder and 25-38 parts of spherical graphite powder.
3. The electrothermal slurry of claim 1 or 2, wherein the graphene powder is a mixture of graphene powder A and graphene powder B, and the weight ratio of graphene powder A to graphene powder B is graphene powder A: graphene powder B = (2-8): 1; wherein the number of layers of the graphene powder A is 10-30, the average sheet diameter of the graphene powder A is 8-20 mu m, the number of layers of the graphene powder B is 3-10, and the average sheet diameter of the graphene powder B is 0.5-3 mu m; the average grain diameter of the spherical graphite powder is 4-15 μm.
4. The electrothermal slurry of claim 3, wherein the weight ratio of the graphene powder A to the graphene powder B is graphene powder A: graphene powder B = (3.5-6): 1.
5. the electrothermal slurry according to claim 1, wherein at least one of the following (a) to (g):
(a) The thermosetting resin is liquid epoxy resin; preferably, the liquid epoxy resin is at least one of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, brominated bisphenol a epoxy resin, bisphenol F epoxy resin and novolac epoxy resin;
(b) The latent curing agent is an imidazole curing agent; preferably, the imidazole curing agent is at least one of 2-ethyl-4-methylimidazole (2E 4 MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E 4 MZ-CN), 2-undecylimidazole (C11Z), 1-cyanoethyl-2-undecylimidazole (C11Z-CN), 1-cyanoethyl-2-undecylimidazole trimellitate (C11Z-CNs), 1-benzyl-2-phenylimidazole (1B 2 PZ);
(c) The thermoplastic resin is at least one of saturated polyester resin, saturated polyurethane resin, polyacrylic resin, polyvinyl butyral and ethylene-vinyl acetate copolymer;
(d) The solvent is at least one of ketone solvent, ether solvent and ester solvent;
(e) The coupling agent is at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconate coupling agent and bimetallic coupling agent;
(f) The dispersant is at least one of amine salt type dispersant, block copolymer type dispersant, acrylate type dispersant, hyperbranched polyester type dispersant and polycarboxylic acid ester type dispersant;
(g) The flatting agent is at least one of an organic silicon type flatting agent, an acrylic type flatting agent and a fluorocarbon type flatting agent.
6. The electrically heated paste according to claim 5, wherein at least one of the following (a) to (f):
(a) The liquid epoxy resin is at least one of bisphenol A epoxy resin E44, bisphenol A epoxy resin E51, hydrogenated bisphenol A epoxy resin 1510, bisphenol F epoxy resin 862, novolac epoxy resin F44 and novolac epoxy resin F51;
(b) The thermoplastic resin is saturated polyester resin, and the relative molecular weight is 15000-35000;
(c) The solvent is at least one of cyclohexanone, diisobutyl ketone, isophorone, ethylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate and DBE
(d) The coupling agent is at least one of a silane coupling agent KH171, a silane coupling agent KH550, a silane coupling agent KH560, a silane coupling agent KH570, a silane coupling agent KH792, a titanate coupling agent KR-TTS, a titanate coupling agent KR-38S and an aluminate coupling agent LD-B-1;
(e) The dispersant is at least one of DISPERBYK-110, DISPERBYK-163, DISPERBYK-180, TEGO Dispers 610 and TEGO Dispers 671;
(f) The leveling agent is at least one of BYK-306, BYK-333, BYK-358N, EFKA-3740 and EFKA-3777.
7. A method for preparing an electrically heated paste according to any of claims 1 to 6, comprising the steps of:
(1) Preparing a first binding phase; weighing thermosetting resin and latent curing agent according to the weight part ratio, and uniformly mixing to obtain a first bonding phase;
(2) Preparing a second binder phase; weighing thermoplastic resin and a solvent according to the weight percentage, heating for dissolving, and cooling to obtain a second binding phase;
(3) Weighing a first bonding phase, a second bonding phase, a coupling agent, a dispersing agent and a flatting agent according to the weight part ratio, and uniformly mixing to obtain a slurry matrix;
(4) And mixing and grinding the slurry matrix, the graphene powder and the spherical graphite powder, filtering and defoaming in vacuum to obtain the electrothermal slurry.
8. The method for preparing electrothermal slurry according to claim 7, wherein in the step (1), the rotation speed of mixing is 500-1500rpm, and the mixing time is 0.5-2h; in the step (2), the heating temperature is 50-90 ℃, the heating time is 3-8h, and the temperature is cooled to room temperature; in the step (3), the mixing speed is 500-1500rpm, and the mixing time is 0.5-2h.
9. The method for preparing electrothermal slurry according to claim 7, wherein in the step (4), grinding is performed twice, and the first grinding is performed by mixing and grinding the slurry matrix and the graphene powder to obtain a mixture; the second grinding is to mix and grind the mixture and the spherical graphite powder; filtering with 50-200 mesh gauze; preferably, the rotation speed of the first grinding is 2000-3000rpm, the time of the first grinding is 3-6h, the rotation speed of the second grinding is 1500-2500rpm, and the time of the first grinding is 1-2.5h.
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