CN115499958A - High-temperature-resistant electric heating slurry and preparation method thereof - Google Patents
High-temperature-resistant electric heating slurry and preparation method thereof Download PDFInfo
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- 239000002002 slurry Substances 0.000 title claims abstract description 66
- 238000005485 electric heating Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000007613 slurry method Methods 0.000 title description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000006258 conductive agent Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- 229920000728 polyester Polymers 0.000 claims abstract description 28
- 229920001225 polyester resin Polymers 0.000 claims abstract description 23
- 239000004645 polyester resin Substances 0.000 claims abstract description 23
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 229920002545 silicone oil Polymers 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- -1 polydimethylsiloxane Polymers 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 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 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 150000007974 melamines Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 150000001721 carbon Chemical class 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 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 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000013021 overheating Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000005562 fading Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/60—Heating arrangements wherein the heating current flows through granular powdered or fluid material, e.g. for salt-bath furnace, electrolytic heating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-temperature-resistant electric heating slurry and a preparation method thereof, belonging to the field of functional slurry, and comprising 10-30 parts of organic silicon modified polyester, 5-50 parts of carbon material conductive agent, 5-40 parts of solvent, 1-5 parts of auxiliary agent and 3-20 parts of curing agent. According to the preparation method, the hydroxyl-terminated silicone oil and the hydroxyl saturated polyester resin are combined into a block polymer through chemical bonds, and the curing agent participates in a crosslinking reaction in the slurry, so that the temperature resistance of the formed dry film can be remarkably improved; the carbon-based material conductive agents can be tightly arranged when the bonding resin is filled, so that a high-efficiency conductive channel is formed, the resistance of a dry film formed by the slurry is low, the conductive heating performance is excellent, the excellent heat conduction performance is improved by the ordered arrangement of the carbon-based material conductive agents, the local temperature overheating energy is quickly and uniformly diffused by the heat conduction channel when the carbon-based material conductive agents are electrified and heated, and the service life is prolonged.
Description
Technical Field
The invention relates to functional slurry, in particular to high-temperature-resistant electrothermal slurry and a preparation method thereof.
Background
The electrothermal slurry is also called as conductive heating slurry, and the novel functional slurry which generates far infrared rays through molecule and atom collision and vibration under the electrified condition after film forming generates heat has wide application in the fields of industrial heat preservation, home heating, intelligent wearing and the like and has excellent market prospect.
At present, most of the basic adhesive components of the electric heating slurry are common conventional resins, and the electric heating slurry is easy to age and has a defect in temperature resistance. The prepared electric heating slurry is only suitable for medium-low temperature heating scenes, is easy to yellow, crack and pulverize under the long-term high-temperature heating use condition, and limits the use range of the electric heating slurry. Part of factory pure organic silicon resin is used as a bonding component, and metal powder is used as a conductive agent to prepare the temperature-resistant conductive slurry, but the pure organic silicon resin has poor mechanical strength, adhesive force and medium resistance, and can only meet few application scenes; in addition, the metal powder conductive agent is easy to oxidize, expensive and difficult to popularize in the market.
So far, the research of high temperature resistant electric heating slurry mainly stays in the selection and the proportion of the binding resin and the conductive agent, and the research technology of the molecular structure design of the binding resin and the synergistic temperature resistant effect of the conductive agent is rarely reported. In particular to a brand new process for preparing high temperature resistant electric heating slurry by using organic silicon modified polyester as binder resin and carbon series materials with special structures as conductive agents.
Disclosure of Invention
Based on the above, in order to solve the problems that the electrothermal slurry in the prior art is easy to yellow, crack and pulverize after being heated at high temperature for a long time, the invention provides a high-temperature resistant electrothermal slurry, which has the following specific technical scheme:
the high-temperature-resistant electric heating slurry comprises the following preparation raw materials in parts by mass:
10-30 parts of organic silicon modified polyester, 5-50 parts of carbon material conductive agent, 5-40 parts of solvent, 1-5 parts of auxiliary agent and 3-20 parts of curing agent;
and the organic silicon modified polyester is an organic silicon-saturated polyester block copolymer, and the synthesis reaction formula of the organic silicon-saturated polyester block copolymer is as follows:
the method comprises the following steps:
step two:
Further, the carbon-based material conductive agent is one or a mixture of two of flake conductive graphite, spherical conductive carbon black, tubular carbon nanotubes, single-layer graphene and multi-layer graphene.
Further, the solvent is one or more of DMF, NMP, PMA, PM, DPM, BCS, cyclohexane, dichloromethane and xylene.
Further, the auxiliary agent is one or more of a flatting agent, a dispersing agent, a defoaming agent and a wetting agent.
Further, the curing agent is one of trimethylol melamine, hexamethylol melamine, methylated melamine and butylated melamine.
In addition, the application provides a preparation method of the high-temperature-resistant electric heating slurry, which comprises the following steps:
adding hydroxyl-terminated silicone oil and isophorone diisocyanate into a reaction kettle, starting stirring, dehydrating for 30min at 70 ℃ under a vacuum condition, then dropwise adding a diluted catalyst into the reaction kettle under the protection of nitrogen, reacting for 2h to 4h, then adding hydroxyl saturated polyester into the reaction kettle, heating to 80-90 ℃ after uniformly stirring, reacting for 3h to 4h, and obtaining an organic silicon modified polyester resin, wherein the system is a transparent solution;
adding the organic silicon modified polyester resin, the carbon series material conductive agent, the solvent and the auxiliary agent into a reactor, adjusting a disc type stirrer to 200r/min-300r/min, dispersing for 30min-60min, increasing the stirring speed to 1000r/min-5000r/min, and stirring for 2h-4h to obtain a mixture A;
grinding the mixture A, adjusting the distance between the roller shafts, ensuring that the fineness of the slurry reaches below 10um after passing through a machine 1~2 times, filtering and discharging, then adjusting the viscosity to 3000 cps-8000 cps, adding a curing agent, and fully and uniformly stirring to obtain the high-temperature resistant electric heating slurry.
Further, the hydroxyl-terminated silicone oil is hydroxyl-terminated linear polydimethylsiloxane, the molecular weight is 500 to 10000, and the hydroxyl content is 5 to 15 percent.
Further, according to the molar ratio, -OH: -NCO =1:2.
Further, the catalyst is one or a mixture of two of organic tin, organic bismuth and stannous octoate.
Further, the hydroxyl value of the hydroxyl saturated polyester is 25 mg KOH/g to 50 mg KOH/g, and the glass transition temperature is 40 ℃ to 80 ℃.
In the scheme, hydroxyl-terminated silicone oil and hydroxyl saturated polyester resin are combined into a block polymer through chemical bonds, the temperature resistance is improved by an organic silicon chain segment, and the flexibility, the corrosion resistance and the weather resistance are improved by a saturated polyester chain segment; in addition, the components interact with each other, the curing agent participates in a crosslinking reaction in the slurry, the temperature resistance of the slurry can be obviously improved, the carbon-series material conductive agents can be tightly arranged when the bonding resin is filled, an efficient conductive channel is formed, the dry film resistance formed by the slurry is low, the conductive heating performance is excellent, the excellent heat conduction performance is improved by the ordered arrangement of the carbon-series material conductive agents, the over-heat energy of the local temperature is rapidly and uniformly diffused by the heat conduction channel when the power-on heating work is carried out, and the service life is further prolonged.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The high-temperature-resistant electric heating slurry in one embodiment of the invention comprises the following preparation raw materials in parts by mass:
10-30 parts of organic silicon modified polyester, 5-50 parts of carbon material conductive agent, 5-40 parts of solvent, 1-5 parts of auxiliary agent and 3-20 parts of curing agent;
and the organic silicon modified polyester is an organic silicon-saturated polyester block copolymer, and the synthesis reaction formula of the organic silicon-saturated polyester block copolymer is as follows:
the method comprises the following steps:
step two:
wherein R is 1 is-CH 3 , R 2 is-C x H 2x+1 Or an aliphatic ring group, and m, n and x are natural integers.
In one embodiment, the carbon-based material conductive agent is one or a mixture of two of flake conductive graphite, spherical conductive carbon black, tubular carbon nanotubes, single-layer graphene and multi-layer graphene.
In one embodiment, the solvent is one or more of DMF, NMP, PMA, PM, DPM, BCS, cyclohexane, dichloromethane, xylene.
In one embodiment, the auxiliary agent is one or more of a leveling agent, a dispersing agent, a defoaming agent and a wetting agent.
In one embodiment, the leveling agent is one or a mixture of two of aralkyl modified silicone oil, polyester modified silicone oil, polyether modified silicone oil, acrylic modified polysiloxane and fluorine modified acrylate.
In one embodiment, the dispersant is one or more of comb polyurethane, phenolic derivatives, polyacrylic acid sodium salt, amide salt compounds and alkyl polyoxyethylene ether ammonium phosphate salt.
The defoaming agent is an organic silicon defoaming agent.
In one embodiment, the wetting agent is one or more of dike 245, dike 270, dike 4000, dike 4100, and dike 346.
In one embodiment, the curing agent is one of trimethylolmelamine, hexamethylolmelamine, methylated melamine, and butylated melamine.
In one embodiment, the reaction formula of the curing agent participating in the reaction is as follows:
wherein, R thereof 3 is-CH 2 OH、-CH 2 OC 4 H 9 、-CH 2 OCH 3 ，R 4 is-H, -CH 2 OH、-CH 2 OC 4 H 9 、-CH 2 OCH 3 ；R 5 Is a group formed after the dehydration reaction of a reactant, and m and n are natural integers.
In addition, the application provides a preparation method of the high-temperature-resistant electric heating slurry, which comprises the following steps:
adding hydroxyl-terminated silicone oil and isophorone diisocyanate into a reaction kettle, starting stirring, dehydrating for 30min at 70 ℃ under a vacuum condition, then dropwise adding a diluted catalyst into the reaction kettle under the protection of nitrogen, reacting for 2h to 4h, then adding hydroxyl saturated polyester into the reaction kettle, heating to 80-90 ℃ after uniformly stirring, reacting for 3h to 4h, and obtaining an organic silicon modified polyester resin, wherein the system is a transparent solution;
adding the organic silicon modified polyester resin, the carbon series material conductive agent, the solvent and the auxiliary agent into a reactor, adjusting a disc type stirrer to 200r/min-300r/min, dispersing for 30min-60min, increasing the stirring speed to 1000r/min-5000r/min, and stirring for 2h-4h to obtain a mixture A;
grinding the mixture A, adjusting the distance between the roller shafts, ensuring that the fineness of the slurry reaches below 10um after passing through a machine 1~2 times, filtering and discharging, then adjusting the viscosity to 3000 cps-8000 cps, adding a curing agent, and fully and uniformly stirring to obtain the high-temperature resistant electric heating slurry.
In one embodiment, the hydroxyl-terminated silicone oil is hydroxyl-terminated linear polydimethylsiloxane, the molecular weight is 500 to 10000, and the hydroxyl content is 5 to 15 percent.
In one embodiment, the molar ratio of-OH: -NCO =1:2.
In one embodiment, the catalyst is one or a mixture of two of organic tin, organic bismuth and stannous octoate.
In one embodiment, the hydroxyl value of the hydroxyl saturated polyester is 25 mg KOH/g to 50 mg KOH/g, the glass transition temperature is 40 ℃ to 80 ℃, and the amount of material-OH = -NCO.
According to the scheme, the hydroxyl-terminated silicone oil and the hydroxyl saturated polyester resin are combined into a block polymer through chemical bonds, the temperature resistance is improved by the organic silicon chain segment, and the flexibility, the corrosion resistance and the weather resistance are improved by the saturated polyester chain segment; in addition, the components interact with each other, the curing agent participates in a crosslinking reaction in the slurry, the temperature resistance of the slurry can be obviously improved, the carbon-series material conductive agents can be tightly arranged when the bonding resin is filled, an efficient conductive channel is formed, the dry film resistance formed by the slurry is low, the conductive heating performance is excellent, the excellent heat conduction performance is improved by the ordered arrangement of the carbon-series material conductive agents, the over-heat energy of the local temperature is rapidly and uniformly diffused by the heat conduction channel when the power-on heating work is carried out, and the service life is further prolonged.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
a preparation method of high-temperature-resistant electrothermal slurry comprises the following steps:
adding hydroxyl-terminated linear polydimethylsiloxane and isophorone diisocyanate into a reaction kettle according to a molar ratio of-OH: -NCO =1:2, starting stirring, dehydrating for 30min at 70 ℃ under a vacuum condition, dropwise adding diluted organic tin into the reaction kettle under the protection of nitrogen, reacting for 4h, adding hydroxyl saturated polyester into the reaction kettle, heating to 90 ℃ after uniformly stirring, reacting for 3h, and obtaining an organic silicon modified polyester resin, wherein the system is a transparent solution;
adding 30 parts of organic silicon modified polyester resin, 20 parts of carbon material conductive agent, 35 parts of cyclohexane and 5 parts of auxiliary agent into a reactor, adjusting a disc type stirrer to 300r/min, dispersing for 40min, increasing the stirring speed to 5000r/min, and stirring for 2h to obtain a mixture A;
grinding the mixture A, adjusting the distance between the rollers, ensuring that the fineness of the slurry is below 10um after the slurry passes through the machine for 1~2 times, filtering and discharging, then adjusting the viscosity to 3000-8000 cps, adding 10 parts of trimethylol melamine, and fully and uniformly stirring to obtain the high-temperature-resistant electric heating slurry.
Example 2:
a preparation method of high-temperature-resistant electrothermal slurry comprises the following steps:
according to a molar ratio of-OH =1:2, adding hydroxyl-terminated linear polydimethylsiloxane and isophorone diisocyanate into a reaction kettle, starting stirring, dehydrating for 30min at 70 ℃ under a vacuum condition, then dropwise adding diluted organic tin into the reaction kettle under the protection of nitrogen, reacting for 4h, then adding hydroxyl saturated polyester into the reaction kettle, heating to 90 ℃ after uniformly stirring, and reacting for 4h, wherein the system is a transparent solution, so as to obtain organic silicon modified polyester resin;
adding 31 parts of organic silicon modified polyester resin, 25 parts of carbon material conductive agent, 35 parts of cyclohexane and 1 part of auxiliary agent into a reactor, adjusting a disc type stirrer to 300r/min, dispersing for 60min, increasing the stirring speed to 2000r/min, and stirring for 3h to obtain a mixture A;
grinding the mixture A, adjusting the distance between the rollers, ensuring that the fineness of the slurry is below 10um after the slurry passes through the machine for 1~2 times, filtering and discharging, then adjusting the viscosity to 3000-8000 cps, adding 8 parts of trimethylol melamine, and fully and uniformly stirring to obtain the high-temperature-resistant electric heating slurry.
Example 3:
a preparation method of high-temperature-resistant electrothermal slurry comprises the following steps:
adding hydroxyl-terminated linear polydimethylsiloxane and isophorone diisocyanate into a reaction kettle according to a molar ratio of-OH: -NCO =1:2, starting stirring, dehydrating at 70 ℃ for 30min under a vacuum condition, dropwise adding diluted organic tin into the reaction kettle under the protection of nitrogen, reacting for 4h, adding hydroxyl saturated polyester into the reaction kettle, heating to 85 ℃ after uniformly stirring, reacting for 4h, and obtaining an organic silicon modified polyester resin, wherein the system is a transparent solution;
adding 28 parts of organic silicon modified polyester resin, 22 parts of carbon material conductive agent, 30 parts of cyclohexane and 4 parts of auxiliary agent into a reactor, adjusting a disc type stirrer to 250r/min, dispersing for 50min, increasing the stirring speed to 2500r/min, and stirring for 3h to obtain a mixture A;
grinding the mixture A, adjusting the distance between the rollers, ensuring that the fineness of the slurry is below 10 mu m after the mixture A passes through the machine for 1~2 times, filtering and discharging, then adjusting the viscosity to 3000-8000 cps, adding 16 parts of hexamethylol melamine, and fully and uniformly stirring to obtain the high-temperature resistant electric heating slurry.
Comparative example 1:
a preparation method of high-temperature-resistant electrothermal slurry comprises the following steps:
adding 28 parts of polyester resin, 22 parts of carbon material conductive agent, 30 parts of cyclohexane and 4 parts of auxiliary agent into a reactor, adjusting a disc type stirrer to 250r/min, dispersing for 50min, increasing the stirring speed to 2500r/min, and stirring for 3h to obtain a mixture A;
grinding the mixture A, adjusting the distance between the rollers, ensuring that the fineness of the slurry is below 10 mu m after the mixture A passes through the machine for 1~2 times, filtering and discharging, then adjusting the viscosity to 3000-8000 cps, adding 16 parts of hexamethylol melamine, and fully and uniformly stirring to obtain the electric heating slurry.
Comparative example 2:
a preparation method of high-temperature-resistant electrothermal slurry comprises the following steps:
according to a molar ratio of-OH =1:2, adding hydroxyl-terminated linear polydimethylsiloxane and isophorone diisocyanate into a reaction kettle, starting stirring, dehydrating for 30min at 70 ℃ under a vacuum condition, then dropwise adding diluted organic tin into the reaction kettle under the protection of nitrogen, reacting for 4h, then adding hydroxyl saturated polyester into the reaction kettle, heating to 85 ℃ after uniformly stirring, and reacting for 4h, wherein the system is a transparent solution, so as to obtain organic silicon modified polyester resin;
adding 28 parts of organic silicon modified polyester resin, 22 parts of copper powder conductive agent, 30 parts of cyclohexane and 4 parts of auxiliary agent into a reactor, adjusting a disc type stirrer to 250r/min, dispersing for 50min, increasing the stirring speed to 2500r/min, and stirring for 3h to obtain a mixture A;
grinding the mixture A, adjusting the distance between roller shafts, ensuring that the fineness of the slurry reaches below 10um after passing through a machine for 1~2 times, filtering and discharging, then adjusting the viscosity to 3000-8000 cps, adding 16 parts of hexamethylol melamine, and fully and uniformly stirring to obtain the electric heating slurry.
Comparative example 3:
a preparation method of high-temperature-resistant electrothermal slurry comprises the following steps:
adding hydroxyl-terminated linear polydimethylsiloxane and isophorone diisocyanate into a reaction kettle according to a molar ratio of-OH: -NCO =1:2, starting stirring, dehydrating at 70 ℃ for 30min under a vacuum condition, dropwise adding diluted organic tin into the reaction kettle under the protection of nitrogen, reacting for 4h, adding hydroxyl saturated polyester into the reaction kettle, heating to 85 ℃ after uniformly stirring, reacting for 4h, and obtaining an organic silicon modified polyester resin, wherein the system is a transparent solution;
adding 28 parts of organic silicon modified polyester resin, 22 parts of carbon material conductive agent, 30 parts of cyclohexane and 4 parts of auxiliary agent into a reactor, adjusting a disc type stirrer to 250r/min, dispersing for 50min, increasing the stirring speed to 2500r/min, and stirring for 3h to obtain a mixture A;
grinding the mixture A, adjusting the distance between the rollers, ensuring that the fineness of the slurry reaches below 10um after passing through the machine for 1~2 times, filtering and discharging, then adjusting the viscosity to 3000-8000 cps, adding 16 parts of triethanolamine, and fully and uniformly stirring to obtain the electric heating slurry.
The high-temperature resistant electric heating pastes prepared in the examples 1 to 3 and the electric heating pastes prepared in the comparative examples 1 to 3 are subjected to related performance tests, and the test method comprises the following steps: the electric heating pastes of examples 1 to 3 and comparative examples 1 to 3 were coated on a PI substrate, respectively, dried at a temperature of 150 ℃ for 30min, and then tested for conductivity, temperature resistance, flexibility, weather resistance, corrosion resistance, hereinafter, sheet resistance, in a test specification of 25 μm, with the results shown in table 1 below.
Table 1:
as is clear from the data analysis in table 1, the electric heating paste of the present application has conductivity, does not pulverize at 350 ℃ for 3 hours, is excellent in weather resistance, is not easily catalyzed, is not sticky, and does not fade even when it is scrubbed with methyl ethyl ketone for 50 times. The electric heating slurry has excellent flexibility and excellent temperature resistance, weather resistance and corrosion resistance. The difference between the comparative example 1 and the example 3 is that the pulverization phenomenon occurs when the polyester resin is adopted instead of the organic silicon modified polyester resin in the comparative example 1, which shows that the organic silicon modified polyester resin is adopted in the application and can be helpful for improving the temperature resistance of the electrothermal slurry; comparative example 2 differs from example 3 only in that in comparative example 2, the carbon-based material conductive agent is replaced with a copper powder conductive agent, but a powdering phenomenon occurs, and the conductive paste is hardly conductive, has poor flexibility, is embrittled and discolored, which indicates that the addition of the carbon-based material conductive agent in the present application can contribute to the improvement of the weather resistance, temperature resistance and corrosion resistance of the conductive paste, and contributes to the obtainment of a product excellent in flexibility; comparative example 3 is different from example 3 only in that a curing agent is used, triethanolamine is used in the comparative example 3 instead of hexamethylol melamine in the example 3, and it can be seen from the comparative example 3 that the use of different curing agents causes the phenomena of chalking, poor conductivity, stickiness and fading of the electrothermal paste. Therefore, from the above data, it can be seen that the components of the present application act synergistically to obtain an electrothermal slurry having temperature resistance, weather resistance and corrosion resistance.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The high-temperature-resistant electric heating slurry is characterized by comprising the following preparation raw materials in parts by mass: 10-30 parts of organic silicon modified polyester, 5-50 parts of carbon material conductive agent, 5-40 parts of solvent, 1-5 parts of auxiliary agent and 3-20 parts of curing agent; and the organic silicon modified polyester is an organic silicon-saturated polyester block copolymer, and the synthesis reaction formula of the organic silicon-saturated polyester block copolymer is as follows:
the method comprises the following steps:
step two:
wherein R is 1 is-CH 3 , R 2 is-C x H 2x+1 Or aliphatic ring group, m, n and x are natural integers.
2. The high-temperature-resistant electrothermal slurry according to claim 1, wherein the carbon-based material conductive agent is one or a mixture of two of flake conductive graphite, spherical conductive carbon black, tubular carbon nanotubes, single-layer graphene and multi-layer graphene.
3. The high temperature resistant electrothermal slurry of claim 1, wherein the solvent is one or more of DMF, NMP, PMA, PM, DPM, BCS, cyclohexane, dichloromethane, and xylene.
4. The high-temperature-resistant electrothermal slurry according to claim 1, wherein the auxiliary agent is one or more of a leveling agent, a dispersing agent, a defoaming agent and a wetting agent.
5. The high-temperature-resistant electrothermal slurry according to claim 1, wherein the curing agent is one of trimethylol melamine, hexamethylol melamine, methylated melamine and butylated melamine.
6. A method for preparing a high-temperature resistant electrothermal slurry, which is used for preparing the high-temperature resistant electrothermal slurry of any one of claims 1 to 5, and comprises the following steps:
adding hydroxyl-terminated silicone oil and isophorone diisocyanate into a reaction kettle, starting stirring, dehydrating for 30min at 70 ℃ under a vacuum condition, then dropwise adding a diluted catalyst into the reaction kettle under the protection of nitrogen, reacting for 2h to 4h, then adding hydroxyl saturated polyester into the reaction kettle, heating to 80-90 ℃ after uniformly stirring, reacting for 3h to 4h, and obtaining an organic silicon modified polyester resin, wherein the system is a transparent solution;
adding the organic silicon modified polyester resin, the carbon series material conductive agent, the solvent and the auxiliary agent into a reactor, adjusting a disc type stirrer to 200r/min-300r/min, dispersing for 30min-60min, increasing the stirring speed to 1000r/min-5000r/min, and stirring for 2h-4h to obtain a mixture A;
grinding the mixture A, adjusting the distance between the rollers, ensuring that the fineness of the slurry reaches below 10um after passing through the machine for 1~2 times, filtering and discharging, then adjusting the viscosity to 3000cps to 8000cps, adding a curing agent, and fully and uniformly stirring to obtain the high-temperature resistant electric heating slurry.
7. The preparation method according to claim 6, wherein the hydroxyl-terminated silicone oil is hydroxyl-terminated linear polydimethylsiloxane, the molecular weight is 500 to 10000, and the hydroxyl content is 5 to 15 percent.
8. The method of claim 6, wherein the molar ratio is-OH: -NCO =1:2.
9. The preparation method according to claim 6, wherein the catalyst is one or a mixture of two of organic tin, organic bismuth and stannous octoate.
10. The method of claim 6, wherein the hydroxyl value of the hydroxyl-saturated polyester is 25 mg KOH/g to 50 mg KOH/g, and the glass transition temperature is 40 ℃ to 80 ℃.
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