CN108329474A - A kind of one-component additional organosilicon impregnating varnish organic siliconresin and its preparation method and application - Google Patents
A kind of one-component additional organosilicon impregnating varnish organic siliconresin and its preparation method and application Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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Abstract
Application the invention discloses a kind of one-component additional organosilicon impregnating varnish organic siliconresin and preparation method thereof and in preparing low volatilization one-component additional organosilicon impregnating varnish, the one-component additional organosilicon impregnating varnish organic siliconresin, general structure are (Me3SiO0.5)m(MeHSiO)n(MeViSiO)q(PhSiO1.5)t, the integer that m is 1~20, the integer that n is 1~30, the integer that q is 1~10, the integer that t is 2~60；Preparation method is：Using alkoxysilane mixture as raw material, it is prepared successively through hydrolysis-condensation reaction, end capping reaction and post-processing.The present invention is prepared for a kind of narrow molecular weight distribution by above-mentioned technique, the extremely low one-component additional organosilicon impregnating varnish organic siliconresin of remaining hydrogen chloride content, it is extremely low in the volatile quantity of 200 DEG C/1h using the one-component additional organosilicon impregnating varnish that it is prepared as raw material.
Description
Technical field
The present invention relates to the technical fields of organic siliconresin, and in particular to a kind of one-component additional organosilicon impregnating varnish use
Organic siliconresin and preparation method thereof and the application in preparing low volatilization one-component additional organosilicon impregnating varnish.
Background technology
It is the important insulating materials of one kind for painting base that silicone impregnating varnish, which is with organic siliconresin, be it is a kind of have it is highly cross-linked
The thennoset polysiloxane system of structure, organic group is connected using Si-O-Si as main chain, on silicon atom has highly cross-linked net
The polysiloxane of shape structure.Silicone impregnating varnish is different by crosslinking curing mode, can be divided into condensed type and add-on type.Condensation
Type silicone impregnating varnish is the silicone prepolymer that will contain the groups such as Si-OH, Si-OR, under catalyst action or heating
Further condensation cross-linking is at solid product；Additional organosilicon impregnating varnish is by the polysiloxanes of the key containing Si-Vi and containing Si-
The siloxanes of H keys occurs hydrosilylation reaction and is crosslinked under the action of catalyst.
Compared with condensed type liquid silicone impregnating varnish, additional organosilicon impregnating varnish has paint sample itself without organic molten
Agent is free from environmental pollution, it is small not generate by-product, shrinking percentage in the curing process, can deep cure, with short production cycle and efficient
The advantages that.Currently, predominating insulation one of of the additional organosilicon impregnating varnish as motor, passes through vacuum pressure impregnation motor
Rotor is greatly improved the electrical of motor, mechanics, heat conduction and barrier propterty, extends the service life of motor.Add-on type is organic
Silicon impregnating varnish should have low volatility, good permeability, high temperature resistant and high-insulativity.
Additional organosilicon impregnating varnish is usually by base resin (polymethyl-benzene base vinylsiloxane), crosslinking agent (poly- first
Base phenyl hydrogen siloxane), active viscosity-controlling agent (the substantially same base resin of its molecular composition), catalyst (transition metal such as platinum,
The complex of nickel, rhodium etc.), inhibitor composition.
As 105295720 A of Publication No. CN Chinese patent literature in disclose a kind of silicone impregnating varnish and its system
Preparation Method and application are made after being allocated by organic-silicone prepolymer A, organic-silicone prepolymer B, catalyst and inhibitor mixed
It is standby to obtain.Range of viscosities of the silicone impregnating varnish of acquisition under conditions of 23 ± 2 DEG C is 600~2000mpas, 180~
Cure fugitive constituent under conditions of 200 DEG C and is no more than 2%.Major defect is existing for the technical solution, the silicone impregnating varnish
It is made of two kinds of key components, as dual composition addition type silicone impregnating varnish, the industrially prepared of this kind of silicone impregnating varnish is drawn
Play high cost and complexity；In addition, to cure fugitive constituent under conditions of 180~200 DEG C minimum for the silicone impregnating varnish
0.9%, although meeting standard GB/T 15022-2007, cannot be satisfied some has the content of fugitive constituent the skill of requirements at the higher level
Art field.
It is for another example disclosed in the Chinese patent literature of 101070386 A of Publication No. CN and a kind of preparing one pack system silicon containing H-
The method of the organic siliconresin of the addition-crosslinkable of oxygen alkane is made of mono-component organic silicone resin, but disadvantage is raw material whole
Using chlorosilane mixture, a large amount of HCl is released in hydrolytic process, environmental pollution and equipment is easily caused to corrode, and reacts acute
It is strong, it is difficult to control.Although 0.01~1.0% concentration of aqueous solution of the alkali for the use of pH value being 7.0~8.5 in the preparation process washs
Including the phase of the organic siliconresin of the addition-crosslinkable of one pack system siloxanes containing H- is to reduce remaining HCl contents, but the washers
Dehydrogenation reaction easily occurs for skill, reduces hydrogen content in silicones.
Therefore, it is necessary to develop a kind of novel to low volatilization more environment-friendly, of low cost and simple for process, single group
Divide the preparation method of additional organosilicon impregnating varnish.
Invention content
The present invention is directed to the problems of the prior art, provides a kind of one-component additional organosilicon impregnating varnish organosilicon
Resin, narrow molecular weight distribution, remaining hydrogen chloride content is extremely low, organic as the low volatilization one-component add-on type of raw material preparation using it
Silicon impregnating varnish, it is extremely low in the volatile quantity of 200 DEG C/1h.
Specific technical solution is as follows：
A kind of one-component additional organosilicon impregnating varnish organic siliconresin, general structure are (Me3SiO0.5)m
(MeHSiO)n(MeViSiO)q(PhSiO1.5)t, wherein：
The integer that m is 1~20, the integer that n is 1~30, the integer that q is 1~10, the integer that t is 2~60.
Preferably, the one-component additional organosilicon impregnating varnish organic siliconresin, the m in general structure is 3
~12 integer, the integer that n is 3~15, the integer that q is 3~8, the integer that t is 6~25；Number-average molecular weight be 2000~
6000, weight average molecular weight is 3500~9500, and molecular weight distribution index is not more than 2.0；
In the organic siliconresin, HCl contents are less than 0.05ppm.
The invention also discloses the preparation method of above-mentioned one-component additional organosilicon impregnating varnish organic siliconresin, with
Alkoxysilane mixture is raw material, is prepared successively through hydrolysis-condensation reaction, end capping reaction and post-processing；
The alkoxysilane mixture is comprising phenyl T unit, methyl hydrogen D units, methyl ethylene D units and three
The composition of methyl M units；
The phenyl T unit is phenyltrimethoxysila,e and/or phenyl triethoxysilane；Methyl hydrogen D units are
Methyl hydrogen dimethoxysilane and/or methyl hydrogen diethoxy silane；Methyl ethylene D units are methyl ethylene dimethoxy
Silane and/or methyl vinyl diethoxysilane；Trimethyl M units are trimethylmethoxysilane and/or trimethyl ethoxy
Base silane.
The present invention provide it is a kind of using the mixture of alkoxy silane as raw material, through hydrolysis, polycondensation, sealing end, drying, alcohol extract
Etc. the techniques method for preparing one-component additional organosilicon impregnating varnish organic siliconresin, specially：
(1) alkoxysilane mixture is added into reactor, after being warming up to 30~60 DEG C, then is added dropwise to the acidity of metering
Catalyst is warming up to 60~80 DEG C again, after reacting 3~8h, is cooled to room temperature；
(2) organic solvent A is added in the reaction solution obtained to step (1), organic phase is obtained after extraction, liquid separation, wash
Organic solvent is removed after to neutrality, then obtains silicane hydrolysate after further condensation reaction under vacuum condition；
(3) silicane hydrolysate prepared by step (2) is mixed with organic solvent B and trim,ethylchlorosilane, at 30~80 DEG C
It is stirred to react after 3~8h and alcohols material A is added, keep the reaction temperature the reaction was continued 2~4h；
(4) reaction solution that step (3) obtains is washed to neutrality, organic phase is obtained after extraction, liquid separation, drying is added
Organic solvent is evaporated off after filtering in agent, obtains trimethyl silicon substrate terminated silane hydrolysate；Alcohols material B is added, through extracting, is divided
Upper layer alcohol phase is removed after liquid, lower layer's product obtains the one-component additional organosilicon impregnating varnish through vacuum removal low-boiling-point substance and uses
Organic siliconresin.
In step (1)：
The acidic catalyst can be selected from the acid solutions, preferably hydrochloric acid solution such as hydrochloric acid, sulfuric acid, the quality of HCl
Score is 3~15%, the hydrochloric acid solution that further preferably mass fraction of HCl is 5~10%.In 30~60 DEG C of temperature and stir
It mixes down, the acidic catalyst can be added by dropwise addition mode in reactor, and time for adding is not more than 30min.
Preferably, in the alkoxysilane mixture, phenyl T unit, methyl hydrogen D units, methyl ethylene D are mono-
Member and the molar ratio of trimethyl M units are 2~6:1~3:1:0.5~2；Further preferably 2.5~3.5:1.3~1.6:1:
1.2~1.6.Using the alkoxysilane mixture of different ratio, different group contents can be prepared, different number-average molecular weights have
Machine silicones.
Preferably, in water and alkoxysilane mixture in the acidic catalyst molar ratio of alkoxy be 2~
8:1；Further preferably 3~5:1.Acidic catalyst is warming up to 60~80 DEG C after being added, the reaction was continued 3~8h, into one
Step reinforces hydrolysis and condensation reaction.
In step (2)：
The organic solvent A needs immiscible with water, and is easy to and water stratification, preferably be selected from benzene, toluene, dichloromethane,
At least one of petroleum ether that petroleum ether that chloroform, boiling range are 30~60, boiling range are 60~90, ethyl acetate；Organic solvent A
Quality be 0.5~2 times of alkoxysilane mixture quality.
Since alkoxysilane mixture hydrolysis-condensation reaction is heterogeneous reaction, condensation reaction is insufficient, product molecule
Amount distribution is wide, and oligomer is high, causes volatile quantity under high temperature big.Contracting can be quickly evaporated off in heated under vacuum hydrolysate
Close product alcohol and water, promote silicone hydroxyl between and silicone hydroxyl and siloxy between condensation reaction, effectively reduce oligomer, subtract
Volatile quantity under few high temperature.
Preferably, the temperature of the further condensation reaction is 50~150 DEG C, the reaction time is 2~4h；Described
Pressure under vacuum condition is less than 100hPa, is further preferably no larger than 50hPa.
In step (3), remaining silicone hydroxyl can be to organic siliconresin impregnating varnish in the silicane hydrolysate prepared by step (2)
Solidification and viscosity stability bring adverse effect, need to carry out trim,ethylchlorosilane end capping reaction in the presence of an organic.
Preferably, the organic solvent B is selected from benzene, toluene, dichloromethane, chloroform, the oil that boiling range is 30~60
At least one of ether, the petroleum ether that boiling range is 60~90, ethyl acetate；The quality of organic solvent B is silane hydrolyzate amount of substance
0.5~1 times.
After end capping reaction carries out a period of time, also needing addition alcohols material A, the reaction was continued, the mesh that alcohols material A is added
The excessive trim,ethylchlorosilane for being with being added in end capping reaction react, be translated into trimethylalkyoxys iotalane.It compares
Alcohol is first added in the mode of operation for directly removing excessive trim,ethylchlorosilane by washing, the present invention, then is washed to
Neutrality can avoid generating trimethyl silanol and HCl in water-washing process, reduce emulsification, improves washing efficiency.Preferably, described
Alcohols material A, can be absolute ethyl alcohol can also be absolute methanol.
Further preferably, the mass ratio of the trim,ethylchlorosilane and silicane hydrolysate is 1~5：100；Described three
The molar ratio of methylchlorosilane and alcohols material A are 1:1~5.
The end capping reaction and alcoholysis reaction of step (3) will produce a small amount of HCl, and it is acidity to cause system.In organic solvent
In the presence of terminated silane hydrolysate is washed, can remove overwhelming majority HCl, but due in organic phase micro-moisture deposit
HCl is being caused to be difficult to completely remove.Therefore, it in step (4), increases in the organic phase after washing and drier is added, by
It is more easy to be adsorbed in the complex that drier is formed with water in HCl, by filtering out drier, HCl in organic phase can be significantly reduced
Content so that HCl contents are down to 0~1ppm.
Preferably, the drier is neutral drier, such as anhydrous sodium sulfate, anhydrous magnesium sulfate or anhydrous chlorination
Calcium.
Further preferably, the quality of the drier is the 1~5% of organic layer quality.
In step (4), also add alcohol extraction process, the alcohols material B by taking absolute methanol or absolute ethyl alcohol as an example as
Extractant.Due to the polar organic solvent that alcohol is strong hydrogen bonding power, the larger polysiloxanes hydrogen bond force of molecular weight is weak, and polarity is low, because
This, the solubility of alcohol wherein is small, and the two is insoluble system.And oligosiloxane polarity is strong, and it is good with alcohol compatibility, extracted by alcohol
Trimethyl silicon substrate terminated silane hydrolysate is taken, oligomer in silicone impregnating varnish can be further decreased.When using acetic acid second
When ester, dichloromethane isopolarity solvent, since its hydrogen bond force is weak, larger polysiloxanes and oligosiloxane have with molecular weight
Preferable dissolubility can not play extraction.Preferably, the alcohols material B and trimethyl silicon substrate terminated silane water
It is 0.5~2 to solve amount of substance ratio:1, further preferably 1:1.
The invention also discloses a kind of low volatilization one-component additional organosilicon impregnating varnish, raw material includes above-mentioned organosilicon
Resin, catalyst and inhibitor.
Preferably, the catalyst is platinum-divinyl tetramethyl disiloxane complex, for example, congratulating Li Shi lifes
The Karst platinum catalyst of production.In terms of platinum, the quality of catalyst is 10~300ppm of raw material gross mass；Further preferably 20
~100ppm.
Preferably, the inhibitor is selected from 1- ethynylcyclohexanols, 3,5- dimethyl -3- hexin -1- alcohol, 3- first
The quality of at least one of base -1- butine -3- alcohol, diallyl maleate, diallyl fumarate, inhibitor is that raw material is total
The 0.01~0.1% of quality.
Further preferably, the organic siliconresin, the integer that the m in general structure is 4~8, the integer that n is 5~12,
The integer that q is 3~8, the integer that t is 9~24；Number-average molecular weight is 2100~4800, and weight average molecular weight is 3550~8650, point
Son amount breadth coefficient is not more than 1.9；
In the organic siliconresin, HCl contents are not higher than 0.02ppm.
The preparation method of the low volatilization one-component additional organosilicon impregnating varnish is, by organic siliconresin, catalyst
It is uniformly mixed with inhibitor.
It is found through experiment that the one-component additional organosilicon impregnating varnish being prepared using above-mentioned preferred raw material, 200
DEG C/volatile quantity of 1h is extremely low, it is less than 0.1%.
Compared with prior art, the invention has the advantages that：
The present invention provides a kind of one-component additional organosilicon impregnating varnish organic siliconresins, are hydrogeneous simultaneously, contain second
The one-component crosslinkable polymer of alkenyl group, molecular weight distribution index are not more than 2.0, and remaining HCl contents are less than 0.05ppm；
The present invention also provides the preparation methods of the one-component additional organosilicon impregnating varnish organic siliconresin, using alkane
Oxysilane mixture is common raw material, and reaction process is mildly controllable, is nearly free from hydrogen chloride, and useful environment is protected and avoided
Etching apparatus；Using vacuum condition heat condensation, alcohol extraction process, oligomer and low-boiling-point substance in silicone impregnating varnish are effectively reduced
Content reduces silicone impregnating varnish volatile quantity under high temperature；Organic phase after being washed using neutral desiccant dryness, filters out drier
Afterwards, remaining hydrogen chloride content in organic phase is substantially reduced；The preparation process is simple, of low cost；
It is low the present invention also provides being prepared using the one-component additional organosilicon impregnating varnish with organic siliconresin as raw material
Volatilize one-component additional organosilicon impregnating varnish, extremely low in the volatile quantity of 200 DEG C/1h, is less than 0.1%.
Specific implementation mode
Below by embodiment, invention is further described in detail, raw materials used commercially available in embodiment.
Embodiment 1
It is packed into 2mol in 5000 milliliters of vials equipped with blender, heating, condenser distillation and dropping funel
(480g)PhSi(OEt)3、1mol(134g)MeHSi(OEt)2、1mol(160g)MeViSi(OEt)2、0.5mol(52g)
Me3SiOMe is heated to 60 DEG C.Under stiring, 699g15% hydrochloric acid (containing HCl105g, water 594g) is instilled by dropping funel,
Time for adding is 25min.80 DEG C are warming up to, 8h is reacted.Reaction finishes, and is cooled to room temperature, and 900g ethyl acetate is added.Stirring, it is quiet
It sets, divides and remove sour water.500mL × 3 time organic layer is washed to neutrality, ethyl acetate is evaporated off.150 DEG C are warming up to, in vacuum pressure
3h is maintained under 50hPa, obtains 510g silicane hydrolysates.
500g ethyl acetate is added into above-mentioned 510g silicane hydrolysates, 25g trim,ethylchlorosilanes are warming up to 60 DEG C, instead
Answer 4h.45g absolute ethyl alcohols, the reaction was continued 4h is added.Reaction finishes, washing 500mL × 3 time organic layer to neutrality.In organic phase
45g anhydrous sodium sulfates, dry 2h is added, organic layer becomes clear by muddiness, filters drier.Ethyl acetate is evaporated off, obtains
500g trimethyl silicon substrate terminated silane hydrolysates.1000g absolute methanols are added, stir, stand, divides and goes to upper layer.Lower layer's product exists
It under the conditions of vacuum pressure 50hPa, is heated to 120 DEG C and low-boiling-point substance is evaporated off, obtain 450g one-component additional organosilicon resins.
0.5g platinum-divinyl tetramethyl disiloxane is added into obtained 450g one-component additional organosilicon resins
Composition catalyst (Karst catalyst, a concentration of 20000ppm of platinum) and 0.05g1- ethynylcyclohexanols, are stirred
To low volatilization one-component additional organosilicon impregnating varnish.
The present embodiment synthesis one-component additional organosilicon resin nuclear magnetic resonance spectroscopy (1H NMR):7.5,7.2,
5.8,4.7,3.7,1.1,0.02ppm.Wherein, chemical shift 7.2-7.5 absorption peaks are silicon phenyl hydrogen absorption peak, chemical shift
5.8 absorption peaks are silico ethylene base hydrogen absorption peak, and 4.7 absorption peak of chemical shift is silicon hydrogen-based hydrogen absorption peak, and chemical shift 3.7 absorbs
Peak is OCH in silicon ethyoxyl2Hydrogen absorption peak, 1.1 absorption peak of chemical shift are CH in silicon ethyoxyl3Hydrogen absorption peak, chemical shift
0.02 absorption peak is silicon methyl hydrogen absorption peak.
The infrared absorption spectrum (FT-IR) of the one-component additional organosilicon resin of the present embodiment synthesis：2959,2170,
1595,1430,1260,1131,1029,840,755cm-1.Wherein, 2959cm-1Stretching absorbance peak, 2170cm are vibrated for C-H-1
For silicon hydrogen absorption peak, 1595cm-1And 1430cm-1For silico ethylene base and silicon phenyl absorption peak, 1260cm-1And 840cm-1For silicon first
Base absorption peak, 1131cm-1For silicon ethyoxyl absorption peak, 1029cm-1For silica absorption peak, 755cm-1For silicon phenyl absorption peak.
(dimethyl silicone polymer is standard specimen to the one-component additional organosilicon resin GPC of the present embodiment synthesis, and toluene is stream
Dynamic phase)：Mn=3500, Mw=6650, molecular weight distribution index：1.9.
It is found that the structural formula of one-component additional organosilicon resin manufactured in the present embodiment is (Me3SiO0.5)4
(MeHSiO)8(MeViSiO)8(PhSiO1.5)16。
One-component additional organosilicon resin hydrogen chloride content (ion chromatograph detection) manufactured in the present embodiment：
0.02ppm。
Low volatilization one-component additional organosilicon impregnating varnish manufactured in the present embodiment is in 200 DEG C of 1h volatile quantities：0.07%.
Insulation performance under normality after low volatilization one-component additional organosilicon impregnating varnish solidification manufactured in the present embodiment：Electrically
Intensity is 23.5Mv/m, and volume resistivity is 7.5 × 1014Ω m, dielectric dissipation factor 0.09%.
Embodiment 2
It is packed into 6mol in 10000 milliliters of vials equipped with blender, heating, condenser distillation and dropping funel
(1188g)PhSi(OMe)3、3mol(402g)MeHSi(OEt)2、1mol(132g)MeViSi(OMe)2、2.0mol(236g)
Me3SiOEt is heated to 30 DEG C.Under stiring, 3874g3% hydrochloric acid (containing HCl116g, water 3758g) is instilled by dropping funel,
Time for adding is 30min.60 DEG C are warming up to, 3h is reacted.Reaction finishes, and is cooled to room temperature, and 1000g dichloromethane is added.Stirring, it is quiet
It sets, divides and remove sour water.1000mL × 3 time organic layer is washed to neutrality, dichloromethane is evaporated off.50 DEG C are warming up to, in vacuum pressure
4h is maintained under 80hPa, obtains 1370g silicane hydrolysates.
700g dichloromethane is added into above-mentioned 1370g silicane hydrolysates, 15g trim,ethylchlorosilanes are warming up to 30 DEG C, instead
Answer 8h.10g absolute methanols, the reaction was continued 2h is added.Reaction finishes, washing 1000mL × 3 time organic layer to neutrality.In organic phase
25g anhydrous magnesium sulfates, dry 2h is added, organic phase becomes clear by muddiness, filters drier.Dichloromethane is evaporated off, obtains
1280g trimethyl silicon substrate terminated silane hydrolysates.700g absolute ethyl alcohols are added, stir, stand, divides and goes to upper layer.Lower layer's product exists
It under the conditions of vacuum pressure 50hPa, is heated to 120 DEG C and low-boiling-point substance is evaporated off, obtain 1150g one-component additional organosilicon resins.
15g platinum-two silica of divinyl-tetramethyl is added into obtained 1150g one-component additional organosilicon resins
Alkane composition catalyst (Karst catalyst, a concentration of 20000ppm of platinum) and 1g diallyl maleates are stirred
It is even to obtain low volatilization one-component additional organosilicon impregnating varnish.
One-component additional organosilicon resin manufactured in the present embodiment1H NMR:7.5,7.2,5.8,4.7,3.7,3.6,
1.1,0.03ppm；
One-component additional organosilicon resin FT-IR manufactured in the present embodiment：2960,2160,1600,1430,1260,
1130,1030,850,760cm-1；
(dimethyl silicone polymer is standard specimen to one-component additional organosilicon resin GPC manufactured in the present embodiment, and toluene is stream
Dynamic phase)：Mn=4800, Mw=8650, molecular weight distribution index：1.8；
It is found that the structural formula of one-component additional organosilicon resin manufactured in the present embodiment is (Me3SiO0.5)8
(MeHSiO)12(MeViSiO)4(PhSiO1.5)24。
One-component additional organosilicon resin hydrogen chloride content (ion chromatograph detection) prepared by the present embodiment 2：
0.02ppm。
Low volatilization one-component additional organosilicon impregnating varnish manufactured in the present embodiment is in 200 DEG C of 1h volatile quantities：0.05%.
Insulation performance under normality after low volatilization one-component additional organosilicon impregnating varnish solidification manufactured in the present embodiment：Electrically
Intensity is 22.8Mv/m, and volume resistivity is 8.0 × 1014Ω m, dielectric dissipation factor 0.08%.
Embodiment 3
It is packed into 3.0mol in 5000 milliliters of vials equipped with blender, heating, condenser distillation and dropping funel
(720g)PhSi(OEt)3、1.5mol(201g)MeHSi(OEt)2、1mol(160g)MeViSi(OEt)2、1.5mol(177g)
Me3SiOEt is heated to 45 DEG C.Under stiring, 1271g8% hydrochloric acid (containing HCl101g, water 1170g) is instilled by dropping funel,
Time for adding is 20min.70 DEG C are warming up to, 5h is reacted.Reaction finishes, and is cooled to room temperature, and 1500g petroleum ethers (boiling range 60- is added
90).Stirring is stood, and is divided and is removed sour water.500mL × 3 time organic layer is washed to neutrality, petroleum ether is evaporated off.80 DEG C are warming up to, true
2h is maintained under pneumatics power 30hPa, obtains 750g silicane hydrolysates.
700g petroleum ethers (boiling range 60-90), 25g trim,ethylchlorosilanes, heating are added into above-mentioned 750g silicane hydrolysates
To 60 DEG C, 4h is reacted.40g absolute ethyl alcohols, the reaction was continued 2h is added.Reaction finishes, and washing 1000mL × 3 time organic layer is into
Property.40g anhydrous calcium chlorides, dry 2h are added in organic phase, organic phase becomes clear by muddiness, filters drier.Stone is evaporated off
Oily ether obtains 700g trimethyl silicon substrate terminated silane hydrolysates.700g absolute methanols are added, stir, stand, divides and goes to upper layer.Under
Layer product is heated to 120 DEG C and low-boiling-point substance is evaporated off, obtain 650g one-component additional organosilicons under the conditions of vacuum pressure 50hPa
Resin.
2.5g platinum-two silica of divinyl-tetramethyl is added into obtained 650g one-component additional organosilicon resins
Alkane composition catalyst (Karst catalyst, a concentration of 20000ppm of platinum) and 0.25g diallyl fumarates, are stirred
Uniformly obtain low volatilization one-component additional organosilicon impregnating varnish.
One-component additional organosilicon resin manufactured in the present embodiment1H NMR:7.5,7.2,5.8,4.7,3.7,1.2,
0.01ppm；
One-component additional organosilicon resin FT-IR manufactured in the present embodiment：2960,2159,1600,1430,1259,
1130,1030,850,760cm-1；
(dimethyl silicone polymer is standard specimen to one-component additional organosilicon resin GPC manufactured in the present embodiment, and toluene is stream
Dynamic phase)：Mn=2100, Mw=3550, molecular weight distribution index：1.7；
It is found that the structural formula of one-component additional organosilicon resin manufactured in the present embodiment is (Me3SiO0.5)5
(MeHSiO)5(MeViSiO)3(PhSiO1.5)9。
One-component additional organosilicon resin hydrogen chloride content (ion chromatograph detection) manufactured in the present embodiment：
0.01ppm。
Low volatilization one-component additional organosilicon impregnating varnish manufactured in the present embodiment is in 200 DEG C of 1h volatile quantities：0.1%.
Insulation performance under normality after low volatilization one-component additional organosilicon impregnating varnish solidification manufactured in the present embodiment：Electrically
Intensity is 22.3Mv/m, and volume resistivity is 7.3 × 1014Ω m, dielectric dissipation factor 0.11%.
Comparative example 3-1
It using raw material and preparation process same as Example 3, differs only in, when preparing silicane hydrolysate, is evaporated off
After organic solvent, further heat condensation technique is not carried out under vacuum, specially：
It is packed into 3.0mol in 5000 milliliters of vials equipped with blender, heating, condenser distillation and dropping funel
(720g)PhSi(OEt)3、1.5mol(201g)MeHSi(OEt)2、1mol(160g)MeViSi(OEt)2、1.5mol(177g)
Me3SiOEt is heated to 45 DEG C.Under stiring, 1271g8% hydrochloric acid (containing HCl101g, water 1170g) is instilled by dropping funel,
Time for adding is 20min.70 DEG C are warming up to, 5h is reacted.Reaction finishes, and is cooled to room temperature, and 1500g petroleum ethers (boiling range 60- is added
90).Stirring is stood, and is divided and is removed sour water.500mL × 3 time organic layer is washed to neutrality, petroleum ether is evaporated off, obtains 750g silane hydrolyzates
Object.
700g petroleum ethers (boiling range 60-90), 25g trim,ethylchlorosilanes, heating are added into above-mentioned 750g silicane hydrolysates
To 60 DEG C, 4h is reacted.40g absolute ethyl alcohols, the reaction was continued 2h is added.Reaction finishes, and washing 1000mL × 3 time organic layer is into
Property.40g anhydrous calcium chlorides, dry 2h are added in organic phase, organic phase becomes clear by muddiness, filters drier.Stone is evaporated off
Oily ether obtains 700g trimethyl silicon substrate terminated silane hydrolysates.700g absolute methanols are added, stir, stand, divides and goes to upper layer.Under
Layer product is heated to 120 DEG C and low-boiling-point substance is evaporated off, obtain 650g one-component additional organosilicons under the conditions of vacuum pressure 50hPa
Resin.
2.5g platinum-two silica of divinyl-tetramethyl is added into obtained 650g one-component additional organosilicon resins
Alkane composition catalyst (Karst catalyst, a concentration of 20000ppm of platinum) and 0.25g diallyl fumarates, are stirred
Uniformly obtain one-component additional organosilicon impregnating varnish.
Additional organosilicon resin GPC prepared by this comparative example (dimethyl silicone polymer is standard specimen, and toluene is mobile phase)：
Mn=1500, Mw=3500, molecular weight distribution index：2.3.
One-component additional organosilicon resin hydrogen chloride content (ion chromatograph detection) prepared by this comparative example：
0.01ppm。
One-component additional organosilicon impregnating varnish prepared by this comparative example is in 200 DEG C/1h volatile quantities：1.0%.
Comparative example 3-2
It using raw material and preparation process same as Example 3, differs only in, after trim,ethylchlorosilane end capping reaction
The organic layer of washing, without desiccant dryness technique, specially：
It is packed into 3.0mol in 5000 milliliters of vials equipped with blender, heating, condenser distillation and dropping funel
(720g)PhSi(OEt)3、1.5mol(201g)MeHSi(OEt)2、1mol(160g)MeViSi(OEt)2、1.5mol(177g)
Me3SiOEt is heated to 45 DEG C.Under stiring, 1271g8% hydrochloric acid (containing HCl101g, water 1170g) is instilled by dropping funel,
Time for adding is 20min.70 DEG C are warming up to, 5h is reacted.Reaction finishes, and is cooled to room temperature, and 1500g petroleum ethers (boiling range 60- is added
90).Stirring is stood, and is divided and is removed sour water.500mL × 3 time organic layer is washed to neutrality, petroleum ether is evaporated off.80 DEG C are warming up to, true
2h is maintained under pneumatics power 30hPa, obtains 750g silicane hydrolysates.
700g petroleum ethers (boiling range 60-90), 25g trim,ethylchlorosilanes, heating are added into above-mentioned 750g silicane hydrolysates
To 60 DEG C, 4h is reacted.40g absolute ethyl alcohols, the reaction was continued 2h is added.Reaction finishes, and washing 1000mL × 3 time organic layer is into
Property.Petroleum ether and low-boiling-point substance is evaporated off, obtains 700g trimethyl silicon substrate terminated silane hydrolysates.700g absolute methanols are added, stir,
It stands, divides and go to upper layer.Lower layer's product is heated to 120 DEG C and low-boiling-point substance is evaporated off, it is mono- to obtain 650g under the conditions of vacuum pressure 50hPa
Composition addition type organic siliconresin.
2.5g platinum-two silica of divinyl-tetramethyl is added into obtained 650g one-component additional organosilicon resins
Alkane composition catalyst (Karst catalyst, a concentration of 20000ppm of platinum) and 0.25g diallyl fumarates, are stirred
Uniformly obtain one-component additional organosilicon impregnating varnish.
(dimethyl silicone polymer is standard specimen to one-component additional organosilicon resin GPC prepared by this comparative example, and toluene is stream
Dynamic phase)：Mn=2100, Mw=3550, molecular weight distribution index：1.7.
One-component additional organosilicon resin hydrogen chloride content (ion chromatograph detection) prepared by this comparative example：10ppm.
One-component additional organosilicon impregnating varnish prepared by this comparative example is in 200 DEG C/1h volatile quantities：0.2%.
Comparative example 3-3
It using raw material and preparation process same as Example 3, differs only in, trimethyl silicon substrate terminated silane hydrolysate
Methanol extraction technique is not carried out, specially：
It is packed into 3.0mol in 5000 milliliters of vials equipped with blender, heating, condenser distillation and dropping funel
(720g)PhSi(OEt)3、1.5mol(201g)MeHSi(OEt)2、1mol(160g)MeViSi(OEt)2、1.5mol(177g)
Me3SiOEt is heated to 45 DEG C.Under stiring, 1271g8% hydrochloric acid (containing HCl101g, water 1170g) is instilled by dropping funel,
Time for adding is 20min.70 DEG C are warming up to, 5h is reacted.Reaction finishes, and is cooled to room temperature, and 1500g petroleum ethers (boiling range 60- is added
90).Stirring is stood, and is divided and is removed sour water.500mL × 3 time organic layer is washed to neutrality, petroleum ether is evaporated off.80 DEG C are warming up to, true
2h is maintained under pneumatics power 30hPa, obtains 750g silicane hydrolysates.
700g petroleum ethers (boiling range 60-90), 25g trim,ethylchlorosilanes, heating are added into above-mentioned 750g silicane hydrolysates
To 60 DEG C, 4h is reacted.40g absolute ethyl alcohols, the reaction was continued 2h is added.Reaction finishes, and washing 1000mL × 3 time organic layer is into
Property.40g anhydrous calcium chlorides, dry 2h are added in organic phase, organic phase becomes clear by muddiness, filters drier.
It removes petroleum ether and low-boiling-point substance at 50hPa120 DEG C under reduced pressure, obtains 700g single-component organic silicon resins.
2.5g platinum-two silica of divinyl-tetramethyl is added into obtained 700g one-component additional organosilicon resins
Alkane composition catalyst (Karst catalyst, a concentration of 20000ppm of platinum) and 0.25g diallyl fumarates, are stirred
Uniformly obtain one-component additional organosilicon impregnating varnish.
(dimethyl silicone polymer is standard specimen to one-component additional organosilicon resin GPC prepared by this comparative example, and toluene is stream
Dynamic phase)：Mn=1550, Mw=5200, molecular weight distribution index：3.3.
The standby one-component additional organosilicon resin hydrogen chloride content (ion chromatograph detection) of this comparative example：0.01ppm.
One-component additional organosilicon impregnating varnish prepared by this comparative example is in 200 DEG C/1h volatile quantities：2.0%.
Claims (10)
1. a kind of one-component additional organosilicon impregnating varnish organic siliconresin, which is characterized in that general structure is
(Me3SiO0.5)m(MeHSiO)n(MeViSiO)q(PhSiO1.5)t, the integer that m is 1~20, the integer that n is 1~30, q is 1~10
Integer, t be 2~60 integer.
2. one-component additional organosilicon impregnating varnish organic siliconresin according to claim 1, it is characterised in that：
The integer that m in the general structure of the organic siliconresin is 3~12, the integer that n is 3~15, the integer that q is 3~8, t
For 6~25 integer；Number-average molecular weight is 2000~6000, and weight average molecular weight is 3500~9500, and molecular weight distribution index is not
More than 2.0；
In the organic siliconresin, HCl contents are less than 0.05ppm.
3. a kind of preparation side of one-component additional organosilicon impregnating varnish organic siliconresin according to claim 1 or 2
Method, which is characterized in that using alkoxysilane mixture as raw material, made successively through hydrolysis-condensation reaction, end capping reaction and post-processing
It is standby to obtain；
The alkoxysilane mixture is comprising phenyl T unit, methyl hydrogen D units, methyl ethylene D units and trimethyl
The composition of M units；
The phenyl T unit is phenyltrimethoxysila,e and/or phenyl triethoxysilane；Methyl hydrogen D units are methyl
Hydrogen dimethylamino oxysilane and/or methyl hydrogen diethoxy silane；Methyl ethylene D units are methylvinyldimethoxysilane
And/or methyl vinyl diethoxysilane；Trimethyl M units are trimethylmethoxysilane and/or front three base oxethyl silicon
Alkane.
4. the preparation method of one-component additional organosilicon impregnating varnish organic siliconresin according to claim 3, special
Sign is, specially：
(1) alkoxysilane mixture is added into reactor, after being warming up to 30~60 DEG C, then is added dropwise to the acidic catalyst of metering
Agent is warming up to 60~80 DEG C again, after reacting 3~8h, is cooled to room temperature；
(2) organic solvent A is added in the reaction solution obtained to step (1), organic phase is obtained after extraction, liquid separation, in being washed to
Organic solvent is removed after property, then silicane hydrolysate is obtained after further condensation reaction under vacuum condition；
(3) silicane hydrolysate prepared by step (2) is mixed with organic solvent B and trim,ethylchlorosilane, is stirred at 30~80 DEG C
Alcohols material A is added after reacting 3~8h, keeps the reaction temperature the reaction was continued 2~4h；
(4) reaction solution that step (3) obtains is washed to neutrality, organic phase is obtained after extraction, liquid separation, drier, mistake is added
Organic solvent is evaporated off after filter, obtains trimethyl silicon substrate terminated silane hydrolysate；Alcohols material B is added, is gone after extraction, liquid separation
Except upper layer alcohol phase, lower layer's product obtains the one-component additional organosilicon impregnating varnish organosilicon through vacuum removal low-boiling-point substance
Resin.
5. the preparation method of one-component additional organosilicon impregnating varnish organic siliconresin according to claim 4, special
Sign is, in step (1)：
The acidic catalyst is selected from hydrochloric acid solution, and HCl mass fractions are 3~15%, and the acidic catalyst is in 30min
Interior addition finishes；
In the alkoxysilane mixture, phenyl T unit, methyl hydrogen D units, methyl ethylene D units and trimethyl M are mono-
The molar ratio of member is 2~6:1~3:1:0.5~2；
The molar ratio of alkoxy is 2~8 in water and alkoxysilane mixture in the acidic catalyst:1.
6. the preparation method of one-component additional organosilicon impregnating varnish organic siliconresin according to claim 4, special
Sign is, in step (2)：
The organic solvent A be selected from benzene, the petroleum ether that toluene, dichloromethane, chloroform, boiling range are 30~60, boiling range be 60~
At least one of 90 petroleum ether, ethyl acetate；
The temperature of the further condensation reaction is 50~150 DEG C, and the time is 2~4h, and the pressure under vacuum condition is less than
100hPa。
7. the preparation method of one-component additional organosilicon impregnating varnish organic siliconresin according to claim 4, special
Sign is, in step (3)：
The organic solvent B be selected from benzene, the petroleum ether that toluene, dichloromethane, chloroform, boiling range are 30~60, boiling range be 60~
At least one of 90 petroleum ether, ethyl acetate；
The mass ratio of the trim,ethylchlorosilane and silicane hydrolysate is 1~5：100；
The molar ratio of the trim,ethylchlorosilane and alcohols material A are 1:1~5；
The alcohols material A is absolute methanol or absolute ethyl alcohol.
8. the preparation method of one-component additional organosilicon impregnating varnish organic siliconresin according to claim 4, special
Sign is, in step (4)：
The drier is neutral drier, and the quality of drier is the 1~5% of organic phase quality；
The alcohols material B is absolute methanol or absolute ethyl alcohol；
The alcohols material B is 0.5~2 with trimethyl silicon substrate terminated silane hydrolysate mass ratio:1.
9. a kind of low volatilization one-component additional organosilicon impregnating varnish, which is characterized in that raw material includes such as claims 1 or 2 institute
One-component additional organosilicon impregnating varnish organic siliconresin, catalyst and the inhibitor stated.
10. low volatilization one-component additional organosilicon impregnating varnish according to claim 9, which is characterized in that described urges
Agent is platinum-divinyl tetramethyl disiloxane complex, in terms of platinum, the quality of catalyst be raw material gross mass 10~
300ppm；
The inhibitor be selected from 1- ethynylcyclohexanols, 3,5- dimethyl -3- hexin -1- alcohol, 3- methyl-1s-butine -3- alcohol,
At least one of diallyl maleate, diallyl fumarate, the quality of inhibitor be raw material gross mass 0.01~
0.1%.
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| CN111574716A (en) * | 2019-12-31 | 2020-08-25 | 杭州师范大学 | Low-hydroxyl hydrogen-containing vinyl phenyl organic silicon resin and preparation method thereof |
| CN111592651A (en) * | 2019-12-31 | 2020-08-28 | 杭州师范大学 | Low-hydroxyl hydrogen-containing vinyl phenyl organic silicon resin and preparation method thereof |
| CN113956839A (en) * | 2021-11-05 | 2022-01-21 | 南京科矽新材料科技有限公司 | Fluorescent film adhesive for packaging high-power LED flip chip |
| CN114230795A (en) * | 2022-01-14 | 2022-03-25 | 万华化学集团股份有限公司 | Method for continuously preparing controllable high molecular weight MQ resin at low power |
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| CN111592651B (en) * | 2019-12-31 | 2022-02-01 | 杭州师范大学 | Low-hydroxyl hydrogen-containing vinyl phenyl organic silicon resin and preparation method thereof |
| CN113956839A (en) * | 2021-11-05 | 2022-01-21 | 南京科矽新材料科技有限公司 | Fluorescent film adhesive for packaging high-power LED flip chip |
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