CN116913585A - High-temperature-resistant polyimide enameled wire and preparation method thereof - Google Patents
High-temperature-resistant polyimide enameled wire and preparation method thereof Download PDFInfo
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- CN116913585A CN116913585A CN202310739677.6A CN202310739677A CN116913585A CN 116913585 A CN116913585 A CN 116913585A CN 202310739677 A CN202310739677 A CN 202310739677A CN 116913585 A CN116913585 A CN 116913585A
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- enameled wire
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- resistant polyimide
- polyimide
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 84
- 239000004642 Polyimide Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003973 paint Substances 0.000 claims abstract description 46
- 239000004020 conductor Substances 0.000 claims abstract description 32
- 239000011162 core material Substances 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 24
- -1 2- (5-aminopyridin-2-yl) -1-phenyl-benzimidazol-5-yl-amino Chemical group 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 229920005575 poly(amic acid) Polymers 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 210000003298 dental enamel Anatomy 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 2
- 238000001953 recrystallisation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010257 thawing Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004962 Polyamide-imide Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- PQHCQWFFYWTDHE-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)-2-benzofuran-1,3-dione Chemical compound FC(C(C(F)(F)F)C1=C2C(C(=O)OC2=O)=CC=C1)(F)F PQHCQWFFYWTDHE-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/065—Insulating conductors with lacquers or enamels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/16—Insulating conductors or cables by passing through or dipping in a liquid bath; by spraying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/306—Polyimides or polyesterimides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention belongs to the technical field of polyimide materials, and provides a high-temperature-resistant polyimide enameled wire and a preparation method thereof. The high-temperature-resistant polyimide enameled wire comprises a conductor core material and a polyimide paint film coated on the conductor core material, wherein the polyimide paint film has a structural formula shown in a formula I:wherein n represents a polymerization degree, and n is 50-200; x is the followingAny one of the substituents:ar comprises at least one of the following structures:
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-temperature-resistant polyimide enameled wire and a preparation method thereof.
Background
Enameled wires are also called electromagnetic wires and comprise a bare conductor and insulating paint coated outside the bare conductor, are widely applied to the fields of motors, electric appliances, inductors, transformers and household appliances, and with the development of the age and the progress of technology, the military and civil fields all provide higher requirements on the temperature resistance level of the enameled wires.
The performance of the enameled wire is greatly dependent on the quality and performance of the enameled wire paint film, and the ideal enameled wire paint film has good insulativity, high temperature resistance, low temperature resistance and chemical corrosion resistance, certain mechanical strength and good binding force on copper wires. At present, the types of wire enamel films mainly comprise polyurethane, polyester, polyimide, polyamide imide and composite coating wire enamel, wherein the polyimide wire enamel is the insulating enamel with the highest temperature resistance grade in the current wire enamel, and the long-term use temperature can reach more than 220 ℃.
At present, polyamide-imide paint composite polyimide paint or polyamide-imide paint composite polyester paint is generally used as an outer insulating layer of a copper conductor, and polyimide enameled wires have good heat resistance, but the paint has poor adhesiveness with the copper conductor; the latter has good adhesion but poor heat resistance. Poor adhesion can cause the enameled wire to produce the phenomenon of paint removal in the use, influences the quality of motor, has restricted the application of enameled wire in actual production.
Disclosure of Invention
The invention aims at: at least one defect in the prior art is overcome, and a high-temperature-resistant polyimide enameled wire and a preparation method thereof are provided, so that the adhesiveness between polyimide enameled wire paint and a conductor core material is improved.
In order to achieve the above object, the present invention provides a high temperature resistant polyimide enameled wire, which comprises a conductor core material and a polyimide paint film coated on the conductor core material, wherein the polyimide paint film has a structural formula shown in formula I:
wherein n represents a polymerization degree, and n is 50-200;
x is any one of the following substituents:
-H -CH 3 -CF 3 -C 2 H 5
ar comprises at least one of the following structures:
according to one embodiment of the high temperature resistant polyimide enameled wire of the invention, the polyimide paint film preferably comprises any one of the following structures:
in order to achieve the aim of the invention, the invention also provides a preparation method of the high-temperature-resistant polyimide enameled wire, which comprises the following steps:
1) Mixing diamine monomer, dianhydride monomer and organic solvent in protective atmosphere, and performing solution polycondensation reaction to obtain polyamic acid solution; and
2) Coating the polyamic acid solution prepared in the step 1) on the surface of a conductor core material, removing a solvent and completing imidization reaction to obtain a high-temperature-resistant polyimide enameled wire with the surface of the conductor core material coated with a polyimide paint film;
wherein the diamine monomer has the following structure:
x is any one of the following substituents:
-H -CH 3 -CF 3 -C 2 H5
the dianhydride monomer comprises at least one of the following structures:
according to one embodiment of the preparation method of the high temperature resistant polyimide enameled wire, the molar ratio of the diamine monomer to the dianhydride monomer is 1:1-1.3.
According to one embodiment of the preparation method of the high temperature resistant polyimide enameled wire, the organic solvent is N, N-dimethylacetamide, N-methylpyrrolidone or N, N-dimethylformamide.
According to one embodiment of the preparation method of the high-temperature-resistant polyimide enameled wire, the temperature of polycondensation reaction is-20-25 ℃ and the reaction time is 4-16h.
According to one embodiment of the method for preparing a high temperature resistant polyimide enameled wire of the invention, the solid content of the polyamic acid solution is 15 to 25 weight percent.
According to one embodiment of the preparation method of the high-temperature-resistant polyimide enameled wire, before coating, the polyamic acid solution is subjected to standing and defoaming, the defoaming temperature is between-20 and 25 ℃, and the defoaming time is between 6 and 30 hours.
According to one embodiment of the preparation method of the high-temperature-resistant polyimide enameled wire, the temperature of the solvent is 80-200 ℃ and the time is 3-12h.
According to one embodiment of the preparation method of the high-temperature-resistant polyimide enameled wire, the imidization reaction is carried out at the temperature of 120-400 ℃ for 3-12 hours.
Compared with the prior art, the polyimide paint film of the high-temperature-resistant polyimide enameled wire has a structural formula shown in a formula I, and the high thermal stability and excellent mechanical properties of a polyimide material are reserved. The high-temperature resistant polyimide paint is obtained by polymerizing a diamine monomer containing benzimidazole and pyridine groups and a dianhydride monomer, and the adhesion and the bonding strength of the polyimide paint with a metal copper conductor are improved by introducing benzimidazole and pyridine heterocycle into a polyimide main chain and utilizing the metal chelation of lone pair electrons on pyridine N atoms while maintaining the heat resistance of the polyimide paint. The polyimide enameled wire provided by the invention has excellent heat resistance, high bonding strength, higher softening breakdown temperature and higher breakdown voltage than the national standard, and has excellent application value.
Drawings
The high Wen Juxian sub-enameled wire and the preparation method thereof are described in detail below with reference to the accompanying drawings and detailed description, wherein:
fig. 1 is an infrared chart of the high temperature resistant polyimide enameled wire prepared in examples 1 to 3 of the invention.
Fig. 2 is a dynamic thermo-mechanical diagram of the high temperature resistant polyimide enameled wire prepared in examples 1 to 3 of the invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention will be described in further detail with reference to the accompanying drawings and examples. It should be understood that the examples described in this specification are for the purpose of illustrating the invention only and are not intended to limit the invention.
The invention provides a high-temperature-resistant polyimide enameled wire which comprises a conductor core material and a polyimide paint film coated on the conductor core material, wherein the polyimide paint film has a structural formula shown in a formula I:
wherein n represents a polymerization degree, and n is 50-200;
x is any one of the following substituents:
-H -CH 3 -CF 3 -C 2 H 5
ar comprises at least one of the following structures:
according to one embodiment of the high temperature resistant polyimide enamel wire of the present invention, the polyimide film preferably includes any one of the following structures:
the invention provides a preparation method of a high-temperature-resistant polyimide enameled wire, which comprises the following steps:
1) Mixing diamine monomer, dianhydride monomer and organic solvent in protective atmosphere, and performing solution polycondensation reaction to obtain polyamic acid solution; and
2) Coating the polyamic acid solution prepared in the step 1) on the surface of a conductor core material, removing a solvent and completing imidization reaction to obtain a high-temperature-resistant polyimide enameled wire with the surface of the conductor core material coated with a polyimide paint film;
wherein the diamine monomer has the following structure:
x is any one of the following substituents:
-H -CH 3 -CF 3 -C 2 H5
the dianhydride monomer comprises at least one of the following structures:
according to one embodiment of the method for manufacturing a high Wen Juxian sub-enamelled wire according to the invention, the conductor core is preferably a copper conductor core. The protective atmosphere is not particularly specified, and a protective atmosphere well known in the art, such as nitrogen or argon, may be used. The diamine monomer, the dianhydride monomer and the solvent are preferably mixed by adding the diamine monomer to the solvent and then adding the dianhydride monomer, and the mixing is preferably performed under stirring conditions, and the stirring speed is not particularly required, and the stirring speed well known in the art is adopted. The mixing time is not particularly limited as long as the diamine monomer, the dianhydride monomer and the solvent can be uniformly mixed.
The molar ratio of diamine monomer to dianhydride monomer is 1:1-1.3, preferably 1:1-1.25, when the dianhydride monomer is a mixture of the two dianhydride monomers, the preparation method of the high-temperature resistant polyimide enameled wire is the same as the preparation method adopting one dianhydride monomer.
According to one embodiment of the method for preparing a high Wen Juxian sub-enameled wire according to the invention, the organic solvent is preferably an aprotic solvent, such as N, N-dimethylacetamide, N-methylpyrrolidone or N, N-dimethylformamide, preferably N, N-dimethylacetamide or N-methylpyrrolidone. The N, N-dimethylacetamide or N-methylpyrrolidone is preferably dried before use, and the specific method of drying is not particularly limited, and drying methods using organic solvents well known in the art may be employed.
According to one embodiment of the method for preparing a high Wen Juxian sub-enameled wire according to the invention, the temperature of the polycondensation reaction is between-20 ℃ and 25 ℃, preferably between-5 ℃ and 20 ℃, most preferably 10 ℃. The reaction time of the polycondensation reaction is 4 to 16 hours, preferably 6 to 12 hours.
According to one embodiment of the method for preparing the high Wen Juxian sub-enamelled wire of the present invention, the solid content of the polyamic acid solution is 15 to 25wt%.
After completion of the polymerization reaction, according to one embodiment of the present invention, it is preferable to further include subjecting the resultant system to a standing deaeration and thawing treatment to obtain a polyamic acid solution. According to one embodiment of the method for preparing the high Wen Juxian sub-enamelled wire of the present invention, the polyamic acid solution is subjected to standing and deaeration before coating, the deaeration temperature is-20 ℃ to 25 ℃, and the deaeration temperature is selected to be-20 ℃ to 0 ℃, and more preferably is-20 ℃ to-10 ℃. The defoaming time is 6-30 hours, preferably 12-24 hours. The standing and defoaming can overflow bubbles generated by mixing in the system, and the completely bubble-free and uniform polyamic acid paint liquid is obtained. The thawing temperature is not particularly limited, and may be any thawing temperature known in the art, such as normal temperature. The thawing treatment time is preferably 30 to 60min, more preferably 30 to 40min.
The coating process of the conductor core material is not particularly limited, and a coating process well known in the art is adopted, and the thickness of a paint film after coating is preferably 20-100 μm.
According to one embodiment of the method for preparing the high Wen Juxian sub-enamelled wire of the invention, the obtained wet film is subjected to solvent removal treatment after coating is completed. The temperature for removing the solvent is 70 ℃ to 200 ℃, preferably 80 ℃ to 180 ℃, more preferably 120 ℃ to 180 ℃. The solvent removal treatment time is 3 to 12 hours, preferably 3 to 6 hours. There is no particular requirement on the apparatus used for the solvent removal treatment, and a solvent removal treatment apparatus known in the art may be used. According to one embodiment of the present invention, the solvent removal treatment is preferably performed under a temperature programmed condition, preferably a temperature programmed condition of 80 ℃ for 1h,140 ℃ for 1h, and 200 ℃ for 1h.
After the solvent is removed, the obtained paint film is subjected to imidization reaction, wherein the imidization reaction temperature is preferably 120-400 ℃, and the imidization time is preferably 3-12h. According to one embodiment of the present invention, the imidization reaction is preferably performed under a temperature-programmed condition, preferably, the temperature-programmed condition is heated at 200℃to 230℃for 1 to 2 hours, at 250℃to 300℃for 1 to 2 hours, and at 310℃to 400℃for 1 to 2 hours. It will be appreciated that the temperature programming conditions are preferably selected based on the different target products.
The preparation method of the high-temperature-resistant Wen Juxian sub-enameled wire is simple and easy to operate, can realize industrial production, has good heat resistance of a paint film, has breakdown voltage and softening breakdown temperature which are both obviously higher than the national standard of 240-level polyimide enameled copper round wire, and can meet the production requirement of the high-temperature-resistant polyimide enameled wire. Aiming at the defect of poor adhesion between the traditional enameled wire and the metal copper conductor, the polyimide paint film of the high-temperature-resistant polyimide enameled wire has a structural formula shown in a formula I, and the high thermal stability and excellent mechanical properties of a polyimide material are reserved. The high-temperature resistant polyimide paint is obtained by polymerizing a diamine monomer containing benzimidazole and pyridine groups and a dianhydride monomer, and the adhesion and the bonding strength of the polyimide paint with a metal copper conductor are improved by introducing benzimidazole and pyridine heterocycle into a polyimide main chain and utilizing the metal chelation of lone pair electrons on pyridine N atoms while maintaining the heat resistance of the polyimide paint. The polyimide enameled wire provided by the invention has excellent heat resistance, high bonding strength, higher softening breakdown temperature and higher breakdown voltage than the national standard, and has excellent application value.
The technical scheme of the present invention will be clearly and completely described in the following examples. The embodiments described in this specification are only some, but not all, embodiments of the invention. 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 fall within the scope of the invention. Unless otherwise indicated, all raw material components are commercially available products well known to those skilled in the art.
Preparation of 2- (5-aminopyridin-2-yl) -1-phenyl-benzimidazol-5-amino
S1, adding 15g of 5-aminopyridine acid, 105ml of sulfoxide chloride and 5ml of N, N-dimethylformamide into a round-bottomed flask, adding a condensing tube to react with a balloon at 80 ℃ for about 5 hours, and removing most of sulfoxide chloride by rotary evaporation; adding a certain amount of tetrahydrofuran, shaking uniformly, steaming, repeating for three times to remove residual thionyl chloride to obtain 5-aminopyridine acyl chloride.
S2, adding 15.46g N-benzene-1, 2, 4-triamine, 10.99g of triethylamine and 140ml of tetrahydrofuran into a round-bottomed flask, slowly dripping 5-aminopyridine acyl chloride in an ice-water bath environment, controlling the whole process temperature within 10 ℃, reacting for 12 hours, removing tetrahydrofuran and redundant acyl chloride by rotary evaporation, adding a large amount of methanol into the rest solid, stirring uniformly, rotary evaporating, removing redundant acyl chloride, repeating for 3 times, finally adding a large amount of methanol again, stirring uniformly, and performing suction filtration and drying to obtain the 5-amino-N- (5-amino-2- (phenylamino) phenyl) pyridine amide (21.82 g).
S3, putting the product of the last step and 20.71g of p-toluenesulfonic acid monohydrate and 218.2ml of sulfolane into a round-bottom flask, reacting for 10 hours at 200 ℃, pouring the reaction liquid into water, stirring uniformly, filtering and drying, dissolving the solid into 225ml of DMSO solution at 90 ℃, cooling to room temperature, recrystallizing for 24 hours, filtering, washing with ethanol, and drying to obtain 2- (5-nitropyridin-2-yl) -1-phenyl-benzimidazole-5-nitro (12.16 g).
S4, adding 1.21g of palladium-carbon and 121.6ml of ethanol into a round-bottom flask, heating to 80 ℃, slowly adding 16.84g of hydrazine hydrate, reacting for 5 hours, filtering the palladium-carbon, pouring the filtrate into water, and carrying out suction filtration and drying to obtain the 2- (5-aminopyridine-2-yl) -1-phenyl-benzimidazole-5-amino.
Example 1
Under the protection of nitrogen, 10g of 2- (5-aminopyridine-2-yl) -1-phenyl-benzimidazole-5-amino (monomer 2- (5-aminopyridine-2-yl) -1-phenyl-benzimidazole-5-amino is prepared by the process as above) is added into 75g of N, N-dimethylacetamide, stirred and mixed under the ice water bath condition, 14.7417g of hexafluoroisopropyl phthalic anhydride is added, stirring is continued, the viscosity of a stirring time prolonged system is increased, 54.9g of N, N-dimethylacetamide is added, the solid content of the obtained system is 16.0wt%, the polymerization reaction is started for 12 hours from the completion of solvent addition, the reaction device is removed, the bottle mouth is sealed, and the bottle mouth is kept in a refrigerator at the temperature of minus 10 ℃ for 12 hours, so that a polyamide acid solution (PAA paint) with uniform color is obtained;
the PAA paint is thawed for 30min at room temperature, then coated on a copper conductor core material with the diameter of 0.5mm and the thickness of a paint film of 20-100 mu m, the coated copper conductor core material is transferred into a baking oven, and the solvent is removed according to a heating program of 80 ℃ for one hour, 160 ℃ for one hour and 200 ℃ for one hour. Then imidization reaction is carried out according to a heating program of 200 ℃ for one hour, 280 ℃ for one hour and 350 ℃ for one hour, and the polyimide enameled wire shown in the formula I-1 is obtained after the temperature of the baking furnace is reduced to the room temperature, wherein n is 50-150.
Example 2
Under the protection of nitrogen, 10g of 2- (5-aminopyridine-2-yl) -1-phenyl-benzimidazole-5-amino (monomer 2- (5-aminopyridine-2-yl) -1-phenyl-benzimidazole-5-amino is prepared by the process as above) is added into 61g of N, N-dimethylacetamide, and is stirred and mixed under the ice water bath condition, 10.2943g of 4,4' -oxydiphthalic anhydride is added for continuous stirring, 54g of N, N-dimethylacetamide is added along with the increase of the viscosity of a stirring time, the solid content of the obtained system is 15.0wt%, the polymerization reaction is started for 12 hours from the completion of the solvent addition, a reaction device is taken down, a bottle mouth is sealed, and the mixture is left in a refrigerator at the temperature of minus 10 ℃ for defoaming to obtain a polyamide acid solution (PAA paint) with uniform color;
the PAA paint is thawed for 30min at room temperature, then coated on a copper conductor core material with the diameter of 0.5mm and the thickness of a paint film of 20-100 mu m, the coated copper conductor core material is transferred into a baking oven, and the solvent is removed according to a heating program of 80 ℃ for one hour, 160 ℃ for one hour and 200 ℃ for one hour. Then imidization reaction is carried out according to a heating program of 200 ℃ for one hour, 280 ℃ for one hour and 320 ℃ for one hour, and the polyimide enameled wire shown in the formula I-2 is obtained after the temperature of the baking furnace is reduced to the room temperature, wherein n is 50-150.
Example 3
Under the protection of nitrogen, 10g of 2- (5-aminopyridine-2-yl) -1-phenyl-benzimidazole-5-amino (monomer 2- (5-aminopyridine-2-yl) -1-phenyl-benzimidazole-5-amino is prepared by the process as above) is added into 53g of N, N-dimethylacetamide, and is stirred and mixed under the ice water bath condition, 7.4389g of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride is added, stirring is continued, the viscosity of a stirring time is prolonged, 16.8g of N, N-dimethylacetamide is added, the solid content of the obtained system is 20.0wt%, the polymerization reaction is started for 12 hours from the completion of solvent addition, a reaction device is taken down, a bottle mouth is sealed, and the mixture is left in a refrigerator at the temperature of minus 10 ℃ for defoaming for 12 hours, so that a polyamide acid solution (PAA paint) with uniform color is obtained;
the PAA paint is thawed for 30min at room temperature, then coated on a copper conductor core material with the diameter of 0.5mm and the thickness of a paint film of 20-100 mu m, the coated copper conductor core material is transferred into a baking oven, and the solvent is removed according to a heating program of 80 ℃ for one hour, 160 ℃ for one hour and 200 ℃ for one hour. Then imidization reaction is carried out according to a heating program of 200 ℃ for one hour, 280 ℃ for one hour, 320 ℃ for one hour and 380 ℃ for one hour, and the polyimide enameled wire with the formula I-3 is obtained after the temperature of the baking furnace is reduced to room temperature, wherein n is 50-150.
Test example 1
As shown in FIG. 1, the infrared spectrograms of the high temperature resistant polyimide enameled wire prepared in the examples 1-3 show typical characteristic absorption peaks of imide and benzimidazole at 1770cm < -1 > (symmetrical telescopic vibration peak of imide carbonyl), 1724cm < -1 > (asymmetrical telescopic vibration peak of imide carbonyl) and 1370cm < -1 > (C-N vibration peak), respectively, and the result shows that the polyimide enameled wire with the structure shown in the examples 1-3 is successfully prepared in the invention.
Test example 2
The polyimide enameled wires prepared in examples 1 to 3 were subjected to dynamic thermo-mechanical analysis under a nitrogen atmosphere at a heating rate of 10 c/min using DMA Q800, and the results are shown in fig. 2 and table 1.
Test example 3
The performance test results of the enamelled wire according to the GB/T6109.22 QY-1/240 pair example are as follows:
TABLE 1 test of enamelled wire Performance of examples 1-3
As can be seen from Table 1, the enameled wires prepared in examples 1 to 3 are excellent in performance: the glass transition temperature of the polyimide paint film prepared by the invention is 347-408 ℃ (the peak temperature of a loss tangent-temperature curve), and the polyimide paint film has excellent high temperature resistance, and has stable softening breakdown and breakdown voltage which are both obviously higher than the national standard of 240-level polyimide enamelled copper round wires. The high-temperature-resistant polyimide enameled wire provided by the invention has high heat-resistant grade, smooth paint film surface, uniform color, good flexibility, strong adhesion with a metal copper conductor, and higher softening breakdown temperature and breakdown voltage than national standards. The preparation method has the advantages of simple process, easy operation, low production cost, less three-waste pollution, easy realization of industrial production and improvement of the technological level of the polyimide enameled wire.
The present invention is also capable of suitable alterations and modifications in the above-described embodiments, in light of the above principles. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (17)
1. The high-temperature-resistant polyimide enameled wire comprises a conductor core material and a polyimide paint film coated on the conductor core material, and is characterized in that the polyimide paint film has a structural formula shown in a formula I:
wherein n represents a polymerization degree, and n is 50-200;
x is any one of the following substituents:
ar comprises at least one of the following structures:
2. the high temperature resistant polyimide wire enamel according to claim 1, wherein the polyimide film preferably comprises any one of the following structures:
3. the preparation method of the high-temperature-resistant polyimide enameled wire is characterized by comprising the following steps of:
1) Mixing diamine monomer, dianhydride monomer and organic solvent in protective atmosphere, and performing solution polycondensation reaction to obtain polyamic acid solution; and
2) Coating the polyamic acid solution prepared in the step 1) on the surface of a conductor core material, removing a solvent and completing imidization reaction to obtain a high-temperature-resistant polyimide enameled wire with the surface of the conductor core material coated with a polyimide paint film;
wherein the diamine monomer has the following structure:
x is any one of the following substituents:
the dianhydride monomer comprises at least one of the following structures:
4. the method for preparing a high temperature resistant polyimide enameled wire according to claim 3, wherein the molar ratio of diamine monomer to dianhydride monomer is 1:1-1.3.
5. The method for preparing a high temperature resistant polyimide enamel wire according to claim 3, wherein the organic solvent is N, N-dimethylacetamide, N-methylpyrrolidone or N, N-dimethylformamide.
6. The method for preparing a high temperature resistant polyimide enameled wire according to claim 3, wherein the temperature of the polycondensation reaction is-20-25 ℃ and the reaction time is 4-16h.
7. The method for preparing a high temperature resistant polyimide enameled wire according to claim 3, characterized in that the solid content of the polyamic acid solution is 15 to 25 weight percent.
8. The method for preparing a high temperature resistant polyimide enameled wire according to claim 3, characterized in that before coating, the polyamic acid solution is subjected to standing and defoaming at a temperature of-20 ℃ to 25 ℃ for 6 to 30 hours.
9. The method for preparing a high temperature resistant polyimide enameled wire according to claim 3, characterized in that the temperature of the solvent removal is 80-200 ℃ and the time is 3-12h.
10. The method for preparing a high temperature resistant polyimide enameled wire according to claim 3, characterized in that the imidization reaction is carried out at a temperature of 120-400 ℃ for 3-12 hours.
11. A process for the preparation of 2- (5-aminopyridin-2-yl) -1-phenyl-benzimidazol-5-yl-amino, comprising the steps of:
s1, mixing 5-aminopyridine acid, sulfoxide chloride and N, N-dimethylformamide for reaction, and removing the sulfoxide chloride by rotary evaporation to obtain 5-aminopyridine acyl chloride;
s2, slowly dripping N-benzene-1, 2, 4-triamine, triethylamine and tetrahydrofuran into 5-aminopyridine acyl chloride in an ice water bath environment, performing rotary evaporation to remove tetrahydrofuran and redundant acyl chloride after reaction, adding methanol into the rest solid, performing rotary evaporation after stirring uniformly to remove redundant acyl chloride, adding methanol again, stirring uniformly, performing suction filtration and drying to obtain 5-amino-N- (5-amino-2- (phenylamino) phenyl) pyridine amide;
s3, mixing 5-amino-N- (5-amino-2- (phenylamino) phenyl) pyridine amide, p-toluenesulfonic acid monohydrate and sulfolane for reaction, pouring the reaction solution into water, stirring uniformly, filtering and drying, dissolving the solid in DMSO solution, cooling to room temperature for recrystallization, filtering, washing with ethanol, and drying to obtain 2- (5-nitropyridin-2-yl) -1-phenyl-benzimidazole-5-nitro;
s4, mixing 2- (5-nitropyridin-2-yl) -1-phenyl-benzimidazole-5-nitro, palladium-carbon and ethanol, heating, slowly adding hydrazine hydrate, filtering the palladium-carbon after reaction, pouring filtrate into water, and carrying out suction filtration and drying to obtain 2- (5-aminopyridine-2-yl) -1-phenyl-benzimidazole-5-amino.
12. The preparation method according to claim 11, wherein in step S1, after removing thionyl chloride by rotary evaporation, tetrahydrofuran is added, and after shaking uniformly, the remaining thionyl chloride is removed by rotary evaporation.
13. The preparation method according to claim 11, wherein in step S2, 5-aminopyridine acyl chloride is slowly dripped in an ice-water bath environment, and the whole process is controlled to be within 10 ℃.
14. The process according to claim 11, wherein in step S2, tetrahydrofuran and excess acid chloride are removed by rotary evaporation, methanol is added to the remaining solid, and after stirring, excess acid chloride is removed by rotary evaporation.
15. The preparation method according to claim 11, wherein in step S4, hydrazine hydrate is slowly added to react for 4 to 5 hours after the temperature is raised to 80 ℃.
16. 2- (5-aminopyridin-2-yl) -1-phenyl-benzimidazol-5-amino obtained by the process according to any one of claims 11 to 15.
17. A diamine monomer characterized by having the structure:
wherein X is any one of the following substituents:
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