CN109355013A - A kind of rail traffic high-low temperature resistant impact organosilicon impregnating resin and preparation method thereof - Google Patents
A kind of rail traffic high-low temperature resistant impact organosilicon impregnating resin and preparation method thereof Download PDFInfo
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- CN109355013A CN109355013A CN201811038765.9A CN201811038765A CN109355013A CN 109355013 A CN109355013 A CN 109355013A CN 201811038765 A CN201811038765 A CN 201811038765A CN 109355013 A CN109355013 A CN 109355013A
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C09D7/65—Additives macromolecular
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a kind of rail traffic high-low temperature resistants to impact organosilicon impregnating resin and preparation method thereof, and organosilicon impregnating resin includes the component of following parts by weight meter: 1~30 part, 0.001~0.01 part of platinum complex compound catalyst of the organic-silicon-modified resin of 70~99 parts of organic siliconresin, toughening type.Relative to prior art, organosilicon impregnating resin provided by the invention also has heat-resistance index height, high-low temperature resistant cooling thermal impact power good, can satisfy the requirement of rail traffic motor group in addition to the excellent performance with Conventional insulation paint.
Description
Technical field
The present invention relates to a kind of electric insulation technologies more particularly to a kind of rail traffic high-low temperature resistant to impact organosilicon and soak
Stain resin and preparation method thereof.
Background technique
Organic siliconresin has many advantages, such as that high-fire resistance, electrical insulation properties are excellent, weather resistance is good, in insulation applications
It is widely applied.Common organosilicon impregnating resin is that solvent type impregnating resin contains a large amount of organic solvents, is producing and is applying
It is discharged into atmosphere during work, pollution environment and threat human health.Solventless impregnating insulated paint meets national environmental protection
Policies laws regulation has low VOC (within VOC content 1%) discharge in high-temperature baking solidification process.
Since intermolecular force is weak, paint film intensity is low to be easy traditional organosilicon impregnating resin under harsh working condition
Cracking is fallen.When rail traffic motor is impregnated using traditional organic siliconresin, by the puzzlement of insulated paint problem of Cracking, there are larger
Security risk, for exclude hidden danger need to periodically carry out dipping lacquer or maintenance, significantly increase operation cost.It is traditional organic
Simulating the thick-layer paint block under working condition, (addition electricity respectively is added in 45 × 45 aluminum dish in 10g insulated paint to silicon insulated impregnating resin
Magnetic round wires, magnet strip, M60 nut) and mica tape bar occur comminuted rupture during -55-155 DEG C of cooling thermal impacts,
Also there is a large amount of fish scale-shaped crackles, the cold and hot impact force of high-low temperature resistant in surface layer paint film when insulation bar is impacted under the above conditions
Difference.
Summary of the invention
For overcome the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of rail traffic high-low temperature resistants
Impact organosilicon impregnating resin.Relative to prior art, organosilicon impregnating resin provided by the invention, which removes, has Conventional insulation paint
Excellent performance outside, also have that heat-resistance index is high, high-low temperature resistant cooling thermal impact power is good, can satisfy making for rail traffic motor group
With requiring.
The second object of the present invention is to provide a kind of system of rail traffic high-low temperature resistant impact organosilicon impregnating resin
Preparation Method.Preparation method operation is feasible, is suitble to industrialized production.
An object of the present invention adopts the following technical scheme that realization: a kind of rail traffic high-low temperature resistant impact organosilicon
Impregnating resin, the component including following parts by weight meter: the organic-silicon-modified resin of 70~99 parts of organic siliconresin, toughening type 1~
30 parts, 0.001~0.01 part of platinum complex compound catalyst.
Further, the general structure of the organic siliconresin is (Me3SiO0.5)x(MeSiO1.5)y(Me2SiO)m
(MeHSiO)n(MeViSiO)q(PhSiO1.5)t(Me2SiRSi)z, wherein the integer that x is 1~10, the integer that y is 1~10, m are
1~10 integer, the integer that n is 0~30, the integer that q is 0~30, the integer that t is 1~50, the integer that z is 1~10, R is alkane
Hydrocarbyl chain and/or aryl chain.
Further, alkane chain or aromatic hydrocarbons chain, backbone structure are contained in the main chain of the organic-silicon-modified resin of the toughening type
For R1Me2SiRSiMe2R1, wherein R1It is alkyl chain and/or aryl chain for H and/or Vi (vinyl), R.
Further, the organic-silicon-modified resin of the toughening type is to contain polybutadiene chain link, diphenyl ether chain in strand
The copolymer of section or bisphenol A-type chain link, the molecular weight of the organic-silicon-modified resin of toughening type are 100-100000.
Further, the platinum complex compound catalyst is by chloroplatinic acid and to contain nitrogen phosphate and sulfur, alkynol group, tin, ethylene
The platinum complex compound that the complexing of one or more of based compound is formed.
Further, platinum complex compound catalyst Si―H addition reaction activity low-temperature catalyzed in is low, high-temperature catalytic silicon
Hydrogen addition activity is high；Low-temperature catalyzed reaction temperature is 100 DEG C in described and hereinafter, the reaction temperature of the high-temperature catalytic is high
In 100 DEG C.
The second object of the present invention adopts the following technical scheme that realization: a kind of rail traffic high-low temperature resistant impact organosilicon
The preparation method of impregnating resin, includes the following steps:
1) solvent, water and the hydrolyst that formula ratio is added into reaction vessel, open stirring, and mixing speed regards solution
Subject to homogeneous lotion, material temperature degree is controlled at 30~60 DEG C；
2) siloxanyl monomers of formula ratio are mixed evenly, control reaction temperature is 30~60 DEG C, toward the lotion of step 1)
In be slowly added dropwise siloxanyl monomers, time for adding is controlled at 60-150 minute, after completion of dropwise addition, control temperature of charge 40~80
DEG C, continue to be stirred to react 3~8 hours；
3) water is added to be washed, be layered into the reaction solution of step 2), washing times are 2~3 times, are warming up to again after washing
60-150 DEG C, add formula ratio equilibrium catalyst carry out condensation and balanced reaction, the reaction time 1~5 hour；
4) water is added to be washed, be layered into the reaction solution of step 3), washing times are 3~5 times, remove equilibration catalyst
Agent；
5) it is evaporated under reduced pressure out most of solvent into the reaction solution of step 4), increases temperature later to 190~210 DEG C, controls
Pressure 500pa in reaction vessel processed takes off the time control of low boiling in 1~5h hereinafter, removing low-boiling-point substance；
6) into step 5), the organic-silicon-modified resin of toughening type of addition formula ratio and platinum complex compound catalyst stir 30-
60min is to get organosilicon impregnating resin.
Further, in step 1), the siloxanyl monomers are to include phenyl unit, methyl hydrogen unit, ethylene methacrylic
Base unit, methyl group unit, dimethyl units and closure agent unit composition；
The phenyl unit is the mixing of one or both of phenyltrimethoxysila,e, phenyl triethoxysilane
Object；The methyl hydrogen unit be one of methyl hydrogen dimethoxysilane, methyl hydrogen diethoxy silane or mixture；Institute
Methyl ethylene unit is stated to mix for methylvinyldimethoxysilane, methyl vinyl diethoxysilane are one or two kinds of
Close object；The methyl group unit is the mixture of one or both of methyltrimethoxysilane, methyltriethoxysilane；Institute
State the mixture that dimethyl units are one or both of dimethyldimethoxysil,ne, dimethyl diethoxysilane；Institute
Stating closure agent unit is 1,1,3,3- tetramethyl divinyl disiloxane, 1,1,3,3- tetramethyl disiloxane, hexamethyl two
One of siloxanes or a variety of mixtures.
Further, the solvent is selected from one of toluene, dimethylbenzene, hexamethylene, 90-120 DEG C of boiling range of petroleum ether,
The additive amount of solvent is 0.5~1.5 times of siloxanyl monomers weight；The additive amount of the water is the 2~5 of siloxanyl monomers weight
Times；The additive amount of the hydrolyst is the 0.5%~5% of water weight.
Further, in step 3), the equilibrium catalyst accounts for the 0.005%~4% of siloxanyl monomers material total amount.
Compared with prior art, the beneficial effects of the present invention are:
(1) relative to prior art, organosilicon impregnating resin provided by the invention removes the Optimality with Conventional insulation paint
Can be outer, also have heat-resistance index height, high-low temperature resistant cooling thermal impact power good, can satisfy the requirement of rail traffic motor group,
The security risk that rail traffic motor is greatly alleviated by novel organosilicon impregnating resin extends the longevity of rail traffic motor
Life, reduces the operation cost of rail traffic motor.
(2) in addition, the preparation of the organic siliconresin in novel organosilicon impregnating resin uses based on organic silicon monomer, according to
Secondary to pass through hydrolysis, washing, condensation balanced reaction, wherein using acid to be used as catalyst when hydrolysis, resin is through water after hydrolysis
Washout go acid and by-product after, then by addition acid or alkali be balanced to obtain the organic siliconresin of narrow molecular weight distribution, addition
The organic-silicon-modified resin of part toughening type, platinum complex compound catalyst are modulated.Organosilicon impregnating resin simulation of the invention
Thick-layer paint block, bar under the conditions of extreme operating condition are after 40 periods of -55-155 DEG C/30min+30min cold cycling without going out
Existing crackle.
Detailed description of the invention
Fig. 1 is that the mica tape bar high/low temperature of middle orbit traffic high-low temperature resistant of the present invention impact organosilicon impregnating resin is cold
Thermal shock comparison diagram；
Fig. 2 is the thermal weight loss correlation curve that rail traffic high-low temperature resistant of the present invention impacts organosilicon impregnating resin.
Specific embodiment
In the following, being described further in conjunction with attached drawing and specific embodiment to the present invention, it should be noted that not
Under the premise of conflicting, new implementation can be formed between various embodiments described below or between each technical characteristic in any combination
Example.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field
Rule method.
A kind of rail traffic high-low temperature resistant impact organosilicon impregnating resin, the component including following parts by weight meter: has
1~30 part, 0.001~0.01 part of platinum complex compound catalyst of the organic-silicon-modified resin of 70~99 parts of machine silicone resin, toughening type.
Wherein, the general structure of organic siliconresin is (Me3SiO0.5)x(MeSiO1.5)y(Me2SiO)m(MeHSiO)n
(MeViSiO)q(PhSiO1.5)t(Me2SiRSi)z, wherein the integer that x is 1~10, the integer that y is 1~10, m are 1~10
Integer, the integer that n is 0~30, the integer that q is 0~30, the integer that t is 1~50, the integer that z is 1~10, R are alkyl chain
And/or aryl chain.
The preparation method of organic siliconresin is to there is alkoxysilane mixture as raw material, successively through hydrolysis and hydrolysis
Washing, condensation balanced reaction and balance washing, high-temperature vacuum desolventizing and low-boiling-point substance processing are prepared, and solvent in the middle is each
Inert substances such as the reaction medium, including alkane, aromatic hydrocarbon of kind reactant etc., alkane are the saturated hydrocarbons of C6~C20, preferably hexamethylene
Alkane, dodecane, benzene,toluene,xylene.The hydrolysis or equilibrium catalyst is triethylamine, ethanol amine, hydrochloric acid, sulfuric acid, sulfonic acid
One of salt, quaternary ammonium salt, strong resin are a variety of.
Alkoxysilane mixture is made of at least one siloxanyl monomers, and the siloxanyl monomers are to include phenyl list
One or both of member, methyl hydrogen unit, methyl ethylene unit, methyl group unit, dimethyl units and closure agent unit with
On composition；
The phenyl unit is the mixing of one or both of phenyltrimethoxysila,e, phenyl triethoxysilane
Object；The methyl hydrogen unit be one of methyl hydrogen dimethoxysilane, methyl hydrogen diethoxy silane or mixture；Institute
Methyl ethylene unit is stated to mix for methylvinyldimethoxysilane, methyl vinyl diethoxysilane are one or two kinds of
Close object；The methyl group unit is the mixture of one or both of methyltrimethoxysilane, methyltriethoxysilane；Institute
State the mixture that dimethyl units are one or both of dimethyldimethoxysil,ne, dimethyl diethoxysilane；Institute
Stating closure agent unit is 1,1,3,3- tetramethyl divinyl disiloxane, 1,1,3,3- tetramethyl disiloxane, hexamethyl two
One of siloxanes or a variety of mixtures.
Simple example explanation, when organic siliconresin includes vinyl polysiloxane and/or hydrogeneous silicone resin.Independent vinyl silicon
Methyl ethylene unit is only added when resins synthesis, and methyl hydrogen unit, vinyl silicon are individually then only added when hydrogeneous resins synthesis
The mixing organic siliconresin of resin and hydrogeneous silicone resin then adds vinyl units and hydrogeneous unit.
As further preferred scheme, alkane chain or aromatic hydrocarbons are contained in the main chain of the organic-silicon-modified resin of toughening type
Chain, backbone structure R1Me2SiRSiMe2R1, wherein R1It is alkyl chain and/or aryl chain for H and/or Vi (vinyl), R.
As further preferred scheme, the organic-silicon-modified resin of toughening type is to contain polybutadiene chain in strand
The copolymer of section, diphenyl ether chain link or bisphenol A-type chain link, the molecular weight of the organic-silicon-modified resin of toughening type are 100-100000.
Such as it is selected from organic-silicon-modified polybutadiene toughened resin, organic-silicon-modified diphenyl ether toughened resin, organic-silicon-modified bisphenol-A toughening
One of resin.
As further preferred scheme, the platinum complex compound catalyst is by chloroplatinic acid and to contain nitrogen phosphate and sulfur, alkynol base
The platinum complex compound that the complexing of one or more of group, tin, vinyl compound is formed, is such as selected from platinum triphenyl phosphite network
Close one of object, platinum ethynylcyclohexanol complex compound, platinum acrylamide complex compound, platinum diphenyl sulfide complex compound.
As further preferred scheme, platinum complex compound catalyst Si―H addition reaction activity low-temperature catalyzed in is low,
High-temperature catalytic Si―H addition reaction activity is high；In described low-temperature catalyzed reaction temperature be 100 DEG C and hereinafter, the high-temperature catalytic it is anti-
Answering temperature is higher than 100 DEG C.
The preparation method of organosilicon impregnating resin is impacted in the rail traffic with high-low temperature resistant, is included the following steps:
1) solvent, water and the hydrolyst that formula ratio is added into reaction vessel, open stirring, and mixing speed regards solution
Subject to homogeneous lotion, material temperature degree is controlled at 30~60 DEG C；
2) siloxanyl monomers of formula ratio are mixed evenly, control reaction temperature is 30~60 DEG C, toward the lotion of step 1)
In be slowly added dropwise siloxanyl monomers, time for adding is controlled at 60-150 minute, after completion of dropwise addition, control temperature of charge 40~80
DEG C, continue to be stirred to react 3~8 hours；
3) water is added to be washed, be layered into the reaction solution of step 2), washing times are 2~3 times, are warming up to again after washing
60-150 DEG C, add formula ratio equilibrium catalyst carry out condensation and balanced reaction, the reaction time 1~5 hour；
4) water is added to be washed, be layered into the reaction solution of step 3), washing times are 3~5 times, remove equilibration catalyst
Agent；
5) it is evaporated under reduced pressure out most of solvent into the reaction solution of step 4), increases temperature later to 190~210 DEG C, controls
Pressure 500pa in reaction vessel processed takes off the time control of low boiling in 1~5h, obtains organic siliconresin hereinafter, removing low-boiling-point substance；
6) into step 5), the organic-silicon-modified resin of toughening type of addition formula ratio and platinum complex compound catalyst stir 30-
60min is to get organosilicon impregnating resin.
As further preferred scheme, in step 1), the solvent is selected from toluene, dimethylbenzene, hexamethylene, boiling range 90-
120 DEG C of one of petroleum ether, convenient for washing layering, the additive amount of solvent is 0.5~1.5 times of siloxanyl monomers weight；
The additive amount of the water is 2~5 times of siloxanyl monomers weight；The additive amount of the hydrolyst is the 0.5% of water weight
~5%.
In step 2), methoxyl group, ethyoxyl in siloxane monomer mixture are hydrolyzable groups, and it is anti-that hydrolysis can occur
Silanol, silanol should be generated and obtain silicane hydrolysate after further condensation reaction under the action of catalyst.30~60 DEG C of temperature control reactions,
Silane mixture can be added in reaction vessel by dropwise addition mode, and time for adding was controlled at 60~150 minutes.
Preferably, substitution degree R/Si=1~2 for having base group in the organic siliconresin on silicon atom, that is, have
Every the average of the R group connected on silicon atom in organic siloxane polymer；The molar ratio of phenyl and organic group is Ph/R
=0.1~0.5；Wherein R is organic group, and Si is silicon atom, and Ph is phenyl group.It is mixed using the siloxanyl monomers of different ratio
It is different to close object R/Si and Ph/R, the organic siliconresin of different group contents, different viscosities can be prepared.
As further preferred scheme, in step 3), the washing mainly methanol that generates hydrolysis and ethyl alcohol with
And the equilibrium catalyst of addition washing times 2~3 times, is washed until by system to neutrality by water purification by liquid extraction.The balance
Catalyst accounts for the 0.005%~4% of siloxanyl monomers material total amount.Since hydrolysis generates a large amount of silanol and oligomer and ring
Shape body causes silicone resin molecular weight distribution inhomogenous, reduces the performance after paint solidifies, it is therefore desirable in the work of equilibrium catalyst
Condensation and balanced reaction are carried out under.
As further preferred scheme, in step 4), washing mainly removes the equilibration catalyst added in equilibrium process
Agent washing times 3~5 times, is washed until by system to neutrality.
As further preferred scheme, in step 5), the unreacted oligomer of vacuum removal and ring-type under hot conditions
Body obtains organic siliconresin.
The present invention is prepared for a kind of organic siliconresin that molecular structure is regular by above-mentioned technique, has by adding toughening type
Machine Si modification resin and platinum complex compound catalyst paint, cold-resistant thermal shock resistance properties is (- 55 DEG C/30min- good after paint block solidification
155 DEG C/30min cooling thermal impact does not crack), the high additional organosilicon solvent-free impregnating resin of heat-resistance index.
It is specific embodiment of the present invention below, used raw material, equipment etc. remove special limit in the following embodiments
It can be obtained by buying pattern outside fixed.
Embodiment 1:
Dimethyl diethoxysilane 0.15mol, methylvinyldimethoxysilane are added into constant pressure funnel
0.6mol, phenyltrimethoxysila,e 1.5mol, methyltrimethoxysilane 0.2mol, hexamethyldisiloxane 0.15mol；It is past
Water 150g, toluene 300g, hydrochloric acid 1.5g are added in reaction vessel.Rate of addition is controlled under conditions of 35 DEG C, in 120 minutes
Monomer dropping is finished, 50 DEG C of isothermal reactions 4 hours are warming up to.Then, it is washed to neutrality, takes upper materials.Add into material
Triethylamine is added to be warming up to 110 DEG C of reflux balanced reaction 3 hours.After balance, it is washed to neutrality, upper materials is taken take out very
Empty desolventizing and low-boiling-point substance control and take off 4 hours low boiling time, and 210 DEG C of temperature.Stop heating, cooling discharging tests organosilicon tree
The viscosity of rouge 1 is 1600mpas.
Dimethyl diethoxysilane 0.15mol, methyl hydrogen dimethoxysilane 0.6mol, benzene are added into constant pressure funnel
Base trimethoxy silane 1.5mol, methyltrimethoxysilane 0.2mol, hexamethyldisiloxane 0.3mol；Into reaction vessel
Water 150g, toluene 300g, hydrochloric acid 1.5g is added.Rate of addition is controlled under conditions of 35 DEG C, by monomer dropping in 120 minutes
It finishes, is warming up to 50 DEG C of isothermal reactions 4 hours.Then, it is washed to neutrality, takes upper materials.Into material, addition is to toluene sulphur
Acid is warming up to 110 DEG C of reflux balanced reaction 3 hours.After balance, it is washed to neutrality, upper materials is taken to carry out vacuumizing precipitation
Agent and low-boiling-point substance control and take off 4 hours low boiling time, and 210 DEG C of temperature.Stop heating, cooling discharging tests organic siliconresin 2
Viscosity is 1000mpas.
Organic siliconresin 1 obtained above is mixed with 2 two kinds of resins of organic siliconresin according to mass ratio for 1:1.2, is taken
The organic-silicon-modified polybutadiene toughened resin that parts by weight are 5 parts is added in 80 parts of organic siliconresin of mixing, and parts by weight are added and are
0.002 part of platinum triphenyl phosphite complex compound, stirs evenly to get organosilicon solvent-free impregnating resin, viscosity
1400mpas。
Embodiment 1-1:
As a comparison case, the organic siliconresin synthesized in embodiment 1 is not added into toughened resin, remaining condition is identical.That is,
Two kinds of resins obtained above are mixed according to 1:1.2, the platinum triphenyl phosphite that parts by weight are 0.002 part is added and is complexed
Object stirs evenly up to organosilicon solvent-free impregnating resin, viscosity 1300mpas.
Embodiment 2:
Dimethyl diethoxysilane 0.3mol, methylvinyldimethoxysilane are added into constant pressure funnel
0.8mol, phenyltrimethoxysila,e 1.5mol, methyltrimethoxysilane 0.2mol, hexamethyldisiloxane 0.2mol；It is past
Water 150g, dimethylbenzene 300g, sulfuric acid 1.5g are added in reaction vessel.Rate of addition is controlled under conditions of 35 DEG C, at 120 minutes
It is interior to finish monomer dropping, it is warming up to 50 DEG C of isothermal reactions 3 hours.Then, it is washed to neutrality, takes upper materials.Into material
Addition strong resin is warming up to 150 DEG C of reflux balanced reaction 3 hours.After balance, it is washed to neutrality, upper materials is taken to carry out
Desolventizing and low-boiling-point substance are vacuumized, controls and takes off 4 hours low boiling time, 210 DEG C of temperature.Stop heating, cooling discharging is tested organic
The viscosity of silicone resin 3 is 1500mpas.
Dimethyl diethoxysilane 0.15mol, methyl hydrogen dimethoxysilane 0.6mol, benzene are added into constant pressure funnel
Base trimethoxy silane 1.5mol, methyltrimethoxysilane 0.3mol, hexamethyldisiloxane 0.1mol, hydrogeneous double seal head
0.15mol；Water 150g, dimethylbenzene 300g, sulfuric acid 1.5g are added into reaction vessel.Speed is added dropwise in control under conditions of 35 DEG C
Degree, monomer dropping is finished, be warming up to 50 DEG C of isothermal reactions 3 hours in 120 minutes.Then, it is washed to neutrality, takes upper layer substance
Material.Strong resin is added into material is warming up to 150 DEG C of reflux balanced reaction 3 hours.After balance, it is washed to neutrality, is taken
Upper materials carry out vacuumizing desolventizing and low-boiling-point substance, control and take off 4 hours low boiling time, and 210 DEG C of temperature.Stop heating, it is cooling
Discharging, the viscosity of test organic siliconresin 4 are 1100mpas.
Organic siliconresin 3 obtained above is mixed with 4 two kinds of resins of organic siliconresin according to mass ratio for 1:1.1, is taken
The organic-silicon-modified diphenyl ether toughened resin that parts by weight are 8 parts is added in 70 parts of organic siliconresin of mixing, and parts by weight are added and are
0.002 part of platinum ethynylcyclohexanol complex compound, stirs evenly to get organosilicon solvent-free impregnating resin, viscosity
1300mpas。
Embodiment 3:
Dimethyl diethoxysilane 0.2mol, methylvinyldimethoxysilane 1mol are added into constant pressure funnel,
Phenyltrimethoxysila,e 1.2mol, methyltrimethoxysilane 0.2mol, hexamethyldisiloxane 0.15mol；Hold toward reaction
Water 150g, hexamethylene 300g, sulfuric acid 1.5g are added in device.Rate of addition is controlled under conditions of 35 DEG C, it will be single in 120 minutes
Body is added dropwise, and is warming up to 50 DEG C of isothermal reactions 3 hours.Then, it is washed to neutrality, takes upper materials.Second is added into material
Hydramine is warming up to 100 DEG C of reflux balanced reaction 4 hours.After balance, be washed to neutrality, take upper materials vacuumize it is de-
Solvent and low-boiling-point substance control and take off 4 hours low boiling time, and 210 DEG C of temperature.Stop heating, cooling discharging tests organic siliconresin 5
Viscosity be 1700mpas.
Dimethyl diethoxysilane 0.15mol, methyl hydrogen dimethoxysilane 1.2mol, benzene are added into constant pressure funnel
Base trimethoxy silane 1.2mol, methyltrimethoxysilane 0.3mol, hexamethyldisiloxane 0.3mol；Into reaction vessel
Water 150g, hexamethylene 300g, sulfuric acid 1.5g is added.Rate of addition is controlled under conditions of 35 DEG C, drips monomer in 120 minutes
It adds complete, is warming up to 50 DEG C of isothermal reactions 3 hours.Then, it is washed to neutrality, takes upper materials.Methyl sulphur is added into material
Acid is warming up to 100 DEG C of reflux balanced reaction 3 hours.After balance, it is washed to neutrality, upper materials is taken to carry out vacuumizing precipitation
Agent and low-boiling-point substance control and take off 4 hours low boiling time, and 210 DEG C of temperature.Stop heating, cooling discharging tests organic siliconresin 6
Viscosity is 900mpas.
Organic siliconresin 5 obtained above is mixed with 6 two kinds of resins of organic siliconresin according to mass ratio for 1:1.3, is taken
The organic-silicon-modified bisphenol-A toughened resin that parts by weight are 10 parts is added in 99 parts of organic siliconresin of mixing, and parts by weight are added and are
0.002 part of platinum acrylamide complex compound stirs evenly up to organosilicon solvent-free impregnating resin, viscosity 1300mpas.
Embodiment 4:
Dimethyl diethoxysilane 0.2mol, methylvinyldimethoxysilane 1mol are added into constant pressure funnel,
Phenyltrimethoxysila,e 1.2mol, methyltrimethoxysilane 0.2mol, methyltriethoxysilane 1.3mol, hexamethyl two
Siloxanes 0.2mol；Water 180g, dimethylbenzene 400g, sulfuric acid 2g are added into reaction vessel.It controls and is added dropwise under conditions of 35 DEG C
Speed finished monomer dropping in 120 minutes, was warming up to 50 DEG C of isothermal reactions 4 hours.Then, it is washed to neutrality, takes upper layer
Material.P-methyl benzenesulfonic acid is added into material is warming up to 150 DEG C of reflux balanced reaction 5 hours.After balance, it is washed to
Property, it takes upper materials to carry out vacuumizing desolventizing and low-boiling-point substance, controls and take off 4 hours low boiling time, 210 DEG C of temperature.Stop heating,
Cooling discharging, test organic siliconresin viscosity are 1400mpas.
By 85 parts of organic siliconresin obtained above, the organic-silicon-modified bisphenol-A toughened resin for being 10 parts with parts by weight
The platinum diphenyl sulfide complex compound that parts by weight are 0.002 part is added in mixing, stirs evenly up to organosilicon solvent-free dipping tree
Rouge, viscosity 1350mpas.
Effect assessment and performance detection
1. the organosilicon impregnating resin heat resistance of couple embodiment 1-4 and comparative example 1, the performance of cold-resistant thermal impact carry out
Detection, detection project and result are referring to table 1.
1 the performance test results of table
It is long-term under 80 DEG C of medium temperature conditions the present invention relates to selecting platinum complex compound to can satisfy above-mentioned impregnating resin
Dipping uses, and impregnating resin solidfied material simulates thick-layer under extreme working condition, bar in -55 DEG C/30min-155 DEG C/30min
Cold cycling does not have cracked after 40 periods, be detailed in Fig. 1.The test of impregnating resin solidfied material heat resistance, heat-resistance index reach
To 240 DEG C.Wherein, the cooling thermal impact of above-mentioned organosilicon impregnating resin solidfied material is according to standard GB/T/T 2423.22-2012/
IEC 60068-2-14:2009 test gained.The heat resistance of organosilicon impregnating resin solidfied material is according to machinery industry standard JB/
T 1544-2015 test gained.
Rotary viscosity of the organosilicon impregnating resin of the present invention under the conditions of 25 ± 2 DEG C is in 900~1800mPaS, preferably
1000-1500mPa·S.Wherein, the viscosity of above-mentioned organosilicon impregnating resin is according to standard GB/T/T 24148.4-
2009 test gained.
Fig. 2 is thermogravimetric curve, it can be seen that the calcination in 900 DEG C of air atmospheres, residual quantity are up to 51%, it is seen that have
Very high heat resistance.
The time thermal life t how 300 DEG C of letters spend 90% is tested, is calculated according to formula (1) in JB/T 1544-2015 standard:
1/(273+td)=(lg τ0-lgτ)/b+1/(273+t)……………(1)
τ in formula0--- thermal life boundary value takes 20000h.
It is calculated according to above-mentioned formula and ageing time, the heat-resistance index of organosilicon impregnating resin of the embodiment of the present invention is 220
DEG C or more.
Using the obtained organosilicon solvent-free impregnating resin heat resistance of above-described embodiment 1,2,3,4 and embodiment 1-1 without
Difference, cold-resistant thermal shock resistance properties raising is larger, preferably meets rail traffic motor group and wants to the special of insulated impregnating resin
It asks.
It is deposited in conclusion organosilicon impregnating resin of the invention solves rail traffic insulating paint for motor in the prior art
Cracking and high-low temperature resistant cooling thermal impact be bad, motor reprocesses the high defect of frequency, obtain a kind of high-low temperature resistant cooling thermal impact
Have excellent performance, can be for a long time in the insulated impregnating resin of 220 DEG C or more high temperature, this paint can be widely applied to rail traffic motor
Insulation impregnating.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of rail traffic impacts organosilicon impregnating resin with high-low temperature resistant, which is characterized in that including following parts by weight meter
Component: 1~30 part of the organic-silicon-modified resin of 70~99 parts of organic siliconresin, toughening type, platinum complex compound catalyst 0.001~
0.01 part.
2. rail traffic as described in claim 1 impacts organosilicon impregnating resin with high-low temperature resistant, which is characterized in that described to have
The general structure of machine silicone resin is (Me3SiO0.5)x(MeSiO1.5)y(Me2SiO)m(MeHSiO)n(MeViSiO)q(PhSiO1.5)t
(Me2SiRSi)z, wherein the integer that x is 1~10, the integer that y is 1~10, the integer that m is 1~10, the integer that n is 0~30, q
For 0~30 integer, the integer that t is 1~50, the integer that z is 1~10, R is alkyl chain and/or aryl chain.
3. rail traffic as described in claim 1 impacts organosilicon impregnating resin with high-low temperature resistant, which is characterized in that the increasing
Contain alkane chain or aromatic hydrocarbons chain, backbone structure R in the main chain of the tough organic-silicon-modified resin of type1Me2SiRSiMe2R1, wherein R1For
H and/or Vi (vinyl), R are alkyl chain and/or aryl chain.
4. rail traffic as claimed in claim 3 impacts organosilicon impregnating resin with high-low temperature resistant, which is characterized in that the increasing
The tough organic-silicon-modified resin of type is the copolymer containing polybutadiene chain link, diphenyl ether chain link or bisphenol A-type chain link in strand,
The molecular weight of the organic-silicon-modified resin of toughening type is 100-100000.
5. rail traffic as described in claim 1 impacts organosilicon impregnating resin with high-low temperature resistant, which is characterized in that the platinum
Gold complex catalyst is by chloroplatinic acid and the network containing one or more of nitrogen phosphate and sulfur, alkynol group, tin, vinyl compound
Close the platinum complex compound formed.
6. rail traffic as claimed in claim 5 impacts organosilicon impregnating resin with high-low temperature resistant, which is characterized in that the platinum
Gold complex catalyst Si―H addition reaction activity low-temperature catalyzed in is low, and high-temperature catalytic Si―H addition reaction activity is high；The middle low temperature
The reaction temperature of catalysis is 100 DEG C and hereinafter, the reaction temperature of the high-temperature catalytic is higher than 100 DEG C.
7. the preparation method that organosilicon impregnating resin is impacted in a kind of rail traffic with high-low temperature resistant, which is characterized in that including as follows
Step:
1) solvent, water and the hydrolyst that formula ratio is added into reaction vessel, open stirring, and mixing speed regards solution Cheng Jun
Subject to the lotion of phase, material temperature degree is controlled at 30~60 DEG C；
2) siloxanyl monomers of formula ratio are mixed evenly, control reaction temperature is 30~60 DEG C, slow into the lotion of step 1)
Slow that siloxanyl monomers are added dropwise, time for adding was controlled at 60-150 minutes, after completion of dropwise addition, controlled 40~80 DEG C of temperature of charge, after
It is continuous to be stirred to react 3~8 hours；
3) water is added to be washed, be layered into the reaction solution of step 2), washing times are 2~3 times, are warming up to 60- after washing again
150 DEG C, add formula ratio equilibrium catalyst carry out condensation and balanced reaction, the reaction time 1~5 hour；
4) water is added to be washed, be layered into the reaction solution of step 3), washing times are 3~5 times, remove equilibrium catalyst；
5) it is evaporated under reduced pressure out most of solvent into the reaction solution of step 4), increases temperature later to 190~210 DEG C, control is anti-
Pressure 500pa in container is answered hereinafter, removing low-boiling-point substance, the time for taking off low boiling control in 1~5h；
6) into step 5), the organic-silicon-modified resin of toughening type of addition formula ratio and platinum complex compound catalyst stir 30-
60min is to get organosilicon impregnating resin.
8. preparation method as claimed in claim 7, which is characterized in that in step 1), the siloxanyl monomers are to include benzene
Base unit, methyl hydrogen unit, methyl ethylene unit, methyl group unit, dimethyl units and closure agent unit composition；
The phenyl unit is the mixture of one or both of phenyltrimethoxysila,e, phenyl triethoxysilane；Institute
State methyl hydrogen unit be one of methyl hydrogen dimethoxysilane, methyl hydrogen diethoxy silane or mixture；The first
Base vinyl units are the mixing of methylvinyldimethoxysilane, methyl vinyl diethoxysilane one or two
Object；The methyl group unit is the mixture of one or both of methyltrimethoxysilane, methyltriethoxysilane；It is described
Dimethyl units are the mixture of one or both of dimethyldimethoxysil,ne, dimethyl diethoxysilane；It is described
Closure agent unit is 1,1,3,3- tetramethyl divinyl disiloxane, 1,1,3,3- tetramethyl disiloxane, two silicon of hexamethyl
One of oxygen alkane or a variety of mixtures.
9. preparation method as claimed in claim 7, which is characterized in that in step 1), the solvent is selected from toluene, diformazan
One of benzene, hexamethylene, 90-120 DEG C of boiling range petroleum ether, the additive amount of solvent are the 0.5~1.5 of siloxanyl monomers weight
Times；The additive amount of the water is 2~5 times of siloxanyl monomers weight；The additive amount of the hydrolyst is water weight
0.5%~5%.
10. preparation method as claimed in claim 7, which is characterized in that in step 3), the equilibrium catalyst accounts for siloxanes
The 0.005%~4% of monomer material total amount.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113845841A (en) * | 2021-11-09 | 2021-12-28 | 株洲时代电气绝缘有限责任公司 | Modified organic silicon solvent-free impregnating varnish and preparation method thereof |
| CN114289069A (en) * | 2021-12-31 | 2022-04-08 | 江西贝特利新材料有限公司 | Single-component platinum catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255361A (en) * | 2015-11-03 | 2016-01-20 | 株洲时代新材料科技股份有限公司 | Silicone impregnating varnish as well as preparation method and application thereof |
| CN105295720A (en) * | 2015-11-03 | 2016-02-03 | 株洲时代新材料科技股份有限公司 | Preparation method for organic silicon impregnating varnish |
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2018
- 2018-09-06 CN CN201811038765.9A patent/CN109355013A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255361A (en) * | 2015-11-03 | 2016-01-20 | 株洲时代新材料科技股份有限公司 | Silicone impregnating varnish as well as preparation method and application thereof |
| CN105295720A (en) * | 2015-11-03 | 2016-02-03 | 株洲时代新材料科技股份有限公司 | Preparation method for organic silicon impregnating varnish |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845841A (en) * | 2021-11-09 | 2021-12-28 | 株洲时代电气绝缘有限责任公司 | Modified organic silicon solvent-free impregnating varnish and preparation method thereof |
| CN114289069A (en) * | 2021-12-31 | 2022-04-08 | 江西贝特利新材料有限公司 | Single-component platinum catalyst and preparation method and application thereof |
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