CN103145992A - Vinyl silicon material as well as preparation method and application of vinyl silicon material in preparation of solventless insulating paint of high-temperature motor - Google Patents
Vinyl silicon material as well as preparation method and application of vinyl silicon material in preparation of solventless insulating paint of high-temperature motor Download PDFInfo
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- CN103145992A CN103145992A CN2013100902716A CN201310090271A CN103145992A CN 103145992 A CN103145992 A CN 103145992A CN 2013100902716 A CN2013100902716 A CN 2013100902716A CN 201310090271 A CN201310090271 A CN 201310090271A CN 103145992 A CN103145992 A CN 103145992A
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Abstract
The invention relates to a vinyl silicon material as well as a preparation method and application of the vinyl silicon material in preparation of a solventless insulating paint of a high-temperature motor. The vinyl silicon material disclosed by the invention is heat-resisting, good in compatibility with organic resin (for example, epoxy resin, polyester resin, alkyd resin and polyurethane resin), low in curing temperature, and fast in drying speed; the prepared insulating paints are simple in process, low in cost, high in mechanism strength, excellent in overall performance, low in medium curing temperature and fast in drying speed. The vinyl silicon material is expected to be widely applied to the fields of insulated immersion treatment of the high-temperature motor and electrician.
Description
Technical field
The present invention relates to thing in a kind of vinyl silicon, its preparation method and the application in preparation heat resisting motor solvent-free insulated paint.
Background technology
The traditional manufacturing technology of insullac is mainly with synthesizing various organic resins by copolymerization or blend and adding solidifying agent, catalyst diluent etc. to form, and the silicone resin that adopts in the insullac of the traditional silicone resin class overwhelming majority is solvent-borne type, thereby in the product use procedure because volatile gases is inevitable to the pollution of environment, and need hot setting, consume energy very surprising.Solvent-less organosilicon resin few in number exists viscosity large now, and is active low, needs the deficiencies such as hot setting.Comprehensive, in prior art, silicone based insullac does not meet the oligosaprobic requirement of less energy-consumption.Therefore in order to satisfy the demand of practical application, need exploitation badly and can be used for the technology of preparing that the heat resisting motor solvent-free insulated paint paints with high reactivity non-volatility high-temperature-resistant silicon resin.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high temperature resistant, high reactivity, with organic resin, thing in the vinyl silicon of excellent compatibility is arranged, and it is applicable to the preparation of heat resisting motor solvent-free insulated paint.
The present invention also will provide the preparation method of thing in a kind of vinyl silicon simultaneously.
For solving above technical problem, a kind of scheme that the present invention takes is:
Thing in the vinyl silicon of general formula (I) expression,
(I)
In formula (I), x, y, z, m, n, q are the number between 0～20 independently, and x, and m and n three are not 0, x simultaneously, and y and z three are not that 0, z and q are not 0 simultaneously simultaneously; R
1, R
2, R
3Independently for being selected from methyl, a kind of in vinyl and phenyl.
According to a concrete aspect of the present invention, R
1, R
2, R
3Be methyl or phenyl; Perhaps, R
1, R
2, R
3In have two for methyl, have one to be vinyl.
Preferably, in formula (I), x, y, z, m, n, q are the number between 0～15 independently, more preferably, are the number between 0～10.
According to a preferred aspect, in formula (I), x is the number between 0～5, and y is the number between 1～15, and z is the number between 0～5, and m is the number between 1～12; N is the number between 0～3; Q is the number between 0～3.
Preferably, vinyl silicon is 500～8000 according to the measured number-average molecular weight of GPC method.More preferably, molecular weight is 1000～7500.
Preferably, the humidity index that in vinyl silicon, thing is surveyed according to secant method is 180 ℃～220 ℃.
The total mole number of the phenyl that preferably, connects on the Si atom in thing in silicon, methyl and vinyl is 1.30～1.70; The ratio that in silicon, in thing, phenyl accounts for the total mole number of the phenyl, methyl and the vinyl that connect on the Si atom is 18%～50%; Vinyl mass content in thing in silicon is 0.5%～10%.
The another technical scheme that the present invention takes is: the preparation method of thing in a kind of above-mentioned vinyl silicon, it comprises the steps:
(1), make chlorosilane in the mixed solvent of non-polar organic solvent and polar organic solvent composition, under water exists, issue unboiled water solution reaction generation silanol in 20～50 ℃ of temperature and stirring, hydrolysis time is 2～8 hours, after hydrolysis reaction finishes, separate, obtain the solution of the non-polar solvent of silanol, wherein: described chlorosilane is by dichloromethyl phenylsilane (MePhSiCl
2), dimethyldichlorosilane(DMCS) (Me
2SiCl
2), methyl ethylene dichlorosilane (MeViSiCl
2), phenyl-trichloro-silicane (PhSiCl
3), diphenyl dichlorosilane (Ph
2SiCl
2), vinyl trichloro silane (ViSiCl
3) form according to the required ratio of formula (I), the mole dosage of water is 1～20 times of molar weight of chlorine in chlorosilane; Wherein, the Me represent methylidene, Vi represents vinyl, Ph represents phenyl;
(2), add catalyzer in the solution of the non-polar solvent of step (1) gained silanol, make the polycondensation that refluxes at 80～150 ℃ of temperature, when institute's viscosimetric reaches 500～5000mpa.s to the temperature of reaction, be cooled to 55～62 ℃, add end-capping reagent, continuation is after 55～120 ℃ of lower stirring reaction 0.5～3h, be washed with water to neutrality, divide and remove upper water, concentrated, the water that distillation desolventizing and reaction generate namely gets thing in vinyl silicon, and the structural formula of wherein said end-capping reagent is (SiR
1R
2R
3)
2O or SiR
1R
2R
3Cl, wherein; R
1, R
2, R
3Definition with claim 1, END CAPPED GROUP add quality be silanol quality 0.1%～5%; Described catalyzer is one or more the combination that is selected from as in 2 ethyl hexanoic acid zinc, potassium hydroxide and Tetramethylammonium hydroxide.
Further, in step (1), non-polar organic solvent in described mixed solvent can be for being selected from one or more the combination in dimethylbenzene, toluene, 200# industrial naptha, 120# industrial naptha and sherwood oil, the mass ratio of itself and chlorosilane can be 0.5～3:1, is preferably 1～2.5:1; Polar organic solvent in described mixed solvent can be for being selected from one or more the combination in propyl carbinol, acetone and 1-Methoxy-2-propyl acetate, and the mass ratio of itself and chlorosilane can be 0.5～3.0:1.
Further preferably, in step (1), the mole dosage of water is 4～16 times of molar weight of chlorine in chlorosilane.
further, the implementation process of step (1) is as follows: chlorosilane is dissolved in obtains chlorosilane solution in the described non-polar organic solvent of part, then this chlorosilane solution is added drop-wise to 20 ℃～50 ℃ by dropping funnel, non-polar organic solvent by remainder, in the mixture of polar organic solvent and water, reaction under agitation is hydrolyzed, after hydrolysis reaction finishes, standing, layering, emit lower floor's liquid, extremely neutral the supernatant liquid washing with 30 ℃～65 ℃ deionized waters, obtain mass concentration and be the solution of the non-polar solvent of 20%～30% silanol, continuation is 60～100 ℃ of temperature, pressure-0.08MPa～-concentrate under 0.096MPa, make that in solution, the mass concentration of silanol is increased to 50%～60%.
According to a concrete and preferred aspect, in step (1), chlorosilane is phenyl-trichloro-silicane (PhSiCl
3), vinyl trichloro silane (ViSiCl
3), dimethyldichlorosilane(DMCS) (Me
2SiCl
2), dichloromethyl phenylsilane (MePhSiCl
2), their consumption is 0.10～0.75 (mol ratio) according to Ph/R, and Vi/R is that 0.01～0.5 (mol ratio) feeds intake, and wherein: Ph is phenyl, and R is alkyl (comprising (Me), phenyl (Ph), vinyl (Vi)).More preferably, their consumption is 0.3～0.6 (mol ratio) according to Ph/R, and Vi/R is 0.02～0.10 (mol ratio), and R/Si 1.40～1.60 feeds intake.
Further, catalyzer described in step (2) is 2 ethyl hexanoic acid zinc (zinc content is 9wt%), and the add-on of catalyzer can for 0.1 ‰～50 ‰ of the solution of the non-polar solvent of silanol, be preferably 0.2 ‰～30 ‰.
Further, the end-capping reagent that uses in step (2) can be tri-phenyl chloride (Ph
3SiCl), tetramethyl divinyl disiloxane (［ ViMe
2Si ］
2O), the combination of one or more in hexamethyldisiloxane (MM).
Further, in step (2), the consumption of end-capping reagent is 0.1%～5%(mass concentration of silanol), consumption more preferably is 1.0%～5%(mass concentration of silanol).
Further, be concentrated in 80～100 ℃ of temperature described in step (2), pressure-0.08MPa～-carry out under 0.096MPa.
The invention still further relates to the application of thing in the preparation solvent-free insulated paint in above-mentioned vinyl silicon.
In vinyl silicon of the present invention, thing is according to the size of molecular weight separately, can directly add solidifying agent and other auxiliary agent to be deployed into high-temperature resistant insulating paint for motor, also can coordinate and add with containing hydrogen silicone oil coordination catalyst and other auxiliary agent to be deployed into the special high temperature-resistant insulating paint for motor, also can and add solidifying agent and auxiliary agent is deployed into the silicon-modified epoxy solvent-free insulated paint with itself and epoxy blend.Wherein solidifying agent is one or more in peroxidized t-butyl perbenzoate, dibenzoyl peroxide, dicumyl peroxide; Other auxiliary agent is one or more mixture of metal salt of organic carboxylic acid, acetyl acetone salt, phenyl-vinyl silicon oil and methyl vinyl silicon oil; Coordination catalyst is one or more of Platinic chloride one diethyl phthalate complex compound, Platinic chloride one Virahol complex compound and Platinic chloride one tetramethyl divinyl disiloxane complex compound; Epoxy resin is one or more of E44 type epoxy resin and E51 epoxy resin; Containing hydrogen silicone oil is one or more of Methyl Hydrogen Polysiloxane Fluid and phenyl hydrogen-containing silicon oil.
Compared with prior art, the present invention has following advantage and significant beneficial effect:
Thing in vinyl silicon provided by the invention contains aminomethyl phenyl silica chain link, high temperature resistant, high reactivity, with organic resin (as epoxy resin, vibrin, Synolac, urethane resin), excellent compatibility is arranged by a certain percentage.In this vinyl silicon, thing can be mixed with various solvent-free insulated paints, in use there is no volatile gases, and atmospheric environment is not polluted.In vinyl silicon, the humidity index of thing (secant method) is 180-220 ℃, drying property is that 100 ℃～150 ℃ * 2h solidifies, in 100:10～100:100 ratio, excellent compatibility is arranged all with organic resin (as epoxy resin, vibrin, Synolac, urethane resin), be particularly suitable for preparing the preparation that heat resisting motor is used solvent-free insulated paint.
Embodiment
Thing in the vinyl silicon of general formula provided by the invention (I), x in formula (I), y, z, m, n, q have represented the parameter of the molecular chain structure size of thing in silicon, the mol ratio of the corresponding monomer of its ratio x:y:z:m:n:q=, and x, y, z, m, n, the absolute value of q has characterized macromolecular mean polymerisation degree, and it was determined by the proportioning raw materials of polyreaction, catalyst type and consumption, temperature of reaction and reaction times, can adopt GPC molecular weight determination method in conjunction with elemental microanalysis method, and draw by calculating.In addition, it will be understood by those skilled in the art that, although in general formula (I), each structural unit links together according to a graded, but this is just in order to explain the molecular convenience of thing in vinyl silicon, do not represent in vinyl silicon that in thing, each structural unit connects according to such order, on ordinary meaning, each structural unit is random order and connects.
Easy for describing, in following examples, total group number (molal quantity) of the methyl that will represent to connect on the Si atom in thing in silicon with R/Si, phenyl, vinyl; In the group number that represents to connect on the Si atom with Ph/R, phenyl accounts for the ratio (mol ratio) of all (methyl, phenyl, vinyl) groups; Vi massfraction % represents vinyl proportion (mass percent) in thing in silicon.Their value is calculated by formula method of calculation well-known according to public affairs and is got, and no longer describes here.In addition, adopt gel permeation chromatography (GPC method) to measure to the molecular weight determination of thing in vinyl silicon.The performance of insullac is tested according to the corresponding national standard of insullac.
The present invention will be described in detail below in conjunction with specific embodiment.Below in each embodiment, all raw materials are commercially available.
Embodiment 1
Thing in a kind of vinyl silicon, it prepares as follows:
(1), in the 2000ml there-necked flask that 180g mixed solvent (form: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 ℃, under stirring, dropping is by 80.4g phenyl-trichloro-silicane (PhSiCl
3), 47.8g dimethyldichlorosilane(DMCS) (Me
2SiCl
2), 32.6g diphenyl dichlorosilane (Ph
2SiCl
2), 19.4g vinyl trichloro silane (ViSiCl
3) and the uniform mixed solution that forms of 270g dimethylbenzene, 2h dropwises, and continues to stir 1h, pours in the 3000ml separating funnel, and lower floor's acid solution is emitted in standing, layering.With the 1kg temperature be the deionized water repetitive scrubbing of 35 ℃ to neutral, get the silanol xylene solution, 85～95 ℃ of temperature, pressure-0.08MPa～-to be condensed into solid content under 0.096MPa be 50 ± 2%(mass concentration) the silanol xylene solution.
(2), getting above-mentioned gained solid content is 50 ± 2% silanol xylene solution 200g, the 2 ethyl hexanoic acid zinc (zinc content is 9%) that adds 0.02g, in the 500ml reaction flask in 80～100 ℃ of lower reflux water-dividing polycondensation 2h, be cooled to 60 ℃, add 5g tetramethyl divinyl disiloxane (［ ViMe
2Si ］
2O), continuation is at 60～80 ℃ of lower stirring reaction 2h, then carry out under 100 ℃ underpressure distillation (pressure-0.08MPa～-water that 0.096MPa) forms with solvent in removing system and reaction, obtain slightly opalesque as clear as crystal thick liquid, be thing in vinyl silicon.
In vinyl silicon, the salient features of thing and structural parameter thereof are referring to table 1.
Further calculate as can be known the R/Si=1.50 of thing in vinyl silicon, Ph/R=0.43, Vi mass fraction %=4.1.
Get thing 100g in gained vinyl silicon, E44 epoxy resin 20g, phenyl-vinyl silicon oil 5g, peroxidized t-butyl perbenzoate 2g, aluminium acetylacetonate 0.1g mixes being made into the epoxy modified silicone solvent-free insulated paint.Its salient features is referring to table 2.
Embodiment 2
Thing in a kind of vinyl silicon, it prepares as follows:
(1), in the 2000ml there-necked flask that 180g mixed solvent (form: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 ℃, under stirring, dropping is by 105.8g phenyl-trichloro-silicane (PhSiCl
3), 52.3 dimethyldichlorosilane(DMCS) (Me
2SiCl
2), 9.6g dichloromethyl phenylsilane (MePhSiCl
2), 6.3g methyl ethylene dichlorosilane (MeViSiCl
2) and the even mixed solution that forms of 270g dimethylbenzene, dropwise at 2h, continue to stir 1h, to pour in the 3000ml separating funnel, lower floor's acid solution is emitted in standing, layering.With the temperature of 1kg be 30 ℃ of deionized waters repeatedly to neutral, get the silanol xylene solution, 85～95 ℃ of temperature, pressure-0.08MPa～-to be condensed into solid content under 0.096MPa be 50 ± 2%(mass concentration) the silanol xylene solution.
(2), getting above-mentioned gained solid content is 50 ± 2% silanol xylene solution 200g, the 2 ethyl hexanoic acid zinc (zinc content is 9%) that adds 0.02g, in the 500ml reaction flask in 80～100 ℃ of lower reflux water-dividing polycondensation 2h, be cooled to 60 ℃, add 5g hexamethyldisiloxane (MM), continuation is at 60～80 ℃ of lower stirring reaction 2h, then carry out under 100 ℃ underpressure distillation (pressure-0.08MPa～-water that 0.096MPa) forms with solvent in removing system and reaction, obtain slightly opalesque as clear as crystal thick liquid, be thing in vinyl silicon.
In vinyl silicon, the salient features of thing and structural parameter thereof are referring to table 1.
Further calculate as can be known the R/Si=1.50 of thing in this routine vinyl silicon, Ph/R=0.37, Vi mass fraction %=1.4.
Get thing 100g in gained vinyl silicon, phenyl hydrogen-containing silicon oil 20g, phenyl-vinyl silicon oil 5g, Platinic chloride one tetramethyl divinyl disiloxane complex compound 1g mixes being made into solvent-free insulated paint.Its salient features is referring to table 2.
Embodiment 3
Thing in a kind of vinyl silicon, it prepares as follows:
(1), in the 2000ml there-necked flask that 180g mixed solvent (forming: dimethylbenzene 40g, toluene 128g and 1-Methoxy-2-propyl acetate 12g) and 720g water are housed, at 40 ± 5 ℃, under stirring, with 67.0g phenyl-trichloro-silicane (PhSiCl
3), 30.2g dimethyldichlorosilane(DMCS) (Me
2SiCl
2), 50.3g dichloromethyl phenylsilane (MePhSiCl
2), 26.2g methyl ethylene dichlorosilane (MeViSiCl
2) and the even mixed solution of 270g dimethylbenzene dropwise in 2h, continue to stir 1h, pour standing in the 3000ml separating funnel, layering into, emit lower floor's acid solution.With the temperature of 1kg be 40 ℃ of deionized waters repeatedly to neutral, obtain the silanol xylene solution, 85～95 ℃ of temperature, pressure-0.08MPa～-to be condensed into solid content under 0.096MPa be 50 ± 2%(mass concentration) the silanol xylene solution.
(2), to get above-mentioned gained solid content be 50 ± 2% silanol xylene solution 200g, adds the Tetramethylammonium hydroxide of 0.2g, in 80～100 ℃ of lower reflux water-dividing polycondensation 2h, is cooled to 60 ℃ in the 500ml reaction flask, adds 5g tri-phenyl chloride (Ph
3SiCl), continuation is at 60～80 ℃ of lower stirring reaction 2h, be washed till neutrality with deionized water, standing demix is removed water layer, then carry out under 100 ℃ underpressure distillation (pressure-0.08MPa～-water that 0.096MPa) forms with solvent in removing system and reaction, obtain slightly opalesque as clear as crystal thick liquid, be thing in vinyl silicon.
In vinyl silicon, the salient features of thing and structural parameter thereof are referring to table 1.
Further calculate as can be known the R/Si=1.68 of thing in this routine vinyl silicon, Ph/R=0.35, Vi mass fraction %=5.8.
Get thing 100g in gained vinyl silicon, E51 epoxy resin 20g, phenyl-vinyl silicon oil 5g, peroxidized t-butyl perbenzoate 2g, 2 ethyl hexanoic acid zinc (zinc content is 9%) 1g mixes being made into the epoxy modified silicone solvent-free insulated paint.Its salient features is referring to table 2.
Embodiment 4
Thing in a kind of vinyl silicon, it prepares as follows:
(1), in the 2000ml there-necked flask that 180g mixed solvent (forming: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 ℃, under stirring, with 94.6g phenyl-trichloro-silicane (PhSiCl
3), 19.9g dimethyldichlorosilane(DMCS) (Me
2SiCl
2), 29.8g dichloromethyl phenylsilane (MePhSiCl
2), 34.2g methyl ethylene dichlorosilane (MeViSiCl
2) and the even mixed solution of 270g dimethylbenzene dropwise at 2h, continue to stir 1h, pour standing in the 3000ml separating funnel, layering into, emit lower floor's acid solution.Be that the deionized water of 50 ℃ is repeatedly to neutral with the temperature of 1kg.Get gained silanol xylene solution, 85～95 ℃ of temperature, pressure-0.08MPa～-to be condensed into solid content under 0.096MPa be 50 ± 2%(mass concentration) the silanol xylene solution.
(2), getting above-mentioned gained solid content is 50 ± 2% silanol xylene solution 200g, the 2 ethyl hexanoic acid zinc (zinc content is 9%) that adds 0.02g, in the 500ml reaction flask in 80～100 ℃ of lower reflux water-dividing polycondensation 2h, be cooled to 60 ℃, add 5g tetramethyl divinyl disiloxane (［ ViMe
2Si ］
2O), continuation is at 60～80 ℃ of lower stirring reaction 2h, then carry out under 100 ℃ underpressure distillation (pressure-0.08MPa～-water that 0.096MPa) forms with solvent in removing system and reaction, obtain slightly opalesque as clear as crystal thick liquid, be thing in vinyl silicon.
In vinyl silicon, the salient features of thing and structural parameter thereof are referring to table 1.
Further calculate as can be known the R/Si=1.55 of thing in this routine vinyl silicon, Ph/R=0.39, Vi mass fraction %=7.6.
Get thing 100g phenyl-vinyl silicon oil 25g in gained vinyl silicon, dicumyl peroxide 1.5g, mixing can get high reactivity vinyl organosilicon solvent-free insulated paint.Its salient features is referring to table 2.
Embodiment 5
Thing in a kind of vinyl silicon, it prepares as follows:
(1), in the 2000ml there-necked flask that 180g mixed solvent (dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 ℃, under stirring, with 96.1g phenyl-trichloro-silicane (PhSiCl
3), 28.1g dimethyldichlorosilane(DMCS) (Me
2SiCl
2), 15.6g dichloromethyl phenylsilane (MePhSiCl
2), 34.8g methyl ethylene dichlorosilane (MeViSiCl
2) and the even mixed solution of 270g dimethylbenzene dropwise at 2h, continue to stir 1h, pour standing in the 3000ml separating funnel, layering into, emit lower floor's acid solution.Be that the deionized water of 30 ℃ is repeatedly to neutral with the temperature of 1kg.Get gained silanol xylene solution, 85～95 ℃ of temperature, pressure-0.08MPa～-to be condensed into solid content under 0.096MPa be 50 ± 2%(mass concentration) the silanol xylene solution.
(2), getting above-mentioned gained solid content is 50 ± 2% silanol xylene solution 200g, the potassium hydroxide that adds 0.2g, in 80～100 ℃ of lower reflux water-dividing polycondensation 2h, be cooled to 60 ℃ in the 500ml reaction flask, add 5g tetramethyl divinyl disiloxane (［ ViMe
2Si ］
2O), continuation is at 60～80 ℃ of lower stirring reaction 2h, be washed till neutrality with deionized water, standing demix is removed water layer, then carry out under 100 ℃ underpressure distillation (pressure-0.08MPa～-water that 0.096MPa) forms with solvent in removing system and reaction, obtain slightly opalesque as clear as crystal thick liquid, be thing in vinyl silicon.
In vinyl silicon, the salient features of thing and structural parameter thereof are referring to table 1.
Further calculate as can be known the R/Si=1.55 of thing in this routine vinyl silicon, Ph/R=0.35, Vi mass fraction %=7.7.
Get thing 100g phenyl-vinyl silicon oil 25g in vinyl silicon, dicumyl peroxide 1.5g, mixing can get high reactivity vinyl organosilicon solvent-free insulated paint.Its salient features is referring to table 2.
Embodiment 6
Thing in a kind of vinyl silicon, it prepares as follows:
(1), in the 2000ml there-necked flask that 180g mixed solvent (forming: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 ℃, under stirring, with 66.8g phenyl-trichloro-silicane (PhSiCl
3), 48.9g dimethyldichlorosilane(DMCS) (Me
2SiCl
2), 43.1g methyl ethylene dichlorosilane (MeViSiCl
2) and the even mixed solution of 270g dimethylbenzene dropwise at 2h, continue to stir 1h, pour standing in the 3000ml separating funnel, layering into, emit lower floor's acid solution.Be that the deionized water of 30 ℃ is repeatedly to neutral with the temperature of 1kg.Get gained silanol xylene solution, 85～95 ℃ of temperature, pressure-0.08MPa～-to be condensed into solid content under 0.096MPa be 50 ± 2%(mass concentration) the silanol xylene solution.
(2), get the silanol xylene solution 200g of solid content 50 ± 2%, the 2 ethyl hexanoic acid zinc (zinc content is 9%) that adds 0.02g, in 80～100 ℃ of lower reflux water-dividing polycondensation 2h, be cooled to 60 ℃ in the 500ml reaction flask, add 5g tetramethyl divinyl disiloxane (［ ViMe
2Si ］
2O), continuation is at 60～80 ℃ of lower stirring reaction 2h, then carry out under 100 ℃ underpressure distillation (pressure-0.08MPa～-water that 0.096MPa) forms with solvent in removing system and reaction, obtain slightly opalesque as clear as crystal thick liquid, be thing in vinyl silicon.
In vinyl silicon, the salient features of thing and structural parameter thereof are referring to table 1.
The R/Si=1.68 of thing in this routine vinyl silicon, Ph/R=0.19, Vi mass fraction %=9.6.
Get thing 100g in gained vinyl silicon, phenyl-vinyl silicon oil 25g, dibenzoyl peroxide 1.5g, mixing can get high reactivity vinyl organosilicon solvent-free insulated paint.Its salient features is referring to table 2.
Embodiment 7
Thing in a kind of vinyl silicon, it prepares as follows:
(1), in the 2000ml there-necked flask that 180g mixed solvent (forming: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 ℃, under stirring, with 85.0g phenyl-trichloro-silicane (PhSiCl
3), 64.9 dimethyldichlorosilane(DMCS) (Me
2SiCl
2), 19.6g diphenyl dichlorosilane (Ph
2SiCl
2), 3.0g vinyl trichloro silane (ViSiCl
3) and the even mixed solution of 270g dimethylbenzene dropwise at 2h, continue to stir 1h, pour standing in the 3000ml separating funnel, layering into, emit lower floor's acid solution.Deionized water with 1kg is repeatedly extremely neutral.Get gained silanol xylene solution, 85～95 ℃ of temperature, pressure-0.08MPa～-to be condensed into solid content under 0.096MPa be 50 ± 2%(mass concentration) the silanol xylene solution.
(2), get the silanol xylene solution 200g of solid content 50 ± 2%, the Tetramethylammonium hydroxide that adds 0.2g, in 80～100 ℃ of lower reflux water-dividing polycondensation 2h, be cooled to 60 ℃ in the 500ml reaction flask, add 5g tetramethyl divinyl disiloxane (［ ViMe
2Si ］
2O), continuation is at 60～80 ℃ of lower stirring reaction 2h, be washed till neutrality with deionized water, standing demix is removed water layer, then carry out under 100 ℃ underpressure distillation (pressure-0.08MPa～-water that 0.096MPa) forms with solvent in removing system and reaction, obtain slightly opalesque as clear as crystal thick liquid, be thing in vinyl silicon.
In vinyl silicon, the salient features of thing and structural parameter thereof are referring to table 1.
Further calculate as can be known the R/Si=1.58 of thing in this routine vinyl silicon, Ph/R=0.35, Vi mass fraction %=0.6.
Get thing 100g in gained vinyl silicon, phenyl hydrogen-containing silicon oil 5g, Methyl Hydrogen Polysiloxane Fluid 5g, methyl vinyl silicon oil 15g, Platinic chloride one Virahol complex compound 0.5g, Platinic chloride one diethyl phthalate complex compound 0.5g, mixing can get vinyl silicon hydrogen addition organosilicon solvent-free insullac.Its salient features is referring to table 2.
Embodiment 8
Thing in a kind of vinyl silicon, it prepares as follows:
(1), in the 2000ml there-necked flask that 180g mixed solvent (forming: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 ℃, under stirring, with 85.8g phenyl-trichloro-silicane (PhSiCl
3), 56.6g dimethyldichlorosilane(DMCS) (Me
2SiCl
2), 15.6g diphenyl dichlorosilane (Ph
2SiCl
2), 15.2g vinyl trichloro silane (ViSiCl
3) and the even mixed solution of 270g dimethylbenzene dropwise at 2h, continue to stir 1h, pour standing in the 3000ml separating funnel, layering into, emit lower floor's acid solution.Deionized water with 1kg is repeatedly extremely neutral.Get gained silanol xylene solution, 85～95 ℃ of temperature, pressure-0.08MPa～-to be condensed into solid content under 0.096MPa be 50 ± 2%(mass concentration) the silanol xylene solution.
(2), get the silanol xylene solution 200g of solid content 50 ± 2%, the 2 ethyl hexanoic acid zinc (zinc content is 9%) that adds 0.02g, in 80～100 ℃ of lower reflux water-dividing polycondensation 2h, be cooled to 60 ℃ in the 500ml reaction flask, add 5g tri-phenyl chloride (Ph
3SiCl), continuation is at 60～80 ℃ of lower stirring reaction 2h, then carry out under 100 ℃ underpressure distillation (pressure-0.08MPa～-water that 0.096MPa) forms with solvent in removing system and reaction, obtain slightly opalesque as clear as crystal thick liquid, be thing in vinyl silicon.
In vinyl silicon, the salient features of thing and structural parameter thereof are referring to table 1.
The R/Si=1.50 of thing in this routine vinyl silicon, Ph/R=0.35, Vi mass fraction %=3.2.
Get thing 100g in vinyl silicon, E51 epoxy resin 20g, phenyl-vinyl silicon oil 5g, peroxidized t-butyl perbenzoate 2g, 2 ethyl hexanoic acid zinc (zinc content is 9%) 1g, mixing can get the epoxy modified silicone solvent-free insulated paint.Its salient features is referring to table 2.
In table 1 vinyl silicon, the owner wants performance and structural parameter
1～8 salient features of joining insullac of table 2 embodiment
Above-described embodiment only is explanation technical conceive of the present invention and characteristics; its purpose is to allow person skilled in the art scholar can understand content of the present invention and implement according to this; can not limit protection scope of the present invention with this; all equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. thing in the vinyl silicon of general formula (I) expression,
(I)
In formula (I), x, y, z, m, n, q are the number between 0～20 independently, and x, and m and n three are not 0, x simultaneously, and y and z three are not that 0, z and q are not 0 simultaneously simultaneously; R
1, R
2, R
3Independently for being selected from methyl, a kind of in vinyl and phenyl.
2. thing in vinyl silicon according to claim 1, is characterized in that: R
1, R
2, R
3Be methyl or phenyl; Perhaps, R
1, R
2, R
3In have two for methyl, have one to be vinyl.
3. thing in vinyl silicon according to claim 1, it is characterized in that: the humidity index that in vinyl silicon, thing is surveyed according to secant method is 180 ℃～220 ℃.
4. thing in vinyl silicon according to claim 1, it is characterized in that: the total mole number of the phenyl that connects on the Si atom in thing in silicon, methyl and vinyl is 1.30～1.70; The ratio that in silicon, in thing, phenyl accounts for the total mole number of the phenyl, methyl and the vinyl that connect on the Si atom is 18%～50%; Vinyl mass content in thing in silicon is 0.5%～10%.
5. thing in vinyl silicon according to claim 1, it is characterized in that: described vinyl silicon is 500～8000 according to the measured molecular weight of GPC method.
6. the preparation method of thing in the described vinyl silicon of any one right in a claim 1 to 5, is characterized in that: comprise the steps:
(1), make chlorosilane in the mixed solvent of non-polar organic solvent and polar organic solvent composition, under water exists, issue unboiled water solution reaction generation silanol in 20～50 ℃ of temperature and stirring, hydrolysis time is 2～8 hours, after hydrolysis reaction finishes, separate, obtain the solution of the non-polar solvent of silanol, wherein: described chlorosilane is by dichloromethyl phenylsilane, dimethyldichlorosilane(DMCS), the methyl ethylene dichlorosilane, phenyl-trichloro-silicane, diphenyl dichlorosilane, vinyl trichloro silane forms according to the required ratio of formula (I), the mole dosage of water is 1～20 times of molar weight of chlorine in chlorosilane,
(2), add catalyzer in the solution of the non-polar solvent of step (1) gained silanol, make the polycondensation that refluxes at 80～150 ℃ of temperature, when institute's viscosimetric reaches 500～5000mpa.s to the temperature of reaction, be cooled to 55～62 ℃, add end-capping reagent, continuation is after 55～120 ℃ of lower stirring reaction 0.5～3h, be washed with water to neutrality, divide and remove upper water, concentrated, the water that distillation desolventizing and reaction generate namely gets thing in vinyl silicon, and the structural formula of wherein said end-capping reagent is (SiR
1R
2R
3)
2O or SiR
1R
2R
3Cl, wherein; R
1, R
2, R
3Definition with claim 1, END CAPPED GROUP add quality be silanol quality 0.1%～5%; Described catalyzer is one or more the combination that is selected from as in 2 ethyl hexanoic acid zinc, potassium hydroxide and Tetramethylammonium hydroxide.
7. the preparation method of thing in vinyl silicon according to claim 6, it is characterized in that: in step (1), non-polar organic solvent in described mixed solvent is one or more the combination that is selected from dimethylbenzene, toluene, 200# industrial naptha, 120# industrial naptha and sherwood oil, and the mass ratio of itself and chlorosilane is 0.5～3:1; Polar organic solvent in described mixed solvent is one or more the combination that is selected from propyl carbinol, acetone and 1-Methoxy-2-propyl acetate, and the mass ratio of itself and chlorosilane is 0.5～3.0:1.
8. the preparation method of thing according to claim 6 or 7 described vinyl silicon, it is characterized in that: the implementation process of step (1) is as follows: chlorosilane is dissolved in obtains chlorosilane solution in the described non-polar organic solvent of part, then this chlorosilane solution is added drop-wise to 20 ℃～50 ℃ by dropping funnel, non-polar organic solvent by remainder, in the mixture of polar organic solvent and water, reaction under agitation is hydrolyzed, after hydrolysis reaction finishes, standing, layering, emit lower floor's liquid, extremely neutral the supernatant liquid washing with 30 ℃～65 ℃ deionized waters, obtain mass concentration and be the solution of the non-polar solvent of 20%～30% silanol, continuation is 60～100 ℃ of temperature, pressure-0.08MPa～-concentrate under 0.096MPa, make that in solution, the mass concentration of silanol is increased to 50%～60%.
9. the preparation method of thing in vinyl silicon according to claim 6 is characterized in that: be concentrated in 80～100 ℃ of temperature described in step (2), and pressure-0.08MPa～-carry out under 0.096MPa.
10. the application of thing in the preparation solvent-free insulated paint in the described vinyl silicon of any one claim in claim 1 to 5.
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| CN105348534A (en) * | 2015-11-30 | 2016-02-24 | 苏州太湖电工新材料股份有限公司 | Nanometer silicon dioxide hybrid vinyl phenyl silicon intermediate material and preparing method and application thereof |
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| CN102898649A (en) * | 2012-05-11 | 2013-01-30 | 杭州师范大学 | Refractive index-adjustable MDT silicone resin and preparation method thereof |
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| CN102898649A (en) * | 2012-05-11 | 2013-01-30 | 杭州师范大学 | Refractive index-adjustable MDT silicone resin and preparation method thereof |
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| CN106589377A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Vinyl-phenyl-containing polysiloxane and preparation method thereof |
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| CN113842839A (en) * | 2021-09-11 | 2021-12-28 | 唐山三友硅业有限责任公司 | Preparation method of vinyl-terminated silicone oil and reaction kettle for preparation |
| CN113842839B (en) * | 2021-09-11 | 2024-03-01 | 唐山三友硅业股份有限公司 | Preparation method of vinyl-terminated silicone oil and reaction kettle for preparation |
| CN114045110A (en) * | 2021-12-08 | 2022-02-15 | 刁嘉乐 | Organic silicon solvent-free impregnating resin and preparation method thereof |
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