CN115044234B - Ultraviolet-curable H-level insulating coating composition and preparation method thereof - Google Patents
Ultraviolet-curable H-level insulating coating composition and preparation method thereof Download PDFInfo
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- CN115044234B CN115044234B CN202210706009.9A CN202210706009A CN115044234B CN 115044234 B CN115044234 B CN 115044234B CN 202210706009 A CN202210706009 A CN 202210706009A CN 115044234 B CN115044234 B CN 115044234B
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- acrylate
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- 239000008199 coating composition Substances 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 16
- -1 acrylic ester Chemical class 0.000 claims description 15
- 229920000767 polyaniline Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 11
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 10
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 2
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 33
- 239000011248 coating agent Substances 0.000 abstract description 28
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 31
- 239000003973 paint Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 102220636508 ATPase inhibitor, mitochondrial_E51A_mutation Human genes 0.000 description 3
- 101100029848 Arabidopsis thaliana PIP1-2 gene Proteins 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 101100465519 Arabidopsis thaliana MPA1 gene Proteins 0.000 description 1
- 102100028538 Guanylate-binding protein 4 Human genes 0.000 description 1
- 101001058851 Homo sapiens Guanylate-binding protein 4 Proteins 0.000 description 1
- 101100300012 Mannheimia haemolytica purT gene Proteins 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 101100067996 Mus musculus Gbp1 gene Proteins 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an H-grade insulating outer coating capable of ultraviolet light curing (UV) and a preparation method thereof. The invention uses the mixture of trifunctional acrylate, trimellitic anhydride, epoxy resin, diphenylamine ether, synthesized phenylate acrylate oligomer, acrylate monomer, initiator and the like, has the characteristic of ultraviolet light curing, can greatly improve volume resistivity, reduces dielectric loss and can resist high temperature up to 200 ℃ to prepare the H-level insulating coating. The method provided by the invention has high practicality and good feasibility, and is an effective means for solving the problem of high temperature resistance of the ultraviolet light curing insulating coating.
Description
Technical Field
The invention belongs to the field of ultraviolet light curing paint preparation, and particularly relates to a preparation method of an H-level insulating paint capable of improving ultraviolet light curing high temperature resistance.
Background
The insulating coating is developed together with the electronic industry, particularly the development of the motor is not separated from the advanced insulating coating, and the good insulating coating has good electric performance, thermal performance, mechanical performance and chemical resistance. The dielectric strength (breakdown strength) is higher than 10KV/m; high volume resistivity, room temperature greater than 10Ω m; the product has no flash point, high hardness, 7H and good chemical stability; the heat resistance is good. However, the existing insulating paint is solvent paint, the solid content of the solvent paint is low, the environmental pollution is large, the energy is wasted, and the current development trend is not met.
The ultraviolet curing technology has the characteristics of high efficiency, energy conservation, environmental protection and the like. In particular, the application of environment-friendly and safe materials is promoted in the country in recent years, and the environment-friendly and safe materials are widely applied in the fields of paint, ink and adhesive, so that the development of the environment-friendly and safe materials is quite rapid in recent decades worldwide, and particularly in the field of ultraviolet light curing paint, the environment-friendly and safe materials are greatly developed.
Conventional solvent-borne coating curing is typically carried out by removing the solvent from the polymeric solution by heating, i.e., physical drying, to provide a hardened paint film. The UV curing is to initiate polymerization and crosslinking reaction between low molecular prepolymer or oligomer in the coating and monomer molecules serving as reactive diluents by utilizing the energy of ultraviolet light to obtain a hardened paint film, and chemical drying is realized by forming chemical bonds. The photo-curing coating is also called photosensitive coating, and the ultraviolet light is used as the coating curing energy source and is called ultraviolet light curing coating. The photo-curing coating has the advantages of short curing time (a fraction of a second to a few minutes), low curing temperature and low volatile, and is a new coating variety with energy and resource conservation, no public hazard and high efficiency.
Because the classical ultraviolet light curing coating is composed of acrylate oligomer and acrylate monomer, the structure contains polar group acrylate, so that the polarization can be increased, the dielectric loss can be increased, the volume resistivity can be reduced, and the requirement of the insulating coating can not be met. This will greatly affect the application of uv curable coatings in insulating coatings. The invention aims to provide a preparation method of an ultraviolet-cured high-temperature-resistant H-grade insulating paint.
Ultraviolet curing is most beneficial at present in high efficiency and environmental protection. The curing time is extremely short (generally within 0.3-1 second), so that the efficiency is improved, VOC is not discharged, the method is an effective method for solving the problem that the traditional solvent type paint is not environment-friendly, and the development of the ultraviolet curing paint with high insulativity has important practical effect.
By combining the two performances, we develop an insulating paint with high temperature resistance, and therefore, the development of an ultraviolet light curing insulating paint has important social practical significance.
In the ultraviolet light insulating paint, ultraviolet light curing insulating paint is a very fresh project, few researches exist, and few declaration patents can be found at present, and no industrialization technology exists in our country at present, but there are individual researches, namely "(methyl) acrylic acid modified polyurethane resin of Xiamen Xinzhou science and technology Co., ltd (without advertising the inventor), ultraviolet light curing insulating paint CN103408716A containing the ultraviolet light modified polyurethane resin and nano materials is an ultraviolet light curing paint which uses polyurethane acrylic ester as a main body, has general film forming performance, and the electrical performance improvement of the ultraviolet light curing paint is necessarily improved by adding nano materials; the exception Wang Yanhui, yu Zongping (per se) and the like are that CN112592639B is a phenolic epoxy acrylate which is developed by a preparation method of ultraviolet curing insulating paint for enameled wires, has high temperature resistance of only 155 ℃, is an insulating paint with medium temperature, is completely different from the proposed method, and is solved by synthesizing resin of polyaniline ether, and the effects of different materials, different methods and different methods are also different.
Disclosure of Invention
In order to solve the high temperature resistance of the ultraviolet light curing insulating coating and improve the insulativity, the invention provides an ultraviolet light curing (UV) H-level insulating coating composition, and the insulating coating for solving the high temperature resistance is the purpose of the invention.
The technical scheme of the invention is as follows: an ultraviolet light curing (UV) H-grade insulating coating composition comprises the following components in parts by mass:
a) 40-60 parts of polyaniline ether acrylate resin;
b) 30-50 parts of acrylic ester monomer;
c) Polymerization inhibitor-0.5-1 part;
d) 5-8 parts of photoinitiator;
e) 0.1-0.5 part of colorant;
wherein the polyaniline ether acrylate resin is the reaction product of:
i) A triacrylate;
ii) p-aminophenyl ether;
iii) A polymerization inhibitor;
iv) trimellitic anhydride;
v) a catalyst;
vi) phenolic epoxy resin;
vii) acrylate monomers;
wherein the phenolic epoxy resin has an epoxy value of 170-195eq/100g, the polymerization inhibitor is a phenolic antioxidant, and the catalyst is quaternary ammonium salt or tertiary amine; the acrylic ester monomer is acrylic ester with monofunctional groups containing benzene rings or amide groups; the triacrylate is acrylate with acrylate monomer containing three functional groups.
The polyaniline ether acrylate resin synthesis process is that after polymerization inhibitor, triacrylate and p-aminophenether are added to react for 2 hours at 35-45 ℃ to reach a specified amine value, trimellitic anhydride is added to react for 4 hours at 100-120 ℃ to reach an acid value, phenolic epoxy resin, catalyst and acrylate monomer are added to react for 2 hours at 95-100 ℃, the temperature is controlled for 3 hours at 110-120 ℃, and the acid value is reduced to 5mgKOH/g.
The acrylic ester monomer is any one of 2-phenoxyethyl acrylic ester and 2- (1, 2-cyclohexanedicarboxylic imide) ethyl acrylic ester.
The polymerization inhibitor is p-hydroxyanisole or 2-tertiary butyl hydroquinone.
The catalyst is any one of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bisulfate, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
The triacrylate comprises any one of trimethylolpropane triacrylate, pentaerythritol triacrylate and trimethylolpropane trimethacrylate.
The p-aminophenyl ether is 4,4' -oxydiphenylamine ether.
The composition has high temperature resistance of 200 ℃ in a metal copper wire coating test after ultraviolet light curing, and volume resistivity of 1.0 multiplied by 10 17 The dielectric loss 50HZ reaches 0.001-0.004.
The preparation method of the ultraviolet light curing (UV) H-level insulating coating composition comprises the steps of preparing polyaniline ether acrylate resin and then compounding with other components.
Advantageous effects
The ultraviolet light cured insulating paint coating prepared by the invention has the characteristics of ultraviolet light curing, is efficient and environment-friendly, can greatly improve the breakdown voltage of the insulating paint, and can resist high temperature up to 200 ℃ to reach the H level of the insulating paint. The method provided by the invention has high practicality and good feasibility, is an effective means for solving the problem of ultraviolet curing insulating paint, and is an environment-friendly ultraviolet curing material.
Detailed Description
The reagent used in the present invention is a commercially available conventional product, as long as it is a qualified industrial product, not limited to a manufacturer.
An ultraviolet light curable (UV) class H insulating coating composition comprising, in mass percent:
a) 40-60% of polyaniline ether acrylate resin;
b) Acrylic ester monomer-30-50%;
c) Polymerization inhibitor-0.5-1%;
d) 5-8% of photoinitiator;
e) 0.1-0.5% of coloring agent;
wherein the polyaniline ether acrylate resin is the reaction product of:
i) A triacrylate;
ii) a diphenylamine ether;
iii) A polymerization inhibitor;
iv) trimellitic anhydride;
v) a catalyst;
vi) phenolic epoxy resin;
vii) acrylate monomers.
The phenolic epoxy resin has an epoxy value of 170-195eq/100g, the polymerization inhibitor is a phenolic antioxidant, and the catalyst is quaternary ammonium salt or tertiary amine. The synthetic process of the oligomer resin is that after polymerization inhibitor, triacrylate and diphenylamine ether are added to react for 2 hours at 35-45 ℃ to reach a specified amine value, trimellitic anhydride is added to react for 4 hours at 100-120 ℃ to reach an acid value, phenolic epoxy resin, catalyst and acrylate monomer are added to react for 2 hours at 95-100 ℃, the temperature is controlled to react for 3 hours at 110-120 ℃, and the acid value is reduced to 5mgKOH/g.
The phenolic epoxy resin is standard phenolic epoxy with the epoxy value of 170-195eq/100g, wherein the phenolic epoxy can be preferably products such as E51, E54 and the like which are mature in the market.
The triacrylate is acrylate monomer containing three functional groups, generally but not limited to, trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), and trimethylolpropane trimethacrylate (TMPTMA).
The polymerization inhibitor is a phenolic antioxidant, and the catalyst is quaternary ammonium salt or tertiary amine. Among them, preferred antioxidants are para-Hydroxyanisole (HEQM) and 2-tert-butylhydroquinone MTBHQ. As the quaternary ammonium salt in the catalyst, benzyl triethyl ammonium chloride (TEBA), tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate (TBAB), trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride and the like are commonly used. The catalyst is generally preferably a quaternary ammonium salt, and among the quaternary ammonium salts, benzyl triethyl ammonium chloride (TEBA) and tetrabutylammonium bromide are more preferable.
The polyaniline ether acrylate resin component diphenylamine ether is para-structure p-aminophenyl ether, such as 4,4' -oxydiphenylamine.
The synthesis process of the oligomer in the composition comprises the following steps: adding a polymerization inhibitor, triacrylate and diphenylamine ether to react for 2 hours at 35-45 ℃ to reach a specified amine value, adding trimellitic anhydride to react for 4 hours at 100-120 ℃ to reach an acid value, adding phenolic epoxy resin, a catalyst and an acrylate monomer to react for 2 hours at 95-100 ℃, controlling the temperature to react for 3 hours at 110-120 ℃, and reducing the acid value to 5mgKOH/g.
The diluent monomer is one or more of acrylic ester with monofunctional benzene ring or amide group. Including but not limited to: 2-phenoxyethyl acrylate PHEA, 2- (1, 2-cyclohexanedicarboxylic imide) ethyl acrylate DEA, and the like.
The photoinitiator is mainly an initiator capable of absorbing ultraviolet light at 200-400nm to generate free radicals, and is one or more of 2-hydroxy-2-methyl propiophenone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), diphenyl ketone and methyl o-benzoyl benzoate, and a composition of 1173,184, TPO and the like is generally preferred.
The colorant generally refers to a coloring matter substance containing 20% of transparent dye and mainly plays a role in dyeing.
The ultraviolet light curing coating composition has the advantages that after ultraviolet light curing, the composition is subjected to metal (copper wire) coating test, the high temperature resistance is 200 ℃, the volume resistivity is up to, and the dielectric loss 50HZ is up to 0.001-0.004.
For a better understanding of the present invention, reference will now be made to the following examples, but the scope of the invention as claimed is not limited to the scope of the examples. The experimentally measured values are measured in adaptation to the environment and will vary according to different materials and environments.
Throughout this application, the following terms have the indicated meanings:
adding polymerization inhibitor HEMQ, TMPTA and diphenylamine ether DADPE to react for 2 hours at 35-45 ℃ to reach a specified amine value, adding trimellitic anhydride TMPA to react for 4 hours at 100-120 ℃ to reach an acid value, adding phenolic epoxy resin E51A, reacting for 2 hours at 95-100 ℃ with catalyst TEBA and PHEA, and reacting for 3 hours at 110-120 ℃ with temperature control, wherein the acid value is reduced to 5mgKOH/g. Is denoted as MPA1
EXAMPLE 2 Synthesis of polyaniline ether acrylate resins
Adding polymerization inhibitor HEMQ, PETA and diphenylamine ether DADPE to react for 2 hours at 35-45 ℃ to reach a specified amine value, adding trimellitic anhydride TMPA to react for 4 hours at 100-120 ℃ to reach an acid value, adding phenolic epoxy resin E51A, reacting for 2 hours at 95-100 ℃ with catalyst TEBA and PHEA, and reacting for 3 hours at 110-120 ℃ with temperature control, wherein the acid value is reduced to 5mgKOH/g. Is marked as MPA2
EXAMPLE 3 Synthesis of polyaniline ether acrylate resins
Adding polymerization inhibitor HEMQ, TMPTA, TMPTMA and diphenylamine ether DADPE, reacting at 35-45 ℃ for 2 hours to reach a specified amine value, adding trimellitic anhydride TMPA, reacting at 100-120 ℃ for 4 hours to reach an acid value, adding phenolic epoxy resin E51A, catalyst TEBA and PHEA, reacting at 95-100 ℃ for 2 hours, controlling the temperature at 110-120 ℃ for 3 hours, and reducing the acid value to 5mgKOH/g. Is marked as MPA3
Example 4 preparation of UV-curable insulating coating
The coating was formulated as in Table 1 below
The A and the B are respectively prepared into a coating.
Example 5 preparation of UV-curable coatings
The coating was formulated as in Table 2 below
The components C and D are respectively prepared into the paint.
Example 6 preparation of UV-curable coating
The coating was formulated as in Table 3 below
Example 7
Three groups of coatings of examples 4,5 and 6 were formed into films of 1000mj/cm using 100 μm applicators, respectively 2 Curing under an ultraviolet lamp, and respectively testing the volume resistivity, dielectric coefficient, dielectric loss and high temperature resistance of the curing degree, wherein the test results are as follows:
as can be seen from the table above, the synthesized several resins have high volume resistivity, low dielectric coefficient and dielectric loss, high temperature resistance exceeding 200 ℃ and are H-grade insulating coatings meeting the requirements compared with the comparative common UV cured epoxy resin and polyurethane acrylate in the formula.
Claims (7)
1. The ultraviolet light-curable H-grade insulating coating composition is characterized by comprising the following components in parts by mass:
a) 40-60 parts of polyaniline ether acrylate resin;
b) 30-50 parts of acrylic ester monomer;
c) Polymerization inhibitor-0.5-1 part;
d) 5-8 parts of photoinitiator;
e) 0.1-0.5 part of colorant;
wherein the polyaniline ether acrylate resin is the reaction product of:
i) A triacrylate;
ii) p-aminophenyl ether;
iii) A polymerization inhibitor;
iv) trimellitic anhydride;
v) a catalyst;
vi) phenolic epoxy resin;
vii) acrylate monomers;
wherein the phenolic epoxy resin has an epoxy value of 170-195eq/100g, the polymerization inhibitor is a phenolic antioxidant, and the catalyst is quaternary ammonium salt or tertiary amine; the acrylic ester monomer is acrylic ester with monofunctional groups containing benzene rings or amide groups; the triacrylate is acrylate monomer containing three functional groups; the polyaniline ether acrylate resin synthesis process is that polymerization inhibitor, triacrylate and p-aminophenether are added to react for 2 hours at 35-45 ℃, trimellitic anhydride is added to react for 4 hours at 100-120 ℃, phenolic epoxy resin, catalyst and acrylate monomer are added to react for 2 hours at 95-100 ℃, the temperature is controlled to react for 3 hours at 110-120 ℃, and the acid value is reduced to 5mgKOH/g.
2. The uv curable H-stage insulating coating composition of claim 1, wherein said Vii) acrylate monomer is any of 2-phenoxyethyl acrylate, 2- (1, 2 cyclohexanedicarboxylic imide) ethyl acrylate.
3. The ultraviolet light-curable H-stage insulating coating composition according to claim 1 or 2, wherein the polymerization inhibitor is p-hydroxyanisole or 2-tert-butylhydroquinone.
4. The ultraviolet light-curable H-stage insulating coating composition according to claim 1 or 2, wherein the catalyst is any one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.
5. The uv-curable H-stage insulating coating composition according to claim 1 or 2, wherein the triacrylate comprises any one of trimethylolpropane triacrylate, pentaerythritol triacrylate, and trimethylolpropane trimethacrylate.
6. The uv curable H-stage insulating coating composition of claim 1, wherein the p-aminophenether is 4,4' -oxydiphenylamine ether.
7. The method for preparing the ultraviolet-curable H-level insulating coating composition according to any one of claims 1 to 6, which is characterized in that polyaniline ether acrylate resin is prepared first and then compounded with other components.
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| CN114133869A (en) * | 2021-12-17 | 2022-03-04 | 重庆绿涂腾科技有限公司 | Graphene-modified ultraviolet-curing insulating paint and preparation method thereof |
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