CN102225986A - Environmentally-friendly type solvent-free impregnating resin and preparation method thereof - Google Patents
Environmentally-friendly type solvent-free impregnating resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environmentally-friendly type solvent-free impregnating resin and a preparation method thereof. The impregnating resin comprises: 100 parts by weight of one or more high heat-resistant unsaturated polyester resins, 0 to 100 parts by weight of one or more modified epoxy resins, 50 to 200 parts by weight of one or more novel reactive diluents, 0.1 to 1 parts by weight of one or more polymerization inhibitors, 1.5 to 3.8 parts by weight of one or more initiators and 0 to 2 parts by weight of one or more auxiliary agents. Under the same work conditions, a baking time of the solvent-free impregnating resin is less than about one third of a baking time of the existing conventional solvent-free type impregnating resin utilized for middle and low voltage motors and transformers, and an energy consumption of the solvent-free impregnating resin is lower than about 25% of an energy consumption of the existing conventional solvent-free type impregnating resin middle and low voltage motors and transformers.
Description
Technical field
The present invention relates to a kind of environment-friendly type solvent-free solvent impregnated resin and preparation method thereof, in being mainly used in, the insulation impregnating of low voltage motor and electrical equipment winding coil handles.
Background technology
Solvent impregnated resin is a kind of of insulating material, and the insulation impregnating that is mainly used in motor, transformer and diffusing embedding winding coil is handled, and edge, molding bonded and the dampproof effect of drawing last breath electrifies.The solvent impregnated resin that at present domestic and international high-low pressure motor and electrical equipment are used mainly is that fugitive constituent is big in the solidification process with the dilution of noxious solvents such as vinylbenzene, Vinyl toluene, and smell is big, has caused serious environmental to pollute and the wasting of resources.For consideration, develop a kind of low viscosity, no noxious solvent, to solidify the low environment-friendly type solvent-free solvent impregnated resin of fugitive constituent extremely urgent to environment, resource and human life's health.
Aspect solvent-free impregnating resin, launched extensive studies both at home and abroad in recent years.Some environment-friendly type solvent impregnated resin new variety have been developed abroad, Damisol 3630 resins as Herberts company of Du Pont 4200, E4050 and Switzerland Feng Luo group, matrix resin is a kind of unsaturated polyester-imide resin of single-component, and basic odorlessness solidifies fugitive constituent seldom.Domestic also do not have similar product so far.But, 4200 and E4050 solvent impregnated resin viscosity of E.I.Du Pont Company very big, need switch on heating, application art complexity, apparatus control system requires high, and production efficiency is low, can't use on present electrical equipment and electrical insulation impregnating treatment facility; The hot electric property of rich sieve 3630 solvent impregnated resins is poor, dielectric dissipation factor is big, the service requirements of piezoelectricity machine in being difficult to satisfy.
Therefore, research and develop a kind of low viscosity, no noxious solvent, solidify the environment-friendly type solvent-free solvent impregnated resin that fugitive constituent is low, mesolow is general, to the upgrading of China's insulated impregnating resin product, to the improvement of electrical equipment and electrical industry insulation impregnating processing environment, positive important practical sense is arranged.
Summary of the invention
For the wasting of resources and the problem of environmental pollution that overcomes the styrenic solvent-free impregnating resin, the objective of the invention is on the dielectric properties and stable on heating basis that keep original unsaturated polyester solvent impregnated resin excellence, introduce low viscous modified epoxy, the novel acrylic ester class cross-linking monomer that cooperates high reaction activity is prepared a kind of poisonous solvent, low viscosity, odorlessness, environment-friendly type solvent-free solvent impregnated resin that fugitive constituent is low of not containing.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind of environment-friendly type solvent-free solvent impregnated resin is characterized in that 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.
Preferably, described high heat resistant unsaturated polyester resin be selected from the unsaturated polyester resin, 4,4 of organic-silicon-modified unsaturated polyester resin, the modification of N-benzene maleimide '-one or more arbitrary combination of the bi-maleimide modified unsaturated polyester resin of ditane type, match gram modification metaphenylene unsaturated polyester resin, dicyclopentadiene synthetic unsaturated polyester resin, unsaturated polyester-imide resin;
Preferably, described novel active thinner is selected from phenyl methacrylate, cyclohexyl methacrylate, the methacrylic acid benzyl ester, lauryl methacrylate(LMA), 2-benzene oxygen ethyl-methyl acrylate, cyclohexyl acrylate, the vinylformic acid benzyl ester, dicyclopentadiene acrylate, Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), the dimethacrylate triglycol ester, 1,4-butyleneglycol diacrylate fat, 1,6 hexanediol diacrylate, the dimethacrylate triglycol ester, neopentylglycol dimethacrylate, the glycerol propoxylate triacrylate, the arbitrary combination of one or more of Viscoat 295.
Preferably, described modified epoxy is by being selected from one or more modifier: the Resins, epoxy after vinylformic acid, methacrylic acid, MALEIC ANHYDRIDE, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, the methyl hexahydrophthalic anhydride modification.
Preferably, described Resins, epoxy is selected from glycidyl ether based epoxy resin, glycidyl ester based epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, phenolic Resins, epoxy, Bisphenol F based epoxy resin etc. or its combination.
Preferably, described stopper is selected from one or more arbitrary combination of Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone.
Preferably, described initiator is selected from one or more arbitrary combination of benzoyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, cyclohexanone peroxide, peroxidation (2-ethyl) hecanoic acid t-butyl ester, methylethyl ketone peroxide.
Preferably, described auxiliary agent is selected from one or more arbitrary combination of zinc naphthenate, isocaprylic acid zinc, acetyl acetone salt, boron amide complex compound.
Another object of the present invention is to provide a kind of preparation method of environment-friendly type solvent-free solvent impregnated resin, it is characterized in that said method comprising the steps of:
(1) Resins, epoxy is heated to 70～100 ℃, dropping and Resins, epoxy mol ratio are 0.3～1.1 acrylic acid solution, wherein contain Resorcinol, benzylamine in the acrylic acid solution, the Resorcinol quality is 0.05～1% of an acrylic acid solution quality, and the quality of benzylamine is 0.5～4% of an acrylic acid solution quality, be warmed up to 110～130 ℃ after dropwising, reacted 3-6 hour, and dropped to below the 5mg-KOH/g to acid number, finish reaction, be cooled to room temperature, make modified epoxy;
(2) by the formula rate of claim 1 high heat resistant unsaturated polyester resin, modified epoxy, novel active thinner, stopper, initiator, auxiliary agent are mixed and promptly get the environment-friendly type solvent-free solvent impregnated resin.
Term in the technical solution of the present invention " weight part ", i.e. " parts by weight ", the ratio of weight.0～100 weight part meaning is in 0～100 weight unit of this ingredients constitute of composition total weight.The novel active thinner is selected the novel acrylic ester class cross-linking monomer of high reaction activity for use.
This environment-friendly type solvent-free solvent impregnated resin has 6 components in the optimal technical scheme of the present invention, by weight, this solvent impregnated resin is by 100 parts of high heat resistant unsaturated polyester resins, 0～100 part of modified epoxy, 50～200 parts of novel active thinners, 0.1～1 part of stopper, 1.5～3.8 parts of initiators, 0～2 part of composition of auxiliary agent.
Wherein high heat resistant unsaturated polyester resin is organic-silicon-modified unsaturated polyester resin, the unsaturated polyester resin of N-benzene maleimide modification, 4,4 '-the bi-maleimide modified unsaturated polyester resin of ditane type, metaphenylene unsaturated polyester resin, dicyclopentadiene synthetic unsaturated polyester resin, unsaturated polyester-imide resin etc. or its combination.
Described modified epoxy is a kind of epoxy ester of unsaturated acid, and its modifier can be vinylformic acid, methacrylic acid, MALEIC ANHYDRIDE, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride etc. or its combination.
The preparation method of described modified epoxy is: take by weighing a certain amount of Resins, epoxy in there-necked flask, be heated to 70～100 ℃, drip with the Resins, epoxy mol ratio be that (wherein the Resorcinol quality is 0.05～1% of a vinylformic acid quality for 0.3～1.1 the acrylic acid solution that contains Resorcinol, benzylamine, the quality of benzylamine be the vinylformic acid quality 0.5～4%), after dropwising in 0.5～1 hour, be warmed up to 110～130 ℃, reacted 3-6 hour, drop to below the 5mg-KOH/g to acid number, finish reaction, be cooled to room temperature, make modified epoxy.
The Resins, epoxy that described modified epoxy is used is selected glycidyl ether based epoxy resin, glycidyl ester based epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, novolac epoxy, bisphenol F epoxy resin etc. or its combination for use.Preferentially select glycidyl ether based epoxy resin and bisphenol F epoxy resin for use.
Novel active thinner of the present invention is a phenyl methacrylate, cyclohexyl methacrylate, the methacrylic acid benzyl ester, lauryl methacrylate(LMA), 2-benzene oxygen ethyl-methyl acrylate, cyclohexyl acrylate, the vinylformic acid benzyl ester, dicyclopentadiene acrylate, Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), the dimethacrylate triglycol ester, 1,4-butyleneglycol diacrylate fat, 1,6 hexanediol diacrylate, the dimethacrylate triglycol ester, neopentylglycol dimethacrylate, the glycerol propoxylate triacrylate, Viscoat 295 etc. or its combination.Stopper is Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone etc. or its combination.Initiator is benzoyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, cyclohexanone peroxide, peroxidation (2-ethyl) hecanoic acid t-butyl ester, methylethyl ketone peroxide etc. or their mixture.Auxiliary agent is zinc naphthenate, isocaprylic acid zinc, acetyl acetone salt, boron amide complex compound etc. or its combination.
The preparation method of environment-friendly type solvent-free solvent impregnated resin of the present invention is: by prescription each component is mixed promptly.Use environment-friendly type solvent-free solvent impregnated resin of the present invention, can select impregnation technology according to concrete needs, impregnation technology should be well known in the art, is not described in detail in this.Curing reaction was 2～5 hours between preferably curing schedule adopted 140～150 ℃, generated resin material solid, flexible after solidifying, and had excellent electric insulation, mechanical property and humidity resistance.
With respect to scheme of the prior art, advantage of the present invention is:
Present domestic most solvent-free impregnating resins contain 30%～40% vinylbenzene, some solvent-free continuous dipping resin styrene content even surpass 50%.Vinylbenzene can only the subparticipation crosslinking reaction, and all the other all evaporate in the air, not only can cause the wasting of resources, and contaminate environment, the infringement worker health.The curing fugitive constituent of dipping resin is generally 25%～35% continuously, that is to say the vinylbenzene meeting volatilization loss more than 20% that accounts for total amount, and the availability of final solvent impregnated resin is less than 70%.Environment-friendly type solvent-free solvent impregnated resin of the present invention adopts low viscous modified epoxy; adopt novel active cross-linking monomer, the high heat resistant type unsaturated polyester resin of dilution of high boiling point, low saturation vapour pressure; in the solidification process; reactive monomer all participates in crosslinking reaction; essentially no volatilization loss, environmentally friendly, there is not the danger of burning, blast; help safety and production, meet the trend of environment protection.
Environment-friendly type solvent-free solvent impregnated resin viscosity of the present invention is about 300mPas, and 155 ℃ dielectric dissipation factor is less than 5%.The viscosity of E.I.Du Pont Company 4200 and E4050 is greater than 2000mPas; 155 ℃ of dielectric dissipation factors of rich sieve 3060 are greater than 5%; So environment-friendly type solvent-free solvent impregnated resin of the present invention has tangible technical superiority than prior art.Environment-friendly type solvent impregnated resin of the present invention can solidify down at 140～150 ℃ in 2～5 hours, compared with solvent impregnated resin with the no-solvent type mesolow of present routine, under identical workpiece situation, can shorten the time of curing about 1/3, saved about 25% energy consumption.
Nontoxic, low smelly, tasteless from solvent impregnated resin, the labour protection, the safety in production aspect that are beneficial to the worker are considered, analyze from the raising and the save energy aspect of production efficiency, environment-friendly type solvent-free solvent impregnated resin of the present invention has good market outlook.
In sum, the invention discloses a kind of environment-friendly type solvent-free solvent impregnated resin and preparation method thereof.By weight, this environment-friendly type solvent-free solvent impregnated resin is by 100 parts of high heat resistant unsaturated polyester resins, 0～100 part of modified epoxy, 50～200 parts of novel active thinners, 0.1～1 part of stopper, 1.5～3.8 parts of initiators, 0～2 part of composition of auxiliary agent.Under this environment-friendly type solvent impregnated resin room temperature is low-viscosity (mobile) liquid, coil is had good penetration, and excellent in storage stability and high reactive behavior can be solidified under 130～150 ℃ of conditions and got final product in 2～5 hours, can enhance productivity effectively, save energy, reduce comprehensive cost.Cured article has good electric property, mechanical property and resistance toheat, temperature resistant grade H level.The most important thing is not contain deleterious volatile organic solvent, fugitive constituent is lower than 2% in the solidification process, and basic odorlessness is a kind of nontoxic environment-friendly type solvent-free solvent impregnated resin, can reduce the dipping lacquer environmental pollution to greatest extent, be the upgraded product that improves workman's labor condition.This environment-friendly type solvent-free solvent impregnated resin is suitable for all dippings that hangs down middle piezoelectricity machine, transformer, drips and soak, roll and soak the technology with VPI.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are used to the present invention is described and are not limited to limit the scope of the invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Embodiment 1
Take by weighing the 200g glycidyl methacrylate in there-necked flask, be warmed up to 80 ℃, drip the mixing solutions of 100g vinylformic acid, 0.3g Resorcinol, 2.8g benzylamine, after dropwising, about 1h is warmed up to 115 ℃, behind the reaction 5h, vacuumize, remove responseless vinylformic acid and other small-molecule substance, cool to room temperature makes low viscosity modified epoxy (A).
Take by weighing the 100g metaphenylene unsaturated polyester resin, 58.68g low viscosity modified epoxy (A), 78.51g 1, the 6-hexanediyl ester, 0.1g Resorcinol, 2.37g dicumyl peroxide, 1.54g isocaprylic acid zinc stirs and both gets environment-friendly type, low volatilization solvent-free impregnating resin.
Embodiment 2
Take by weighing bisphenol A type epoxy resin E-51 that 200g purifies through molecular distillation technique in there-necked flask, be warmed up to 80 ℃, drip the mixing solutions of 47g vinylformic acid, 0.24g Resorcinol, 2.5g benzylamine, after about 0.5h dropwises, be warmed up to 130 ℃, react to acid number during less than 3mg-KOH/g, vacuumize, remove responseless vinylformic acid and other small-molecule substance, cool to room temperature gets modified epoxy (B).
Take by weighing 100g unsaturated polyester-imide resin, 25g modified epoxy (B), 71.43g the 1,6 hexanediol diacrylate hexanediyl ester, the 13.5g Ethylene glycol dimethacrylate, the 25g cyclohexyl methacrylate, 0.15g Resorcinol, 2.3g benzoyl peroxide, 0.2g aluminium acetylacetonate, 0.75g zinc naphthenate stirs and both gets environment-friendly type, the solvent-free polyester-imide solvent impregnated resin of low volatilization.
The environment-friendly type for preparing, the solvent-free polyester-imide solvent impregnated resin of low volatilization are solidified 2h down at 150 ℃, obtain the insulating resin of excellent performance.The performance of environment-friendly type solvent-free polyester-imide solvent impregnated resin and cured article thereof sees Table 1.
Table 1 environment-friendly type solvent-free polyester-imide solvent impregnated resin and condensate performance thereof
Embodiment 3
Take by weighing the unsaturated polyester resin of 100g N-benzene maleimide modification, 2 synthetic modified epoxies of 10g embodiment (B), 70.58g dicyclopentadiene acrylate, 20.32g phenyl methacrylate, 10.79g diethyleneglycol dimethacrylate(DEGDMA), 10g dimethyl allene acid glyceride, 0.2g para benzoquinone, 2.3g benzoyl peroxide, 0.2g isocaprylic acid zinc, stir, make high heat resistance, low-volatile environment-friendly type solvent-free solvent impregnated resin.
Embodiment 4
Take by weighing 200g two ((3, the 4-epoxycyclohexyl) methyl) adipic acid ester is in there-necked flask, be warmed up to 90 ℃, drip the mixing solutions of 42g vinylformic acid, 0.33g Resorcinol, 2.5g benzylamine, dropwise at about 1h, be warmed up to 120 ℃, react to acid number during, vacuumize, remove responseless vinylformic acid and other small-molecule substance less than 1mg-KOH/g, cool to room temperature makes modified epoxy (C).
Take by weighing 100g unsaturated polyester-imide resin, 25g modified epoxy (C), the 70g 1,6 hexanediol diacrylate, 30g methacrylic acid benzyl ester, the 20g cyclohexyl acrylate, 0.1g para benzoquinone, 1.2g benzoyl peroxide, 1.3g dicumyl peroxide, 0.75g isocaprylic acid zinc stirs, and makes environment-friendly type solvent-free polyester-imide solvent impregnated resin.
Embodiment 5
Take by weighing 100g metaphenylene unsaturated polyester-imide resin, 70.58g dicyclopentadiene acrylate, 20.24g 1, the 6-hexanediyl ester, 15g methacrylic acid benzyl ester, 0.15g Resorcinol, 2.66g dicumyl peroxide, stir, make high heat resistance, low-volatile environment-friendly type solvent-free polyester-imide solvent impregnated resin.
Embodiment 6
Take by weighing 100g unsaturated polyester-imide resin, 25g modified epoxy (B), the 25g 1,6 hexanediol diacrylate, 17.5g methacrylic acid benzyl ester, 37.5 lauryl methacrylate(LMA), 0.1g Resorcinol, 0.75g isocaprylic acid zinc, 2.2g peroxidation (2-ethyl) hecanoic acid t-butyl ester, stir, make environment-friendly type solvent-free polyester-imide solvent impregnated resin.
Embodiment 7
Take by weighing 200g o-tolyl glycidyl ether, be warmed up to 100 ℃, drip the mixing solutions of 84g vinylformic acid, 0.42g Resorcinol, 2.8g benzylamine, dropwise at about 0.5h, be warmed up to 120 ℃, react to acid number during less than 5mg-KOH/g, vacuumize, remove responseless vinylformic acid and other small-molecule substance, cool to room temperature makes modified epoxy (D).
Take by weighing 100g unsaturated polyester-imide resin, 100g modified epoxy (D), 70.58g dicyclopentadiene acrylate, 80.43g the methacrylic acid benzyl ester, 29.86g 2-benzene oxygen ethyl-methyl acrylate, 0.1g Resorcinol, 0.8g zinc naphthenate, 3.8g dicumyl peroxide stirs, and makes environment-friendly type, the solvent-free polyester-imide solvent impregnated resin of low volatilization.
Embodiment 8
Take by weighing the adjacent benzene type of 100g polyester imine resin, 45.3g modified epoxy (B), 25g 2-benzene oxygen ethyl-methyl acrylate, 15g methacrylic acid benzyl ester, 0.12g MEHQ, 0.9g isocaprylic acid zinc, 0.9g dicumyl peroxide, the 1g peroxidized t-butyl perbenzoate stirs, and makes environment-friendly type, the solvent-free polyester-imide solvent impregnated resin of low volatilization.
Embodiment 9
Take by weighing the 100g metaphenylene unsaturated polyester resin, 37.5g modified epoxy (D), 17.5g1,6-hexanediyl ester, the 16g Ethylene glycol dimethacrylate, the 9g phenyl methacrylate, 0.15g peroxidation (2-ethyl) hecanoic acid t-butyl ester, 0.01g aluminium acetylacetonate, 0.25 isocaprylic acid zinc, 1.8 benzoyl peroxide stirs, and makes environment-friendly type, the solvent-free polyester-imide solvent impregnated resin of low volatilization.
Embodiment 10
Take by weighing the adjacent benzene type of 100g polyester imine resin, 24.52g methacrylic acid benzyl ester, 35.75 dicyclopentadiene acrylate, the 30g Viscoat 295,20g triethylene glycol dimethacrylate, 0.15g 2-Tert. Butyl Hydroquinone, 1.9g benzoyl peroxide, stir, make environment-friendly type solvent-free polyester-imide solvent impregnated resin.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (9)
1. an environment-friendly type solvent-free solvent impregnated resin is characterized in that 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.
2. environment-friendly type solvent-free solvent impregnated resin according to claim 1, it is characterized in that described high heat resistant unsaturated polyester resin be selected from the unsaturated polyester resin, 4,4 of organic-silicon-modified unsaturated polyester resin, the modification of N-benzene maleimide '-one or more arbitrary combination of the bi-maleimide modified unsaturated polyester resin of ditane type, match gram modification metaphenylene unsaturated polyester resin, dicyclopentadiene synthetic unsaturated polyester resin, unsaturated polyester-imide resin.
3. environment-friendly type solvent-free solvent impregnated resin according to claim 1, it is characterized in that described novel active thinner is selected from phenyl methacrylate, cyclohexyl methacrylate, the methacrylic acid benzyl ester, lauryl methacrylate(LMA), 2-benzene oxygen ethyl-methyl acrylate, cyclohexyl acrylate, the vinylformic acid benzyl ester, dicyclopentadiene acrylate, Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), the dimethacrylate triglycol ester, 1,4-butyleneglycol diacrylate fat, 1,6 hexanediol diacrylate, the dimethacrylate triglycol ester, neopentylglycol dimethacrylate, the glycerol propoxylate triacrylate, the arbitrary combination of one or more of Viscoat 295.
4. environment-friendly type solvent-free solvent impregnated resin according to claim 1 is characterized in that described modified epoxy is by being selected from one or more modifier: the Resins, epoxy after vinylformic acid, methacrylic acid, MALEIC ANHYDRIDE, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, the methyl hexahydrophthalic anhydride modification.
5. environment-friendly type solvent-free solvent impregnated resin according to claim 4 is characterized in that described Resins, epoxy is selected from one or more arbitrary combination of glycidyl ether based epoxy resin, glycidyl ester based epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, phenolic Resins, epoxy, Bisphenol F based epoxy resin.
6. environment-friendly type solvent-free solvent impregnated resin according to claim 1, it is characterized in that described stopper is selected from one or more arbitrary combination of Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone.
7. environment-friendly type solvent-free solvent impregnated resin according to claim 1 is characterized in that described initiator is selected from one or more arbitrary combination of benzoyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, cyclohexanone peroxide, peroxidation (2-ethyl) hecanoic acid t-butyl ester, methylethyl ketone peroxide.
8. environment-friendly type solvent-free solvent impregnated resin according to claim 1 is characterized in that described auxiliary agent is selected from one or more arbitrary combination of zinc naphthenate, isocaprylic acid zinc, acetyl acetone salt, boron amide complex compound.
9. the preparation method of an environment-friendly type solvent-free solvent impregnated resin is characterized in that said method comprising the steps of:
(1) Resins, epoxy is heated to 70～100 ℃, dropping and Resins, epoxy mol ratio are 0.3～1.1 acrylic acid solution, wherein contain Resorcinol, benzylamine in the acrylic acid solution, the Resorcinol quality is 0.05～1% of an acrylic acid solution quality, and the quality of benzylamine is 0.5～4% of an acrylic acid solution quality, be warmed up to 110～130 ℃ after dropwising, reacted 3-6 hour, and dropped to below the 5mg-KOH/g to acid number, finish reaction, be cooled to room temperature, make modified epoxy;
(2) by the formula rate of claim 1 high heat resistant unsaturated polyester resin, modified epoxy, novel active thinner, stopper, initiator, auxiliary agent are mixed and promptly get the environment-friendly type solvent-free solvent impregnated resin.
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