CN103130964A - Solvent-free impregnating resin for low voltage motor and medium voltage motor and solidification method - Google Patents
Solvent-free impregnating resin for low voltage motor and medium voltage motor and solidification method Download PDFInfo
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- CN103130964A CN103130964A CN2013100469772A CN201310046977A CN103130964A CN 103130964 A CN103130964 A CN 103130964A CN 2013100469772 A CN2013100469772 A CN 2013100469772A CN 201310046977 A CN201310046977 A CN 201310046977A CN 103130964 A CN103130964 A CN 103130964A
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Abstract
The invention discloses a solvent-free impregnating resin for a low voltage motor and a medium voltage motor. The solvent-free impregnating resin is composed of, by weight, 40-60% of heat-resisting unsaturated polyester resin, 5-10% of benzoxazine imine resin, 10-15% of epoxy resin, 0.5-2.0% of initiator, 7.0-15% of reactive diluent, 7.0-20% of curing agent and 0.1-1.0% of curing accelerator Due to the fact that benzoxazine imine modified unsaturated solvent-free impregnating resin is synthesized by the benzoxazine imine resin, heat resistance of the impregnating resin is improved, and heat resistance of epoxy unsaturated resin is enabled to increase to the heat-resisting level of polyester imide. Besides, compounded with the high-performance curing agent, the fact that defects of short storage life, bad thermal state surface dryness, large shrinking percentage, low hanging paint amount and low cohesive force in general solvent-free resin are overcome is guaranteed. Further, the solvent-free impregnating resin is excellent in combination property, especially, the cohesive force is as high as 241N, and similar impregnating resin can not achieve the cohesive force easily.
Description
Technical field
The present invention relates to a kind of solvent impregnated resin, specifically relate to a kind of low, Medium-voltage motor with solvent-free impregnating resin and curing.
Background technology
In the production process of electromechanics, the dipping of wire loop is a standard operation.Solvent impregnated resin after curing has mechanical fixed coil, prevents chemical corrosion and reduces environmental influence, removes the heat of generation, and the function that electrical isolation is provided.
The heat-resisting solvent-free impregnating resin that H level electrical equipment and electrical coil is used is indispensable important insulating material during current electrical equipment and electrical is made, and abroad this class solvent impregnated resin is all generally the polyester-imide type of using, the domestic phenyl ether series of using before 2000 more.And the domestic multiplex epoxy polyester type of the solvent-free impregnating resin of F level.The solvent impregnated resin better performances of polyester-imide type, but cost is higher, and technological process is more complicated; The solvent impregnated resin of phenyl ether series produces low-molecular material because viscosity is poor during curing, its performance is not high; Unsaturated polyester technique is simple, can accomplish high temperature resistantly, and low as solvent impregnated resin viscosity, the usage period is long, but more crisp after solidifying, shrinking percentage is large, and is easy to crack; The solvent-free impregnating resin of epoxies, material is easy to get, simple process, electromechanical properties are superior, but thermotolerance is not high.
Application number is that the patent documentation of CN201110101053.9 discloses a kind of environment-friendly type solvent-free solvent impregnated resin, and described solvent impregnated resin comprises by the weight part of each component: high heat resistant unsaturated polyester resin: 100 weight parts; Modified epoxy 0～100 weight part; Novel active thinner 50～200 weight parts; Stopper 0.1～1 weight part; Initiator 1.5～3.8 weight parts; Auxiliary agent 0～2 weight part.This solvent-free impregnating resin is compared with solvent impregnated resin with the no-solvent type mesolow of present routine; In identical workpiece situation, this resin can shorten curing the time of 1/3 left and right, saves the energy consumption of 25% left and right.But still can't solve the not high technical problem of solvent-free impregnating resin thermotolerance of the epoxies of present existence.
Summary of the invention
The invention provides a kind of low, Medium-voltage motor solvent-free impregnating resin, this resin solidification good manufacturability, fugitive constituent are little, excellent storage stability, good heat resistance, the cured product physical strength is high, electrical insulation properties good, dielectric loss is little and good flame resistance, can be used for insulating impregnating varnish, insulating encapsulating material field.
A kind of low, Medium-voltage motor solvent-free impregnating resin, by weight percentage, it consists of:
Heat resistant unsaturated polyester resin add the resistance toheat that has greatly improved solvent-free impregnating resin, described heat resistant unsaturated polyester resin our company manufacture voluntarily obtains, and two or more polyprotonic acids, at least a polyvalent alcohol occur under high temperature or catalyst action that micromolecular water is deviate from polycondensation and the polymkeric substance made.
Described polyprotonic acid is Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, m-phthalic acid or fumaric acid.
Described polyvalent alcohol is propylene glycol, glycol ether, three diglycol ethylenes, neopentyl glycol or TriMethylolPropane(TMP).
Described benzoxazine imide resin (formula III), can utilize existing method at first to prepare polyphenyl and oxazines resin during use, graft polymerization reaction occurs with the monomer that contains imine group and worth in i.e. synthetic benzo 6-membered heterocyclic compound-benzoxazine resin (formula I) take phenolic compound, aminated compounds and formaldehyde as raw material, benzoxazine resin under heat effect.Compare with general imide resin, the benzoxazine imide resin does not have small molecules to emit in the forming and hardening process, and the goods porosity is low, approaches zero and shrinks, and curing process is good, and the physical strength of the solvent-free impregnating resin for preparing is good.
() benzoxazine colophony I
(II) bismaleimides
() benzoxazine imide resin III
R wherein
1, R
2Be independently H, alkyl, aryl amine or aryl respectively, for example alkyl can be selected CH
3CH
2-wait, aryl can select C
6H
5-, C
6H
4CH
3-etc.R is
Deng
The described monomer that contains imine group is bismaleimides (formula II) or 4,4-dimethyl diphenyl methane.
Described epoxy resin is one or more in bisphenol A type epoxy resin (E44, E51 that Manufacturing Co., Ltd of nation of Shanghai unit or Ba Ling petrochemical industry epoxy resin division department provide), novolac epoxy (F51, F44 that Ba Ling petrochemical industry epoxy resin division department or Jiangsu Miki Group provide).
Described initiator is one or more in benzoyl peroxide, dicumyl peroxide.
Described reactive thinner is preferably one or more the mixture in vinylbenzene, Vinyl toluene, diallyphthalate acid esters.
Described solidifying agent is that anhydrides, boron amide class, imidazoles, triphenylphosphine are Ji the mixture of one or more of Qi phosphonium salt.For example solidifying agent commonly used comprises one or more in tung oil acid anhydride, phenylimidazole, methyl hexahydrophthalic anhydride.
Described curing catalyst is one or more mixture of metal salt of organic carboxylic acid, acetyl acetone salt.For example, preferred curing catalyst is aluminium acetylacetonate or cobalt naphthenate etc.Perhaps curing catalyst is selected the mixture of aluminium acetylacetonate and three-(dimethylamino methyl) phenol.
The preparation method of above-mentioned benzoxazine imide resin modified heat resistant unsaturated polyester solvent-free impregnating resin is: by formula, each component is mixed and namely get described low, Medium-voltage motor solvent-free impregnating resin.
The present invention also provides the curing of a kind of above-mentioned low, Medium-voltage motor with solvent-free impregnating resin, use that this is low, when Medium-voltage motor is used solvent-free impregnating resin, can select impregnation technology according to concrete needs, impregnation technology should be well known in the art, is not described in detail in this.Preferred condition of cure is to solidify 4-8 hour between 135-150 ℃.
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) the present invention adopts and introduce benzoxazine imide resin looped network shape structure in epoxy unsaturated polyester system, system itself has good consistency and matching, and has advantages of the synchronous curing of unsaturated polyester-epoxy resin-benzoxazine imide resin three systems, be equipped with again high performance solidifying agent and auxiliary agent, make in its solidification process and emit without small molecules, make solvent impregnated resin have to solidify fugitive constituent little, excellent storage stability, cohesive strength high (exceed industry standard 65%), heat radiation and good heat resistance, the cured product physical strength is high, electrical insulation properties is good, dielectric loss is little, the characteristics such as good flame resistance, and with insulated wire, good adhesiveproperties is arranged, and without the verdigris phenomenon.
When (2) reality is used, each component is mixed the solvent impregnated resin that can make high bond strength of the present invention, its manufacturing process is simple and form good stability, is applicable to large and medium-sized low, the Medium-voltage motor of H, C level, specific type of electric machine, the vacuum pressure impregnation of electrical equipment winding and the insulation impregnating that immerses of special heat resisting motor and processes.Simultaneously applicable to the electrical equipment and electrical of various temperature resistant grades, be applicable to also that vat immerses, immerses continuously, VPI impregnation technology, rotary roasting etc. processing requirement.
(3) the present invention has adopted the benzoxazine imide resin to synthesize the imine modified unsaturated solvent-free impregnating resin of benzoxazine, improved the thermotolerance of solvent impregnated resin, make the thermotolerance of epoxy unsaturated polyester rise to the thermal level of polyester-imide, be equipped with the high-performance solidifying agent, guaranteed that this solvent impregnated resin has overcome the conventional solventfree resin shelf lives short, hot surface drying is poor, shrinking percentage is large, hang the shortcomings such as the low and cohesive force of paint amount is not high and, excellent combination property, particularly cohesive force (spiral winding method) is up to 241N, this is that similar solvent impregnated resin is unapproachable.
Embodiment
The present invention will be described in detail below in conjunction with specific embodiment.
Below in each embodiment, heat resisting unsaturated polyester, benzoxazine imide resin have all been selected the product (following related " part " is weight part) of Haining large electric novel material company limited autonomous production forever.
The heat resisting unsaturated polyester preparation:
Less than 15mgKOH/g, Dehydration gets heat resisting unsaturated polyester at 180～220 ℃ of reaction acid numbers for 18 parts of 30 parts of neopentyl glycol, 20 parts of glycol ethers, 25 parts of m-phthalic acids, 12 parts of MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride.
The preparation of benzoxazine imide resin:
(1) will use salt acid for adjusting pH value to 2 after 37 parts of phenol and 35 parts of mixing of formaldehyde, temperature rising reflux 2h, regulate pH to 8-9 with sodium hydroxide again, add again 11 parts, 50 parts of toluene and formaldehyde, drop into 4 in batches, 17 parts of insulation back flow reaction of 4-diaminodiphenylmethane are (the terminal point determining condition is: molding time is 4-5min/170 ℃, the little skill in using a kitchen knife in cookery) to terminal, and vacuum makes benzoxazine colophony after taking out desolventizing.
(2) adding 25 parts of dimethyl formamides in reactor in addition, be warmed up to 100-110 ℃ and add 4,15 parts of 10 parts of 4-diaminodiphenylmethane and bismaleimidess, stirring and dissolving, and (the terminal point determining condition is: molding time is 2.5-3.5min/180 ℃ to terminal at 100-110 ℃ of insulation reaction 1-2h, the little skill in using a kitchen knife in cookery), add 50 parts of benzoxazine colophonies, continuation reacts to terminal under 100-110 ℃ that (the terminal point determining condition is: molding time is 1.5-2.0min/180 ℃, the little skill in using a kitchen knife in cookery) add 20 parts of thinner toluene, namely make the benzoxazine imide resin.
Embodiment 1
Low, Medium-voltage motor according to the present embodiment with the formula of solvent-free impregnating resin are:
Heat resisting unsaturated polyester 60g, benzoxazine imide resin 10g, bisphenol A epoxide resin (E44) 5g, novolac epoxy (F44) 5g, initiator are that dicumyl peroxide (DCP) 1.0 grams, reactive thinner are that diallyphthalate acid esters (DAP) 10 grams, solidifying agent are tung oil acid anhydride 10 grams, promotor cobalt naphthenate 0.2g.
After above-mentioned each component is mixed by formula, namely make low, Medium-voltage motor solvent-free impregnating resin.This solvent impregnated resin in use should be at 145 ℃ of left and right curing reactions 5 hours, i.e. curable film-forming.
Embodiment 2
Low, Medium-voltage motor according to the present embodiment with the formula of solvent-free impregnating resin are:
Heat resisting unsaturated polyester 50g, benzoxazine imide resin 10g, novolac epoxy 15g, initiator are that benzoyl peroxide (BPO) 2.0g, reactive thinner are that vinylbenzene (ST) 15g, solidifying agent are phenylimidazole 7.0g, promotor aluminium acetylacetonate 0.4g.
After above-mentioned each component is mixed by formula, namely make low, Medium-voltage motor solvent-free impregnating resin.This solvent impregnated resin in use should be at 145 ℃ of left and right curing reactions 5 hours, i.e. curable film-forming.
Embodiment 3
Low, Medium-voltage motor according to the present embodiment with the formula of solvent-free impregnating resin are:
Heat resisting unsaturated polyester 45g, benzoxazine imide resin 7g, bisphenol A epoxide resin 10g, novolac epoxy 5g, initiator are that dicumyl peroxide (DCP) 1.0 grams, reactive thinner are that Vinyl toluene 10 grams, solidifying agent are tung oil acid anhydride 20 grams, promotor aluminium acetylacetonate 0.4g.
After above-mentioned each component is mixed by formula, namely make low in, the Medium-voltage Motor solvent-free impregnating resin.This solvent impregnated resin in use should be at 145 ℃ of left and right curing reactions 5 hours, i.e. curable film-forming.
Embodiment 4
Low, Medium-voltage motor according to the present embodiment with the formula of solvent-free impregnating resin are:
Heat resisting unsaturated polyester 40 grams, benzoxazine imide resin 10g, bisphenol A epoxide resin 15g, initiator are that benzoyl peroxide (BPO) 2.0 grams, reactive thinner are that Vinyl toluene 13 grams, solidifying agent are that methyl hexahydrophthalic anhydride 20 grams, promotor are aluminium acetylacetonate 0.2g and three-(dimethylamino methyl) phenol 0.1g.
After above-mentioned each component is mixed by formula, namely make low, Medium-voltage motor solvent-free impregnating resin.This solvent impregnated resin in use should be at 145 ℃ of left and right curing reactions 5 hours, i.e. curable film-forming.
In sum, after each component is mixed by formula, namely get solvent-free impregnating resin of the present invention, this is low, Medium-voltage motor is simple with the solvent-free impregnating resin manufacturing process, form good stability, and stability in storage is good.
Prepare resin and domestic conventional resins (CH1150-VA) and imported from America product (DolphonCC1105) by embodiment 1 and carry out Performance Detection, detected result sees Table 1
Table 1
As shown in Table 1, Solvent-Impregnated Resins of the present invention is to introduce benzoxazine imide resin looped network shape structure to compare with the solvent-free impregnating resin of domestic at present general epoxy-unsaturated polyester type in epoxide modified heat resisting unsaturated polyester system, its thermotolerance is higher, reach the H-C level, and domestic general epoxy polyester type can only reach the F-H level, and over-all properties is better.Simultaneously, Solvent-Impregnated Resins of the present invention 319H of the present invention compares with external similar polyester-imide solvent-free impregnating resin, and performance reaches fully and surpassed same kind of products at abroad,
In addition,, with the beneficial effect of solvent-free impregnating resin low, the Medium-voltage motor of embodiment 1～4 are tested according to the corresponding national standard of insullac with the performance of solvent-free impregnating resin in order to prove low, Medium-voltage motor of the present invention, be the results are shown in Table 2.
The performance test data that table 2 is low, Medium-voltage motor is used solvent-free impregnating resin
As shown in Table 2, low, Medium-voltage motor solvent-free impregnating resin excellent storage stability of the present invention; With low, Medium-voltage motor, the electrical equipment winding that solvent-free impregnating resin of the present invention carries out that insulation impregnating processes, its cohesive strength high (exceed industry standard 65%), good insulation preformance, physical strength are high.
Claims (10)
1. one kind low, Medium-voltage motor solvent-free impregnating resin is characterized in that, by weight percentage, it consists of:
2. low, Medium-voltage motor solvent-free impregnating resin according to claim 1, is characterized in that, described epoxy resin is one or more in bisphenol A type epoxy resin, novolac epoxy.
3. low, Medium-voltage motor solvent-free impregnating resin according to claim 1, is characterized in that, described initiator is one or both in benzoyl peroxide, dicumyl peroxide.
4. low, Medium-voltage motor solvent-free impregnating resin according to claim 1, is characterized in that, described reactive thinner is one or more in vinylbenzene, Vinyl toluene, diallyphthalate acid esters.
5. low, Medium-voltage motor solvent-free impregnating resin according to claim 1, is characterized in that, described solidifying agent is that anhydride curing agent, boron amide solidifying agent, imidazole curing agent, triphenylphosphine are Ji one or more of Qi phosphonium salt.
6. low, Medium-voltage motor solvent-free impregnating resin according to claim 5, is characterized in that, described solidifying agent is one or more in tung oil acid anhydride, phenylimidazole, methyl hexahydrophthalic anhydride.
7. low, Medium-voltage motor solvent-free impregnating resin according to claim 1, is characterized in that, described curing catalyst is one or more of metal salt of organic carboxylic acid, acetyl acetone salt.
8. low, Medium-voltage motor solvent-free impregnating resin according to claim 7, is characterized in that, described curing catalyst is aluminium acetylacetonate or cobalt naphthenate.
9. low, Medium-voltage motor solvent-free impregnating resin according to claim 1, is characterized in that, described curing catalyst is the mixture of aluminium acetylacetonate and three-(dimethylamino methyl) phenol.
10. the curing of a solvent-free impregnating resin, it is characterized in that, described solvent-free impregnating resin is described low, the Medium-voltage motor solvent-free impregnating resin of the arbitrary claim of claim 1-9, and condition of cure is: solidified 4-8 hour between 135-150 ℃.
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| CN104263203A (en) * | 2014-10-09 | 2015-01-07 | 六安市微特电机有限责任公司 | Water-resistant and waterproof solvent-free impregnating varnish and preparation method thereof |
| CN105086735A (en) * | 2014-12-19 | 2015-11-25 | 赵雅珺 | Enameled wire insulation varnish |
| CN106497363A (en) * | 2016-11-03 | 2017-03-15 | 株洲时代电气绝缘有限责任公司 | A kind of wet-heat resisting solvent-free immersion paint and preparation method thereof |
| CN106633586A (en) * | 2016-12-14 | 2017-05-10 | 四川东材科技集团股份有限公司 | Halogen-free phosphate-free flame-retardant unsaturated polyester resin composition and application thereof |
| CN106810919A (en) * | 2017-01-11 | 2017-06-09 | 合肥英索莱特新材料科技有限公司 | Epoxy solventless baking insulating varnish |
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| CN107353642A (en) * | 2017-07-11 | 2017-11-17 | 苏州生益科技有限公司 | Resin combination and prepreg, metal foil laminate and the interlayer dielectric using its making |
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| CN105086735A (en) * | 2014-12-19 | 2015-11-25 | 赵雅珺 | Enameled wire insulation varnish |
| CN106497363A (en) * | 2016-11-03 | 2017-03-15 | 株洲时代电气绝缘有限责任公司 | A kind of wet-heat resisting solvent-free immersion paint and preparation method thereof |
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| CN106633586A (en) * | 2016-12-14 | 2017-05-10 | 四川东材科技集团股份有限公司 | Halogen-free phosphate-free flame-retardant unsaturated polyester resin composition and application thereof |
| CN106810919A (en) * | 2017-01-11 | 2017-06-09 | 合肥英索莱特新材料科技有限公司 | Epoxy solventless baking insulating varnish |
| CN107353643A (en) * | 2017-07-11 | 2017-11-17 | 苏州生益科技有限公司 | A kind of resin combination and prepreg, metal foil laminate and the interlayer dielectric using its making |
| CN107353642B (en) * | 2017-07-11 | 2019-06-04 | 苏州生益科技有限公司 | Resin combination and prepreg, metal foil laminate and the interlayer dielectric made using it |
| CN107353642A (en) * | 2017-07-11 | 2017-11-17 | 苏州生益科技有限公司 | Resin combination and prepreg, metal foil laminate and the interlayer dielectric using its making |
| CN107353643B (en) * | 2017-07-11 | 2019-09-03 | 苏州生益科技有限公司 | A kind of resin combination and prepreg, metal foil laminate and interlayer dielectric using its production |
| CN107384130A (en) * | 2017-08-18 | 2017-11-24 | 株洲时代新材料科技股份有限公司 | A kind of impregnating resin composition and its application |
| CN107384130B (en) * | 2017-08-18 | 2019-06-21 | 株洲时代新材料科技股份有限公司 | A kind of impregnating resin composition and its application |
| CN111440518A (en) * | 2020-04-26 | 2020-07-24 | 山西博拉哲绝缘技术有限公司 | High-heat-resistance environment-friendly refrigerant-resistant insulating impregnating resin and preparation method thereof |
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