CN106811023B - A kind of environment-friendly type wind-driven generator VPI impregnating resin and preparation method thereof - Google Patents
A kind of environment-friendly type wind-driven generator VPI impregnating resin and preparation method thereof Download PDFInfo
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- CN106811023B CN106811023B CN201611113467.2A CN201611113467A CN106811023B CN 106811023 B CN106811023 B CN 106811023B CN 201611113467 A CN201611113467 A CN 201611113467A CN 106811023 B CN106811023 B CN 106811023B
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/307—Other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a kind of environment-friendly type wind-driven generator VPI impregnating resins, by mass percentage, component includes: heat-resisting bicyclic unsaturated polyester resin system, modified epoxy, crosslinking agent, initiator, curing agent and promotor, heat-resisting bicyclic unsaturated polyester resin system is made of heat-resisting bicyclic unsaturated polyester resin and crosslinking agent, and system viscosity is 300~400s；Heat-resisting bicyclic unsaturated polyester resin is prepared at least one polyalcohol through polycondensation reaction by dicyclopentadiene, at least one polyacid；Crosslinking agent is at least one of methyl propenoic acid glycidyl ether, sodium dodecyl allyl base acid esters, diallyphthalate acid esters, trimethylolpropane allyl ester；Modified epoxy is obtained by unsaturated polyester modified.The impregnating resin has the characteristics that excellent storage stability, heat-resist, cured product high mechanical strength, adhesion strength are high, electrical insulation properties are good, dielectric loss is small, water absorption rate is low, applied widely.
Description
Technical field
The present invention relates to the preparation field of impregnating varnish more particularly to a kind of environment-friendly type wind-driven generator VPI impregnating resins
And preparation method thereof.
Background technique
VPI is the abbreviation of technique of vacuum pressure for dipping electrical, i.e. Vacuum Pressure Impregnating.VPI is high pressure
Important technique in the electric appliances such as motor, transformer, power capacitor and paper insulated high voltage power cable and electrical material production
Process, after VPI process, the good insulation preformance of the said goods, temperature rise are reduced, are improved efficiency, increase mechanical strength, solve
The loose phenomenon of operational process prevents the insulation faults such as short circuit, improves moisture protection, prolongs the service life.
Now, domestic each motor manufacturer all employs VPI in production high-voltage motor and small power generation unit substantially
Technology, and also have in the manufacturer of middle-size and small-size low voltage motor and begin to use this technology, therefore in the market to VPI with without molten
Also just increasing, requirement of many producers to solvent-free impregnating resin, in addition to vacuum to be met of the requirement of agent impregnating resin
Pressure impregnation requires the special performance of impregnating varnish outer, it is necessary to which adapting to the drop of each factory in production can lower consumption and multiduty need
Want, it is desirable that height Medium-voltage Motor is general, ordinary motor and special machines are general, big motor and general H-C grades of small machine it is general.So
Can reduce impregnating bath, buying it is convenient, convenient for management, energy-saving.
According to the difference of matrix resin, solvent-free impregnating resin generally can be divided into epoxide resin type, unsaturated polyester type, two
Phenylene ether resins type, polyesterimide type, polyimide type and organic silicon type.And wherein, unsaturated polyester type is due to excellent
Chemical-resistance, anti-moisture performance, electrical insulation properties, viscosity is lower, storage stability preferably, and can be easy to impregnate, become
The Main way of domestic and international solvent-free impregnating resin development.But because it is larger with cure shrinkage, adhesion strength is lower, air
The disadvantage that oxygen inhibition causes dry tack free performance poor, therefore it need to be modified.
The Chinese patent literature of Publication No. CN106046731A discloses a kind of environment friendly heat resistant impregnating resin, composition
Are as follows: heat resistant unsaturated polyester resin, cycloaliphatic epoxy resin and bisphenol A epoxide resin, curing agent, DCP, to tert-butyl o benzene two
Phenol, reactive diluent.The impregnating resin is also disclosed in document can be used for the varnished insulation application of separation generator.The dipping
Resin formula although heat resistance with higher, but that there are dielectric losses mostly is big, adhesion strength is low, water absorption rate is high asks
Topic, and joined reactive diluent in formula, there is also solidify the big problem of fugitive constituent.
Summary of the invention
The present invention provides a kind of environment-friendly type wind-driven generator VPI impregnating resin, which there is storage to stablize
Property good, heat-resist, cured product high mechanical strength, adhesion strength is high, electrical insulation properties are good, dielectric loss is small, water absorption rate
It is the features such as low, applied widely.
Specific technical solution is as follows:
A kind of environment-friendly type wind-driven generator VPI impregnating resin, by mass percentage, component includes:
The heat-resisting bicyclic unsaturated polyester resin system includes heat-resisting bicyclic unsaturated polyester resin and crosslinking agent, body
The viscosity of system is 200~300s, and the test of the viscosity uses 4# flow cup, and test temperature is 25 DEG C, similarly hereinafter；
The heat-resisting bicyclic unsaturated polyester resin is polynary by dicyclopentadiene, at least one polyacid and at least one
Alcohol is prepared through polycondensation reaction；
The crosslinking agent is sodium dodecyl allyl base acid esters, diallyphthalate acid esters, trimethylolpropane two
One of allyl ester is a variety of；
The modified epoxy is obtained by unsaturated polyester modified, and the viscosity of unsaturated polyester (UP) is 500~700s.
The system that solvent-free impregnating resin of the invention is made of heat-resisting bicyclic unsaturated polyester (UP) and extraordinary crosslinking agent, then
Unsaturated polyester modified epoxy blend is prepared with low viscosity, and system itself has good compatibility and matching
Property, and have the advantages that the synchronous solidification of two systems of unsaturated polyester (UP)-epoxy resin, then be equipped with high performance curing agent and friendship
Join agent, makes to release in its solidification process without small molecule, therefore curing process is good.Ensure impregnating resin solidification fugitive constituent it is small,
Excellent storage stability, heat-resist and all kinds of middle glue and dry mica paper tape have good compatibility.Cured product is mechanical strong
The features such as degree is high, electrical insulation properties are good, dielectric loss is small, water absorption rate is small.It is true to be suitable for H, C grades of large and medium-sized high-voltage motors
The varnished insulation of pneumatics power mass-impregnation and electric appliance winding is handled.
Preferably, the polyacid be selected from maleic anhydride, fumaric acid, terephthalic acid (TPA), benzoic acid, oneself two
Acid, dihydromethyl propionic acid, phthalic acid；
The polyalcohol is selected from neopentyl glycol, methyl propanediol or diglycol.
Further preferably, the acid value of the heat-resisting bicyclic unsaturated polyester resin is controlled in 20~25mgKOH/g.
Further preferably, the heat-resisting bicyclic unsaturated polyester resin is dicyclopentadiene: maleic anhydride by molar ratio:
Neopentyl glycol: terephthalic acid (TPA): fumaric acid: methyl propanediol=0.6:0.5:2.3:1.0:1.0:0.6 various of monomer is through contracting
Poly- reaction is prepared.Cooling after viscosity and acid value reach prescribed requirement, a certain amount of crosslinking agent is added, and to be configured to feature viscous
Spend the heat-resisting bicyclic unsaturated polyester resin system of range.
Preferably, the modified epoxy is by above-mentioned unsaturated polyester (UP) and bisphenol A type epoxy resin, phenolic aldehyde ring
One of oxygen resin, para-aminophenol epoxy resin a variety of are made through addition reaction.
Further preferably, it is phthalic anhydride: neopentyl glycol: a contracting diethyl that the unsaturated polyester (UP), which is by molar ratio,
Glycol: benzoic acid: dihydromethyl propionic acid=0.5:1.2:0.45:1.0:0.2 various of monomer through being prepared through polycondensation reaction,
It is used further to the modification of epoxy resin.
Preferably, the initiator is benzoyl peroxide and/or cumyl peroxide；
The curing agent is at least one of anhydride, boron amide class, imidazoles；
The promotor is metal salt of organic carboxylic acid and/or acetyl acetone salt.
Further preferably, the curing agent is tung oil acid anhydride or phenylimidazole；
The promotor is at least one of aluminium acetylacetonate, isooctyl acid potassium, cobalt naphthenate.
Under above-mentioned preferred each raw material, further, by mass percentage, component includes:
The invention also discloses the preparation methods of above-mentioned environment-friendly type wind-driven generator VPI impregnating resin, and steps are as follows:
(1) heat-resisting bicyclic unsaturated polyester resin is mixed with a part of crosslinking agent, obtaining system viscosity is 100~200s
Heat-resisting bicyclic unsaturated polyester resin system；
(2) after evenly mixing by heat-resisting bicyclic unsaturated polyester resin system, another part crosslinking agent and other components, it obtains
To the environment-friendly type wind-driven generator VPI impregnating resin.
The crosslinking agent used in the present invention is divided into two parts addition, and a part is first mixed with heat-resisting bicyclic unsaturated polyester resin
It closes, for adjusting the viscosity of heat-resisting bicyclic unsaturated polyester resin system within the appropriate range.Another part is at other groups
Divide and be added when being blended, it is therefore an objective to adjust the viscosity of impregnating resin.For convenience of production, the crosslinking agent that two parts are added is using identical
Kind, but different cultivars can also be used, it only need to be in the crosslinking agent variety range of above-mentioned restriction.
Impregnating resin according to specific in use, can need to select impregnation technology, impregnation technology should be that this field institute is public
Know, this will not be detailed here.Preferred condition of cure are as follows: solidify 4~6 hours at 140~150 DEG C first, then 170~180
DEG C solidification 8~10 hours.
Due to the implementation of above technical scheme, the invention has the following advantages over the prior art:
Environment-friendly type wind-driven generator VPI impregnating resin disclosed by the invention mainly includes heat-resisting bicyclic unsaturated polyester (UP) tree
Resin system, extraordinary crosslinking agent and modified epoxy, which are uniformly mixed, can be prepared by low viscosity, high bond strength, low dielectric loss
Impregnating resin.Its manufacturing process is simple, composition stability is good, performance stablizes brilliance.
Environment-friendly type wind-driven generator VPI impregnating resin prepared by the present invention is applied widely, is applicable not only to large and medium-sized
The varnished insulation of high-voltage motor vacuum pressure mass-impregnation and electric appliance winding is handled, while being applicable to the electricity of various temperature resistant grades
Machine electric appliance, be also applied for large cylinder immerse, continuously immerse, VPI impregnation technology, rotary roasting etc. technique requirement.
Specific embodiment
Embodiment 1
The formula of environment-friendly type wind-driven generator VPI impregnating resin is as follows in the present embodiment:
Heat-resisting bicyclic unsaturated polyester (UP) is dicyclopentadiene: maleic anhydride: neopentyl glycol: terephthaldehyde by molar ratio
Acid: fumaric acid: methyl propanediol=0.6:0.5:2.3:1.0:1.0:0.6 various of monomer is prepared through polycondensation reaction.
Heat-resisting bicyclic unsaturated polyester (UP) system by above-mentioned preparation heat-resisting bicyclic unsaturated polyester (UP) and trimethylolpropane two
Allyl ester (TMPTA) is mixed to get in mass ratio for 6:4.
Modified epoxy is mixed by the mass ratio of 10:100 by unsaturated polyester (UP) and epoxy resin (bisphenol A type epoxy resin)
After conjunction, obtained through addition reaction.
Unsaturated polyester (UP) is phthalic anhydride: neopentyl glycol: diglycol: benzoic acid: dihydroxy first by molar ratio
Base propionic acid=0.5:1.2:0.45:1.0:0.2 various of monomer through polycondensation reaction through being prepared.
It is cumyl peroxide by heat-resisting 50 grams of bicyclic unsaturated polyester (UP) system, modified epoxy 30g, initiator
(DCP) 0.8 gram, crosslinking agent be 15 grams of trimethylolpropane allyl ester (TMPTA), curing agent be 5 grams of tung oil acid anhydride, promote
Agent cobalt naphthenate 0.4g.
After mixing by formula by above-mentioned each component, environment-friendly type wind-driven generator VPI impregnating resin is obtained.The leaching
When in use, Ying Shouxian solidifies 4~6 hours stain resin at 140~150 DEG C, then solidifies 8~10 hours at 170~180 DEG C,
That is curable film-forming.
The preparation of heat-resisting bicyclic unsaturated polyester (UP) in following heat-resisting bicyclic unsaturated polyester (UP) system used in the examples
Method and dosage be identical as the embodiment, and the crosslinking agent kind used is subject to and is listed in specific embodiment.
Embodiment 2
The formula of the environment-friendly type wind-driven generator VPI impregnating resin of this example are as follows:
50 grams of heat-resisting bicyclic unsaturated polyester (UP), modified epoxy 30g, initiator are benzoyl peroxide (BPO) 1.4
Gram, crosslinking agent be 10 grams of diallyphthalate acid esters (DAP), curing agent is 5 grams of tung oil acid anhydride, promotor aluminium acetylacetonate
0.6g。
After mixing by formula by above-mentioned each component, then with other each components by being formulated after mixing, ring is obtained
Guarantor's type wind-driven generator VPI impregnating resin.When in use, Ying Shouxian is small in 140~150 DEG C of solidifications 4~6 for the impregnating resin
When, then solidify 8~10 hours, i.e. curable film-forming at 170~180 DEG C.
Embodiment 3
The formula of the environment-friendly type wind-driven generator VPI impregnating resin of this example are as follows:
50 grams of heat-resisting bicyclic unsaturated polyester (UP), modified epoxy 30g, initiator are benzoyl peroxide (BPO) 1.6
Gram, crosslinking agent be 10 grams of sodium dodecyl allyl base acid esters, 5 grams of diallyphthalate acid esters (DAP), curing agent are phenyl miaow
3 grams of azoles, promotor aluminium acetylacetonate 0.6g.
After mixing by formula by above-mentioned each component, then with other each components by being formulated after mixing, ring is obtained
Guarantor's type wind-driven generator VPI impregnating resin.When in use, Ying Shouxian is small in 140~150 DEG C of solidifications 4~6 for the impregnating resin
When, then solidify 8~10 hours, i.e. curable film-forming at 170~180 DEG C.
Embodiment 4
The formula of the environment-friendly type wind-driven generator VPI impregnating resin of this example are as follows:
50 grams of heat-resisting bicyclic unsaturated polyester (UP), modified epoxy 30g, initiator are cumyl peroxide (DCP) 0.8
Gram, crosslinking agent be 10 grams of diallyphthalate acid esters (DAP), curing agent is 3 grams of phenylimidazole, promotor isooctyl acid potassium
0.1g and cobalt naphthenate 0.3g.
After mixing by formula by above-mentioned each component, then with other each components by being formulated after mixing, ring is obtained
Guarantor's type wind-driven generator VPI impregnating resin.When in use, Ying Shouxian is small in 140~150 DEG C of solidifications 4~6 for the impregnating resin
When, then solidify 8~10 hours, i.e. curable film-forming at 170~180 DEG C.
Embodiment 5
The formula of the environment-friendly type wind-driven generator VPI impregnating resin of this example are as follows:
50 grams of heat-resisting bicyclic unsaturated polyester (UP), modified epoxy 30g, initiator are cumyl peroxide (DCP) 0.8
Gram, crosslinking agent be 10 grams of trimethylolpropane allyl ester (TMPTA), 5 grams of sodium dodecyl allyl base acid esters, curing agent are paulownia
5 grams of oil anhydride, promotor isooctyl acid potassium 0.1g and cobalt naphthenate 0.3g.
After mixing by formula by above-mentioned each component, then with other each components by being formulated after mixing, ring is obtained
Guarantor's type wind-driven generator VPI impregnating resin.When in use, Ying Shouxian is small in 140~150 DEG C of solidifications 4~6 for the impregnating resin
When, then solidify 8~10 hours, i.e. curable film-forming at 170~180 DEG C.
For the beneficial effect for further proving environment-friendly type wind-driven generator VPI impregnating resin of the present invention, to embodiment 1~
5 performances for preparing product are tested according to the corresponding national standard of insulated paint, the results are shown in Table 1.
Table 1
As shown in Table 1, environment-friendly type wind-driven generator VPI impregnating resin prepared by the present invention have excellent storage stability,
The spies such as heat-resist, cured product high mechanical strength, adhesion strength are high, electrical insulation properties are good, dielectric loss is small, water absorption rate is low
Point.
Further, general H grade epoxy ester type on the product and domestic market prepared by embodiment 1 in the present invention
VPI impregnating resin compare, performance test according to insulated paint national standard carry out, the results are shown in Table 2.
Table 2
As shown in Table 2, environment-friendly type wind-driven generator VPI impregnating resin prepared by the present invention, than domestic general H grade ring
The heat resistance of the VPI impregnating resin of oxygen ester type wants a high grade, maximum feature be dielectric loss is small, adhesion strength is high,
Water absorption rate is low, storage stability is excellent.
Claims (5)
1. a kind of environment-friendly type wind-driven generator VPI impregnating resin, which is characterized in that by mass percentage, component includes:
The heat-resisting bicyclic unsaturated polyester resin system includes heat-resisting bicyclic unsaturated polyester resin and crosslinking agent, system
Viscosity is 100~200s；The heat-resisting bicyclic unsaturated polyester resin by dicyclopentadiene, at least one polyacid at least
A kind of polyalcohol is prepared through polycondensation reaction；
Heat-resisting bicyclic unsaturated polyester (UP) is dicyclopentadiene: maleic anhydride: neopentyl glycol: terephthalic acid (TPA) by molar ratio:
Fumaric acid: methyl propanediol=0.6:0.5:2.3:1.0:1.0:0.6 various of monomer is prepared through polycondensation reaction；
The acid value of the heat-resisting bicyclic unsaturated polyester resin is controlled in 20~25mgKOH/g；
The crosslinking agent is methyl propenoic acid glycidyl ether, sodium dodecyl allyl base acid esters, diallyphthalate acid
At least one of ester, trimethylolpropane allyl ester；
The modified epoxy is obtained by unsaturated polyester modified, and the viscosity of unsaturated polyester (UP) is 500~700s, modified ring
After oxygen resin is mixed with bisphenol A type epoxy resin by the mass ratio of 10:100 by unsaturated polyester (UP), obtained through addition reaction；
Unsaturated polyester (UP) is phthalic anhydride: neopentyl glycol: diglycol: benzoic acid: dihydroxymethyl third by molar ratio
Acid=0.5:1.2:0.45:1.0:0.2 various of monomer is prepared through polycondensation reaction；
The preparation method of the environment-friendly type wind-driven generator VPI impregnating resin, steps are as follows:
(1) heat-resisting bicyclic unsaturated polyester resin is mixed with a part of crosslinking agent, obtaining system viscosity is the resistance to of 100~200s
The bicyclic unsaturated polyester resin system of heat；
(2) after evenly mixing by heat-resisting bicyclic unsaturated polyester resin system, another part crosslinking agent and other components, institute is obtained
The environment-friendly type wind-driven generator VPI impregnating resin stated.
2. environment-friendly type wind-driven generator VPI impregnating resin according to claim 1, which is characterized in that described is heat-resisting
In bicyclic unsaturated polyester resin system, the mass ratio of heat-resisting bicyclic unsaturated polyester resin and crosslinking agent is 6:4.
3. environment-friendly type wind-driven generator VPI impregnating resin according to claim 1, which is characterized in that the initiation
Agent is benzoyl peroxide and/or cumyl peroxide；
The curing agent is at least one of anhydride, boron amide class, imidazoles；
The promotor is metal salt of organic carboxylic acid and/or acetyl acetone salt.
4. environment-friendly type wind-driven generator VPI impregnating resin according to claim 3, which is characterized in that the solidification
Agent is tung oil acid anhydride or phenylimidazole；
The promotor is at least one of aluminium acetylacetonate, isooctyl acid potassium, cobalt naphthenate.
5. environment-friendly type wind-driven generator VPI impregnating resin according to any one of claims 1 to 4, which is characterized in that press matter
Percentages are measured, component includes:
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| CN108440718A (en) * | 2018-01-27 | 2018-08-24 | 嘉兴市新大陆机电有限公司 | Low volatilization trickle resin of a kind of high bond strength and preparation method thereof |
| CN108441132B (en) * | 2018-01-31 | 2020-10-30 | 浙江博菲电气股份有限公司 | Thermosetting resin type insulating self-adhesive tape and preparation method thereof |
| CN108484920B (en) * | 2018-03-08 | 2021-03-23 | 浙江博菲电气股份有限公司 | High-bonding-strength environment-friendly vacuum pressure impregnating resin |
| CN110885543B (en) * | 2019-11-29 | 2022-03-18 | 湖北长海新能源科技有限公司 | Organic silicon modified unsaturated resin insulation impregnating resin and preparation method thereof |
| CN111560101B (en) * | 2020-05-18 | 2022-06-17 | 浙江博菲电气股份有限公司 | Composition for use in VPI process |
| CN112408869A (en) * | 2020-11-19 | 2021-02-26 | 贺州学院 | Styrene-free artificial stone and preparation method thereof |
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