CN111100530A - Water-emulsion epoxy insulating impregnating varnish and preparation method thereof - Google Patents
Water-emulsion epoxy insulating impregnating varnish and preparation method thereof Download PDFInfo
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- CN111100530A CN111100530A CN201911253791.8A CN201911253791A CN111100530A CN 111100530 A CN111100530 A CN 111100530A CN 201911253791 A CN201911253791 A CN 201911253791A CN 111100530 A CN111100530 A CN 111100530A
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- water
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- impregnating varnish
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- epoxy resin
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- 239000000839 emulsion Substances 0.000 title claims abstract description 68
- 239000004593 Epoxy Substances 0.000 title claims abstract description 48
- 239000002966 varnish Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 73
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 73
- 239000007787 solid Substances 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229920003180 amino resin Polymers 0.000 claims abstract description 29
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 10
- 239000006184 cosolvent Substances 0.000 claims abstract description 9
- 150000007530 organic bases Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002383 tung oil Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000539 dimer Substances 0.000 claims description 8
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- 229920003265 Resimene® Polymers 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- -1 dodecyl alcohol ester Chemical class 0.000 claims description 6
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 5
- 229920003275 CYMEL® 325 Polymers 0.000 claims description 5
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 5
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 4
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 4
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920003270 Cymel® Polymers 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000004804 winding Methods 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- 238000009775 high-speed stirring Methods 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 238000002715 modification method Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a water-emulsion epoxy insulating impregnating varnish, which consists of 10-15% of solid epoxy resin, 4-6% of polybasic acid (anhydride), 4-7% of cosolvent/film-forming assistant, 1-3% of neutralizer organic base, 2-5% of amino resin curing agent and the balance of water; firstly, heating the solid epoxy resin and the polybasic acid (anhydride) in a cosolvent at low temperature for melting and dissolving, and then heating for esterification reaction; cooling after the reaction is finished, and dripping organic alkali aqueous solution under the action of high-speed stirring to prepare aqueous epoxy emulsion; and finally, adding amino resin and water for dilution, stirring and dissolving to obtain the water emulsion epoxy insulating impregnating varnish, wherein the cured coating is thin, can be used for impregnating and insulating coil windings and iron cores of small and medium-sized low-voltage motor electrical parts, and has excellent characteristics in the aspects of storage stability, water resistance, mechanical properties and the like.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to water-emulsion epoxy insulating impregnating varnish and a simple preparation method thereof.
Background
In the process of insulating dipping treatment of various domestic motor production enterprises, the adopted insulating dipping paint contains a large amount of flammable, explosive, toxic and harmful solvents such as toluene, xylene, styrene, solvent oil and the like, and diluents, so that environmental pollution of factories and damage to the health of personnel are inevitably caused. With the continuous improvement of environmental protection requirements of various countries, materials used for motor products are subject to stricter and stricter limitations. Therefore, the development and application of the environment-friendly insulating impregnating varnish with low viscosity and low organic volatile is urgent.
Similar to solvent-based insulating impregnating varnish, the curing coating of the water-based insulating impregnating varnish is thinner, so the water-based insulating impregnating varnish can be generally used for the impregnating insulation treatment of parts such as stators, rotors, coil windings, armatures, iron cores and the like of small and medium-sized low-voltage motor and electrical appliances (such as small and medium-sized transformers, starters, generators, compressors and the like). Besides the characteristics of common insulating paint (i.e. solvent type insulating paint), the water-based insulating impregnating varnish also has the characteristics of environmental protection, nonflammability, explosiveness and the like, meets the environmental protection requirement and is more and more popular with users.
The types of the existing water-based insulating paint are mainly divided into two major types, one type is water-soluble insulating paint taking water as a solvent, and the water-soluble insulating paint comprises water-soluble phenolic resin insulating paint, water-soluble alkyd resin insulating paint, water-soluble polyester insulating paint and the like; the other is water-emulsion insulating paint using water as dispersion medium, such as water-emulsion polyurethane insulating paint, water-emulsion epoxy resin insulating paint, etc. Among them, epoxy resins are one of the synthetic resins that have been developed to be water-based in the earliest stage and have the highest productivity because of their excellent properties such as adhesion, corrosion resistance, stability, insulation properties, and mechanical strength.
Since the original epoxy resin is mostly viscous liquid or solid, is soluble in organic solvent and is insoluble in water; the epoxy resin water-based modification needs to introduce hydrophilic polar groups, such as carboxyl, amino, polyoxyethylene chain segments and the like, into a hydrophobic molecular chain of the epoxy resin.
Two common methods for preparing waterborne epoxy resins are: (1) anion modification method: grafting an acrylic polymer on an epoxy resin molecular chain through free radical polymerization reaction; (2) non-ionic modification method: with Lewis acids (e.g. BF)3) As a catalyst, polyethylene glycol is introduced into an epoxy molecular chain through an epoxy etherification ring-opening reaction. The aqueous epoxy resins prepared by the two methods have good performance, but have some inevitable problems, such as large smell and long synthesis time of the aqueous epoxy resin obtained by acrylic acid grafting modification due to the problem of acrylic acid monomer residue, poor stability (easy sedimentation) of the aqueous epoxy resin obtained by nonionic modification, and raw materials (such as BF) used3Ether solution) is toxic and volatile.
Therefore, a method for simply and safely preparing the water-emulsion epoxy resin with better stability and the insulating impregnating varnish thereof needs to be developed.
Disclosure of Invention
One of the purposes of the invention is to provide a water-emulsion epoxy insulating paint impregnating varnish, which overcomes the defects of the preparation of the common water-emulsion epoxy insulating paint and is a synthetic material with excellent electrical, mechanical, heat-resistant and moisture-resistant performances.
The technical scheme adopted by the invention for solving the technical problems is as follows: the water emulsion epoxy insulating impregnating varnish consists of solid epoxy resin 10-15 wt%, polybasic acid (anhydride) 4-6 wt%, cosolvent/filming assistant 4-7 wt%, organic alkali as neutralizer 1-3 wt%, amino resin curing agent 2-5 wt% and water 60-80 wt%.
The solid epoxy resin of the water-emulsion epoxy insulating impregnating varnish is bisphenol A diglycidyl ether type high-molecular-weight curing epoxy resin, wherein the solid epoxy resin comprises one or a mixture of more of solid epoxy resins with the brands of E-06, E-12 and E-20.
The polybasic acid (anhydride) of the water-emulsion epoxy insulating impregnating varnish is one or a mixture of two of adipic acid, sebacic acid, dimer acid, trimellitic anhydride, pyromellitic dianhydride and tung oil anhydride.
The cosolvent or film-forming assistant of the water-emulsion epoxy insulating impregnating varnish is one or a mixture of two of propylene glycol butyl ether, propylene glycol propyl ether, ethylene glycol monobutyl ether, ethylene glycol tertiary butyl ether and dodecyl alcohol ester (Texanol).
The water-emulsion epoxy insulating impregnating varnish is characterized in that a neutralizing agent organic base is one or a mixture of two of triethylamine, diethanolamine, N-dimethylethanolamine and 2-amino-2-methyl-1-propanol (AMP-95).
The water-emulsion epoxy insulating impregnating varnish is characterized in that the amino resin curing agent is one or a mixture of two of Resimene 717 amino resin, Resimene 718 amino resin, Cymel 325 amino resin, Cymel327 amino resin, Cymel 385 amino resin and Jiangsu Sanmu 5717W amino resin.
The second purpose of the invention is to provide a preparation method of the water-emulsion epoxy insulating impregnating varnish, which has simple and easy preparation process, does not use organic solvent and protective agent, has economic and environment-friendly process and is easy for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a simple preparation method of water-emulsion epoxy insulating impregnating varnish comprises the following steps:
(1) adding solid epoxy resin, polybasic acid (anhydride) and cosolvent/coalescing agent into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 110-120 ℃, and stirring for dissolving;
(2) heating to 140-160 ℃ after the materials are completely dissolved and become clear, and reacting for 2-5 hours in a heat preservation way;
(3) cooling to about 70-80 ℃, and slowly dripping a prepared organic alkali water solution into the reaction system through a dropping funnel under the action of rapid stirring; after the dropwise adding is finished within 0.5-1 h, removing the heat source, naturally cooling, and continuously stirring for 2-3 h to prepare the water-based epoxy resin emulsion with the solid content of about 20%;
(4) and (3) stirring the aqueous epoxy resin emulsion, an amino resin curing agent and water according to a certain proportion for 2-3 h, and discharging to obtain the water-emulsion epoxy insulating impregnating varnish with the solid content of about 20%.
The invention has the beneficial effects that: the water-emulsion epoxy insulating impregnating varnish prepared by the invention has a thin cured coating, can be used for impregnating and insulating coil windings and iron cores of small and medium-sized low-voltage motor electrical appliance parts (such as stators, rotors, armatures and the like), and has excellent characteristics in the aspects of storage stability, water resistance, mechanical properties and the like.
Detailed Description
The synthesis and features of the present invention are more clearly illustrated by the following examples, but the scope of the invention as claimed is not limited to the following examples.
Example 1
Adding 100g of solid epoxy resin E-06, 8g of trimellitic anhydride and 40g of ethylene glycol monobutyl ether into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 110 ℃, and stirring for dissolving; heating to 145 ℃ after the materials are completely dissolved and become clear, and reacting for 4 hours in a heat preservation way; then cooling to about 70 ℃, slowly dripping an organic alkali water solution consisting of 12g N, N-dimethylethanolamine and 380g of water into the reaction system through a dropping funnel under the action of rapid stirring, removing a heat source to naturally cool after finishing dripping within 0.5-1 h, and continuously stirring for 2h to prepare a water-based epoxy resin emulsion with the solid content of about 20%; and finally, adding 22.68g of Cymel 325 amino resin with the solid content of about 80 percent and 68.04g of water into the waterborne epoxy resin emulsion, quickly stirring for 3 hours at room temperature, and discharging to obtain the waterborne epoxy insulating impregnating varnish with the solid content of about 20 percent.
Example 2
Adding 100g of solid epoxy resin E-12, 8g of pyromellitic dianhydride and 40g of propylene glycol butyl ether into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 110 ℃, and stirring for dissolving; heating to 160 ℃ after the materials are completely dissolved and become clear, and reacting for 4 hours in a heat preservation way; then cooling to about 70 ℃, slowly dripping an organic alkali water solution consisting of 12g of diethanolamine and 380g of water into the reaction system through a dropping funnel under the action of rapid stirring, removing a heat source for natural cooling after finishing dripping within 0.5-1 h, and continuously stirring for 2h to prepare an aqueous epoxy resin emulsion with the solid content of about 20%; and finally, adding 22.68g of 5717W amino resin with the solid content of about 80% and 68.04g of water into the aqueous epoxy resin emulsion, quickly stirring for 3 hours at room temperature, and discharging to obtain the water-emulsion epoxy insulating impregnating varnish with the solid content of about 20%.
Example 3
Adding 100g of solid epoxy resin E-12, 20g of adipic acid and 40g of ethylene glycol tert-butyl ether into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 120 ℃, and stirring for dissolving; heating to 160 ℃ after the materials are completely dissolved and become clear, and reacting for 4 hours in a heat preservation way; then cooling to about 70 ℃, slowly dripping an organic alkali aqueous solution consisting of 15g N, N-dimethylethanolamine and 425g of water into the reaction system through a dropping funnel under the action of rapid stirring, removing a heat source to naturally cool after finishing dripping within 0.5-1 h, and continuously stirring for 2h to prepare a water-based epoxy resin emulsion with the solid content of about 20%; and finally, adding 21g of Resimene 718 amino resin with the solid content of about 80% and 63g of water into the aqueous epoxy resin emulsion, quickly stirring for 3 hours at room temperature, and discharging to obtain the water-emulsion epoxy insulating impregnating varnish with the solid content of about 20%.
Example 4
Adding 100g of solid epoxy resin E-12, 20g of sebacic acid and 40g of propylene glycol propyl ether into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 120 ℃, and stirring for dissolving; heating to 160 ℃ after the materials are completely dissolved and become clear, and reacting for 4 hours in a heat preservation way; then cooling to about 70 ℃, slowly dripping an organic alkali aqueous solution consisting of 15g N, N-dimethylethanolamine and 425g of water into the reaction system through a dropping funnel under the action of rapid stirring, removing a heat source to naturally cool after finishing dripping within 0.5-1 h, and continuously stirring for 2h to prepare a water-based epoxy resin emulsion with the solid content of about 20%; and finally, adding 24g of Cymel327 amino resin with the solid content of about 80% and 72g of water into the waterborne epoxy resin emulsion, quickly stirring for 3 hours at room temperature, and discharging to obtain the water-emulsion epoxy insulating impregnating varnish with the solid content of about 20%.
Example 5
Adding 100g of solid epoxy resin E-20, 20g of tung oil anhydride and 40g of dodecyl alcohol ester (Texanol) into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 120 ℃, and stirring for dissolving; heating to 145 ℃ after the materials are completely dissolved and become clear, and reacting for 4 hours in a heat preservation way; then cooling to about 70 ℃, slowly dripping an organic alkali aqueous solution consisting of 10g N, N-dimethylethanolamine and 430g of water into the reaction system through a dropping funnel under the action of rapid stirring, removing a heat source to naturally cool after finishing dripping within 0.5-1 h, and continuously stirring for 2h to prepare a water-based epoxy resin emulsion with the solid content of about 20%; and finally, adding 25.2g of Cymel327 amino resin with the solid content of about 80% and 75.6g of water into the waterborne epoxy resin emulsion, quickly stirring for 3 hours at room temperature, and discharging to obtain the water-emulsion epoxy insulating impregnating varnish with the solid content of about 20%.
Example 6
Adding 100g of solid epoxy resin E-12, 8g of trimellitic anhydride, 30g of tung oil anhydride and 40g of ethylene glycol monobutyl ether into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 120 ℃, and stirring for dissolving; heating to 145 ℃ after the materials are completely dissolved and become clear, and reacting for 4 hours in a heat preservation way; then cooling to about 70 ℃, slowly dripping an organic alkaline aqueous solution consisting of 17g N, N-dimethylethanolamine and 495g of water into the reaction system through a dropping funnel under the action of rapid stirring, removing a heat source to naturally cool after finishing dripping within 0.5-1 h, and continuously stirring for 2h to prepare a water-based epoxy resin emulsion with the solid content of about 20%; and finally, adding 31.05g of Resimene 717 amino resin with the solid content of about 80% and 93.15g of water into the aqueous epoxy resin emulsion, quickly stirring for 3 hours at room temperature, and discharging to obtain the water-emulsion epoxy insulating impregnating varnish with the solid content of about 20%.
Example 7
Adding 100g of solid epoxy resin E-12, 8g of trimellitic anhydride, 30g of dimer acid and 40g of ethylene glycol monobutyl ether into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 120 ℃, and stirring for dissolving; heating to 145 ℃ after the materials are completely dissolved and become clear, and reacting for 4 hours in a heat preservation way; then cooling to about 70 ℃, slowly dripping an organic alkaline aqueous solution consisting of 17g of AMP-95 and 495g of water into the reaction system through a dropping funnel under the action of rapid stirring, removing a heat source to naturally cool after finishing dripping within 0.5-1 h, and continuously stirring for 2h to prepare an aqueous epoxy resin emulsion with the solid content of about 20%; and finally, adding 31.05g of Cymel 385 amino resin with the solid content of about 80% and 93.15g of water into the waterborne epoxy resin emulsion, quickly stirring for 3 hours at room temperature, and discharging to obtain the waterborne epoxy insulating impregnating varnish with the solid content of about 20%.
Example 8
Adding 5g of solid epoxy resin E-20 and 30g of dehydrated polyethylene glycol 6000 into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 75-85 ℃, heating to 95 ℃ after the solid epoxy resin and the polyethylene glycol 6000 are completely dissolved and uniformly stirred, dropwise adding a boron trifluoride diethyl etherate catalyst while stirring, and carrying out heat preservation reaction at 95 ℃ for 4 hours to obtain a nonionic emulsifier; heating all the emulsifiers, 195g of solid epoxy resin E-20 and 57.5g of ethylene glycol monobutyl ether to 75-85 ℃, stirring and dissolving uniformly, dripping 479.2g of distilled water under high-speed stirring for emulsification and dilution, and continuously stirring for 2-3 hours after the water is added to prepare an aqueous epoxy emulsion with the solid content of about 30%; and finally, adding 47.9g of Cymel 325 amino resin with the solid content of about 80% and 527g of distilled water into the whole water-based epoxy emulsion, and quickly stirring for 1-2 hours to obtain the water-based epoxy insulating impregnating varnish with the solid content of about 20%.
Example 9
Adding 100g of solid epoxy resin E-20 and 70g of ethylene glycol monobutyl ether into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 100-110 ℃, and stirring for dissolving; then dripping a monomer mixed solution prepared by dissolving 30g of acrylic ester, 5g of butyl acrylate, 5g of styrene and 2g of benzoyl peroxide in advance into the reaction system, stirring while dripping, controlling all the monomer mixed solution to be dripped within 1.5-2 h, and carrying out heat preservation reaction for 3-4 h at 100 ℃ after dripping; cooling to 80 ℃, stopping heating, slowly dripping an organic alkali water solution consisting of 18.5g of triethylamine and 560g of water into the reaction system through a dropping funnel, rapidly stirring while dripping, and continuously stirring for 2 hours after finishing dripping within 0.5-1 hour to prepare an aqueous epoxy resin emulsion with the solid content of about 20%; and finally, adding 29.2g of Cymel 325 amino resin with the solid content of about 80% and 1g of distilled water into the whole aqueous epoxy resin emulsion, and quickly stirring for 1-2 hours to obtain the water-emulsion epoxy insulating impregnating varnish with the solid content of about 20%.
The performance of the water-emulsion epoxy insulating impregnating varnish prepared in the embodiments 1 to 9 is tested, wherein the embodiments 8 and 9 are comparative examples, which relate to the preparation of the water-emulsion epoxy insulating impregnating varnish by using conventional methods (polyethylene glycol nonionic modification method and acrylic acid graft polymerization method, respectively), and the specific test results are shown in the following table (comparison table of performance test results of the water-emulsion epoxy insulating impregnating varnish).
As can be seen from the above table, the water-emulsion epoxy insulating impregnating varnish prepared in embodiments 1 to 9 of the present invention has high bonding strength, electrical strength and temperature index, which indicates that the water-emulsion epoxy insulating impregnating varnish provided by the present invention has good mechanical strength, electrical insulating property and heat resistance; wherein the performance of each aspect of the embodiment 6 is better.
In the process of the invention, one or a mixture of two of adipic acid, sebacic acid, dimer acid, trimellitic anhydride, pyromellitic dianhydride and tung oil anhydride is used as one of hydrophilic modifiers, and the hydrophilic modifier can be introduced into a molecular chain of the high molecular weight solid epoxy resin through controllable high-temperature esterification reaction, so that the molecular chain contains a certain amount of carboxyl groups. Wherein carboxyl can be neutralized by alkali to obtain carboxylate groups with good water solubility, thereby endowing the whole epoxy resin molecular chain with water emulsion; meanwhile, hydroxyl on a side chain of the solid epoxy resin provides a cross-linking point of intermolecular cross-linking reaction for a molecular chain of the water-based epoxy resin.
The invention adopts a simple one-step feeding method and synthesizes the waterborne epoxy resin with better hydrolytic stability and flexibility through high-temperature esterification reaction. In the high-temperature esterification reaction, one or a mixture of two of propylene glycol butyl ether, propylene glycol propyl ether, ethylene glycol monobutyl ether, ethylene glycol tertiary butyl ether and dodecyl alcohol ester (Texanol) is used as a solvent, one or a mixture of two of adipic acid, trimellitic anhydride, pyromellitic dianhydride and tung oil anhydride is used as a hydrophilic modifier, solid epoxy resin and reactants are completely dissolved at a lower temperature to obtain a uniform system, then the temperature is raised to carry out esterification reaction to synthesize aqueous epoxy resin, and then the aqueous epoxy resin is cooled and dropwise added with an organic alkaline aqueous solution to be stirred at a high speed to prepare the aqueous epoxy emulsion. Compared with other methods for synthesizing aqueous epoxy resin or aqueous epoxy emulsion (such as acrylic acid grafting modification method, nonionic modification method and the like), the method has the following advantages: the esterification reaction is carried out in the film-forming cosolvent at a lower temperature instead of a high-temperature molten state, so that the esterification reaction is more controllable (for example, the esterification reaction degree can be controlled by adjusting the reaction temperature and the reaction time), and the occurrence of gelation during high-temperature melting can be effectively avoided; in addition, the reaction is one-step feeding (one-pot method), the esterification reaction temperature is low, the reaction time is short, and the reaction raw materials do not contain toxic, volatile and smelly substances, so that the method for synthesizing the water-based epoxy resin or the water-based epoxy emulsion is simple, energy-saving, environment-friendly and safe; the waterborne epoxy emulsion synthesized by the method has the advantages of good stability, difficult sedimentation and good flexibility.
The invention adopts one or a mixture of two of long-chain acid (anhydride) -sebacic acid, dimer acid and tung oil anhydride as a modifier with hydrophilicity and hydrophobicity, so as to properly reduce the hydrophilicity of the waterborne epoxy resin and further improve the hydrolysis resistance and the storage stability of the waterborne epoxy resin. The ester bond is one of important factors influencing the hydrolytic stability of the aqueous epoxy resin, and the hydrolytic stability of the ester bond is generally improved by introducing a shielding protection group with larger steric hindrance or long hydrophobic alkyl chain around the ester bond. Compared with adipic acid, trimellitic anhydride and pyromellitic dianhydride, sebacic acid, dimer acid and tung oil anhydride are polybasic acid (anhydride) with long alkyl chains, and after the polybasic acid (anhydride) is grafted to an epoxy resin molecular chain through an esterification reaction, the long alkyl chains can form a shielding protection effect on ester bonds, so that the hydrolysis resistance of the ester bonds is improved; in addition, compared with the short-chain polybasic acid (anhydride), the reactivity of the long-chain polybasic acid (anhydride) is reduced, the long-chain polybasic acid (anhydride) is not easy to generate gelation phenomenon when reacting with the epoxy resin, and the reaction is more controllable.
The invention adopts one or a mixture of two of long-chain acid (anhydride) -sebacic acid, dimer acid and tung oil anhydride as a flexible modifier, and can improve the flexibility of the waterborne epoxy resin. Short-chain rigid polybasic acid (anhydride) -adipic acid, trimellitic anhydride and pyromellitic dianhydride mainly endow the waterborne epoxy resin with hydrophilicity, but can also cause the waterborne epoxy resin to have larger rigidity and larger brittleness; and the long-chain flexible polybasic acid (anhydride) -sebacic acid, dimer acid and tung oil anhydride can effectively improve the flexibility of the waterborne epoxy resin.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. The water-emulsion epoxy insulating impregnating varnish is characterized in that: the paint consists of solid epoxy resin 10-15 wt%, polybasic acid (anhydride) 4-6 wt%, cosolvent/filming assistant 4-7 wt%, organic alkali as neutralizer 1-3 wt%, amino resin curing agent 2-5 wt% and water for the rest.
2. The water-emulsion epoxy insulating impregnating varnish according to claim 1, characterized in that the solid epoxy resin is one or a mixture of several of the solid epoxy resins of the designations E-06, E-12, E-20.
3. The water-emulsion epoxy insulating impregnating varnish according to claim 1, characterized in that the polybasic acid (anhydride) is one or a mixture of two of adipic acid, sebacic acid, dimer acid, trimellitic anhydride, pyromellitic dianhydride, and tung oil anhydride.
4. The water-emulsion epoxy insulating impregnating varnish according to claim 1, characterized in that the cosolvent/coalescent is one or a mixture of two of propylene glycol butyl ether, propylene glycol propyl ether, ethylene glycol monobutyl ether, ethylene glycol tertiary butyl ether, and dodecyl alcohol ester (Texanol).
5. The water-emulsion epoxy insulating impregnating varnish according to claim 1, wherein the neutralizing agent organic base is one or a mixture of two of triethylamine, diethanolamine, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol (AMP-95).
6. The water-emulsion epoxy insulating impregnating varnish according to claim 1, wherein the amino resin curing agent is one or a mixture of two of Resimene 717 amino resin, Resimene 718 amino resin, Cymel 325 amino resin, Cymel327 amino resin, Cymel 385 amino resin and Jiangsu Sanmu 5717W amino resin.
7. The preparation method of the water emulsion epoxy insulating impregnating varnish according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) adding solid epoxy resin, polybasic acid (anhydride) and cosolvent/coalescing agent into a reaction bottle provided with a stirring device, a temperature control device and a reflux condensing device, heating to 110-120 ℃, and stirring for dissolving;
(2) heating to 140-160 ℃ after the materials are completely dissolved and become clear, and reacting for 2-5 hours in a heat preservation way;
(3) cooling to 70-80 ℃, and slowly dripping a prepared organic alkali water solution into the reaction system through a dropping funnel under the action of rapid stirring; after the dropwise adding is finished within 0.5-1 h, removing the heat source, naturally cooling, and continuously stirring for 2-3 h to prepare the aqueous epoxy resin emulsion with the solid content of 20%;
(4) and (3) stirring the aqueous epoxy resin emulsion, an amino resin curing agent and water according to a certain proportion for 2-3 h, and discharging to obtain the water-emulsion epoxy insulating impregnating varnish with the solid content of 20%.
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| CN114300805A (en) * | 2021-12-02 | 2022-04-08 | 厦门大学 | An all-solid-state battery with improved interface layer and method for improving electrode interface thereof |
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