CN103145992B - 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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- CN103145992B CN103145992B CN201310090271.6A CN201310090271A CN103145992B CN 103145992 B CN103145992 B CN 103145992B CN 201310090271 A CN201310090271 A CN 201310090271A CN 103145992 B CN103145992 B CN 103145992B
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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 preparing the application in heat resisting motor solvent-free insulated paint.
Background technology
The traditional manufacturing technology of insullac mainly with the various organic resin of synthesis by copolymerization or blended and add solidifying agent, catalyst diluent etc. and form, and the silicone resin overwhelming majority adopted in the insullac of traditional silicone resin class is solvent-borne type, thus in product use procedure because the pollution of volatile gases to environment is inevitable, and need hot setting, consume energy very surprising.It is large then to there is viscosity in solvent-less organosilicon resin now few in number, 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 meet the demand of practical application, the technology of preparing that exploitation can be used for heat resisting motor solvent-free insulated paint high reactivity non-volatility high-temperature-resistant silicon resin paint is needed badly.
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, has thing in the vinyl silicon of excellent compatibility with organic resin, 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 that general formula (I) represents,
(I)
In formula (I), x, y, z, m, n, q are the number between 0 ~ 20 independently, and when x, m and n three is different be 0, x, y and z three different time be 0, z different with q time be 0; R
1, R
2, R
3independently for being selected from methyl, the one in vinyl and phenyl.
According to a concrete aspect of the present invention, R
1, R
2, R
3be methyl or phenyl; Or, R
1, R
2, R
3in have two for methyl, have one for 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 number-average molecular weight measured by GPC method.More preferably, molecular weight is 1000 ~ 7500.
Preferably, in vinyl silicon, thing is 180 DEG C ~ 220 DEG C according to the humidity index that secant method is surveyed.
Preferably, the total mole number of the phenyl in thing, Si atom connected 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 phenyl, methyl and the vinyl that Si atom connects is 18% ~ 50%; The mass content of vinyl in silicon in thing 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 non-polar organic solvent and polar organic solvent composition mixed solvent in, in the presence of water, issue raw hydrolysis reaction in temperature 20 ~ 50 DEG C and stirring and generate silanol, hydrolysis time is 2 ~ 8 hours, after hydrolysis reaction terminates, be separated, obtain the solution of the non-polar solvent of silanol, wherein: described chlorosilane is by dichloromethyl phenylsilane (MePhSiCl
2), dimethyldichlorosilane(DMCS) (Me
2siCl
2), methylvinyldichlorosilane (MeViSiCl
2), phenyl-trichloro-silicane (PhSiCl
3), diphenyl dichlorosilane (Ph
2siCl
2), vinyl trichloro silane (ViSiCl
3) according to the ratio composition needed for formula (I), the mole dosage of water is 1 ~ 20 times of the molar weight of chlorine in chlorosilane; Wherein, Me represents methyl, and Vi represents vinyl, and Ph represents phenyl;
(2), in the solution of the non-polar solvent of step (1) gained silanol, catalyzer is added, make to carry out backflow polycondensation at temperature 80 ~ 150 DEG C, when to temperature of reaction, institute's viscosimetric reaches 500 ~ 5000mpa.s, be cooled to 55 ~ 62 DEG C, add end-capping reagent, continue at 55 ~ 120 DEG C after stirring reaction 0.5 ~ 3h, be washed with water to neutrality, divide and remove upper water, concentrated, the water that distillation generates except desolventizing and reaction, obtain thing in vinyl silicon, 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, add that quality is the quality of silanol 0.1% ~ 5% of END CAPPED GROUP; Described catalyzer is be selected from the combination into one or more in 2 ethyl hexanoic acid zinc, potassium hydroxide and Tetramethylammonium hydroxide.
Further, in step (1), non-polar organic solvent in described mixed solvent can 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 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 the molar weight of chlorine in chlorosilane.
Further, the implementation process of step (1) is as follows: be dissolved in by chlorosilane in the described non-polar organic solvent of part and obtain chlorosilane solution, then this chlorosilane solution is added drop-wise to 20 DEG C ~ 50 DEG C by dropping funnel, by the non-polar organic solvent of remainder, in the mixture of polar organic solvent and water, under agitation be hydrolyzed reaction, after hydrolysis reaction terminates, leave standstill, layering, release lower floor's liquid, with 30 DEG C ~ 65 DEG C deionized waters, supernatant liquid washing is extremely neutral, obtain the solution that mass concentration is the non-polar solvent of the silanol of 20% ~ 30%, continue temperature 60 ~ 100 DEG C, concentrate under pressure-0.08MPa ~-0.096MPa, the mass concentration of silanol in solution is made to be 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, Vi/R is that 0.01 ~ 0.5 (mol ratio) feeds intake, and wherein: Ph is phenyl, 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 (Zn content is 9wt%), and the add-on of catalyzer can be 0.1 ‰ ~ 50 ‰ of the solution of the non-polar solvent of silanol, is preferably 0.2 ‰ ~ 30 ‰.
Further, the end-capping reagent used in step (2) can be tri-phenyl chloride (Ph
3siCl), tetramethyl divinyl disiloxane (［ ViMe
2si ］
2o) one or more the combination, in hexamethyldisiloxane (MM).
Further, in step (2), the consumption of end-capping reagent is 0.1% ~ 5%(mass concentration of silanol), consumption is more preferably 1.0% ~ 5%(mass concentration of silanol).
Further, be concentrated in temperature 80 ~ 100 DEG C described in step (2), carry out under pressure-0.08MPa ~-0.096MPa.
The invention still further relates to thing in above-mentioned vinyl silicon and prepare the application in solvent-free insulated paint.
In vinyl silicon of the present invention, thing is according to the size of respective molecular weight, can directly add solidifying agent and other auxiliary agent is deployed into high-temperature resistant insulating paint for motor, also can coordinate with containing hydrogen silicone oil and add coordination catalyst and other auxiliary agent is deployed into special high temperature-resistant insulating paint for motor, also can add solidifying agent and auxiliary agent is deployed into 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 isopropanol complex 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, tool of the present invention has the following advantages and significant beneficial effect:
Thing in vinyl silicon provided by the invention, containing aminomethyl phenyl silica chain link, high temperature resistant, high reactivity, has excellent compatibility with organic resin (as epoxy resin, vibrin, Synolac, urethane resin) by a certain percentage.In this vinyl silicon, thing can be mixed with various solvent-free insulated paint, does not in use have volatile gases, does not pollute atmospheric environment.In vinyl silicon, the humidity index (secant method) of thing is 180-220 DEG C, drying property is that 100 DEG C ~ 150 DEG C × 2h solidifies, all there is excellent compatibility with organic resin (as epoxy resin, vibrin, Synolac, urethane resin) in 100:10 ~ 100:100 ratio, be particularly suitable for the preparation preparing heat resisting motor 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 represent 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, the absolute value of n, q characterizes macromolecular mean polymerisation degree, and it determined by the proportioning raw materials of polyreaction, catalyst type and consumption, temperature of reaction and reaction times, GPC molecular weight determination method can be adopted in conjunction with elemental microanalysis method, and draw by calculating.In addition, it will be understood by those skilled in the art that, although each structural unit links together according to a graded in general formula (I), but this is just in order to state the molecular convenience of thing in vinyl silicon, do not represent that in vinyl silicon, in thing, each structural unit connects according to such order, on ordinary meaning, each structural unit is that random order connects.
Easy for describing, in following examples, by represent with R/Si in thing, Si atom connects in silicon methyl, phenyl, vinyl total group number (molal quantity); Represent that with Ph/R in the group number that Si atom connects, phenyl accounts for the ratio (mol ratio) of all (methyl, phenyl, vinyl) group; Vi massfraction % represents vinyl proportion (mass percent) in thing in silicon.Their value calculates according to the well-known method of calculation of public affairs by filling a prescription and obtains, and no longer describes here.In addition, gel permeation chromatography (GPC method) is adopted 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.
Below in conjunction with specific embodiment, the present invention will be described in detail.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 (composition: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 DEG C, under stirring, drip 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 of 270g dimethylbenzene composition, 2h dropwises, and continues to stir 1h, pours in 3000ml separating funnel, leaves standstill, layering, releases lower floor acid solution.By 1kg temperature be the deionized water repetitive scrubbing of 35 DEG C to neutral, obtain silanol xylene solution, carrying out being condensed into solid content under temperature 85 ~ 95 DEG C, pressure-0.08MPa ~-0.096MPa is 50 ± 2%(mass concentration) silanol xylene solution.
(2) the silanol xylene solution 200g that above-mentioned gained solid content is 50 ± 2%, is got, add the 2 ethyl hexanoic acid zinc (Zn content is 9%) of 0.02g, in 500ml reaction flask at 80 ~ 100 DEG C reflux water-dividing polycondensation 2h, be cooled to 60 DEG C, add 5g tetramethyl divinyl disiloxane (［ ViMe
2si ］
2o), continue stirring reaction 2h at 60 ~ 80 DEG C, then at 100 DEG C, carry out underpressure distillation (pressure-0.08MPa ~-0.096MPa) to remove the water that in system, solvent and reaction are formed, 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 see table 1.
Further calculating is known, the R/Si=1.50 of thing in vinyl silicon, Ph/R=0.43, Vi mass fraction %=4.1.
Get thing 100g, E44 epoxy resin 20g in gained vinyl silicon, phenyl-vinyl silicon oil 5g, peroxidized t-butyl perbenzoate 2g, aluminium acetylacetonate 0.1g, mixing is made into epoxy modified silicone solvent-free insulated paint.Its salient features is see 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 (composition: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 DEG C, under stirring, drip by 105.8g phenyl-trichloro-silicane (PhSiCl
3), 52.3 dimethyldichlorosilane(DMCS) (Me
2siCl
2), 9.6g dichloromethyl phenylsilane (MePhSiCl
2), 6.3g methylvinyldichlorosilane (MeViSiCl
2) and the Homogeneous phase mixing liquid of 270g dimethylbenzene composition, dropwise at 2h, continue to stir 1h, pour in 3000ml separating funnel, leave standstill, layering, release lower floor acid solution.With the temperature of 1kg be 30 DEG C of deionized waters repeatedly to neutral, obtain silanol xylene solution, carrying out being condensed into solid content under temperature 85 ~ 95 DEG C, pressure-0.08MPa ~-0.096MPa is 50 ± 2%(mass concentration) silanol xylene solution.
(2) the silanol xylene solution 200g that above-mentioned gained solid content is 50 ± 2%, is got, add the 2 ethyl hexanoic acid zinc (Zn content is 9%) of 0.02g, in 500ml reaction flask at 80 ~ 100 DEG C reflux water-dividing polycondensation 2h, be cooled to 60 DEG C, add 5g hexamethyldisiloxane (MM), continue stirring reaction 2h at 60 ~ 80 DEG C, then at 100 DEG C, underpressure distillation (pressure-0.08MPa ~-0.096MPa) is carried out to remove the water that in system, solvent and reaction are formed, 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 see table 1.
Further calculating is known, the R/Si=1.50 of thing, Ph/R=0.37, Vi mass fraction %=1.4 in this routine vinyl silicon.
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, mixing is made into solvent-free insulated paint.Its salient features is see 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 (composition: dimethylbenzene 40g, toluene 128g and 1-Methoxy-2-propyl acetate 12g) and 720g water are housed, at 40 ± 5 DEG C, under stirring, by 67.0g phenyl-trichloro-silicane (PhSiCl
3), 30.2g dimethyldichlorosilane(DMCS) (Me
2siCl
2), 50.3g dichloromethyl phenylsilane (MePhSiCl
2), 26.2g methylvinyldichlorosilane (MeViSiCl
2) and 270g dimethylbenzene Homogeneous phase mixing liquid dropwise in 2h, continue to stir 1h, pour in 3000ml separating funnel leave standstill, layering, release lower floor acid solution.With the temperature of 1kg be 40 DEG C of deionized waters repeatedly to neutral, obtain silanol xylene solution, carrying out being condensed into solid content under temperature 85 ~ 95 DEG C, pressure-0.08MPa ~-0.096MPa is 50 ± 2%(mass concentration) silanol xylene solution.
(2) the silanol xylene solution 200g that above-mentioned gained solid content is 50 ± 2%, is got, add the Tetramethylammonium hydroxide of 0.2g, in 500ml reaction flask at 80 ~ 100 DEG C reflux water-dividing polycondensation 2h, be cooled to 60 DEG C, add 5g tri-phenyl chloride (Ph
3siCl), continue stirring reaction 2h at 60 ~ 80 DEG C, neutrality is washed till with deionized water, stratification removing water layer, then at 100 DEG C, underpressure distillation (pressure-0.08MPa ~-0.096MPa) is carried out to remove the water that in system, solvent and reaction are formed, 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 see table 1.
Further calculating is known, the R/Si=1.68 of thing in the vinyl silicon of this example, Ph/R=0.35, Vi mass fraction %=5.8.
Get thing 100g, E51 epoxy resin 20g in gained vinyl silicon, phenyl-vinyl silicon oil 5g, peroxidized t-butyl perbenzoate 2g, 2 ethyl hexanoic acid zinc (Zn content is 9%) 1g, mixing is made into epoxy modified silicone solvent-free insulated paint.Its salient features is see 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 (composition: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 DEG C, under stirring, by 94.6g phenyl-trichloro-silicane (PhSiCl
3), 19.9g dimethyldichlorosilane(DMCS) (Me
2siCl
2), 29.8g dichloromethyl phenylsilane (MePhSiCl
2), 34.2g methylvinyldichlorosilane (MeViSiCl
2) and 270g dimethylbenzene Homogeneous phase mixing liquid dropwise at 2h, continue to stir 1h, pour in 3000ml separating funnel leave standstill, layering, release lower floor acid solution.Be that the deionized water of 50 DEG C is repeatedly to neutral by the temperature of 1kg.Get gained silanol xylene solution, carrying out being condensed into solid content under temperature 85 ~ 95 DEG C, pressure-0.08MPa ~-0.096MPa is 50 ± 2%(mass concentration) silanol xylene solution.
(2) the silanol xylene solution 200g that above-mentioned gained solid content is 50 ± 2%, is got, add the 2 ethyl hexanoic acid zinc (Zn content is 9%) of 0.02g, in 500ml reaction flask at 80 ~ 100 DEG C reflux water-dividing polycondensation 2h, be cooled to 60 DEG C, add 5g tetramethyl divinyl disiloxane (［ ViMe
2si ］
2o), continue stirring reaction 2h at 60 ~ 80 DEG C, then at 100 DEG C, carry out underpressure distillation (pressure-0.08MPa ~-0.096MPa) to remove the water that in system, solvent and reaction are formed, 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 see table 1.
Further calculating is known, the R/Si=1.55 of thing in the vinyl silicon of this example, Ph/R=0.39, Vi mass fraction %=7.6.
Get thing 100g phenyl-vinyl silicon oil 25g, dicumyl peroxide 1.5g in gained vinyl silicon, mixing can obtain high reactivity vinyl organosilicon solvent-free insulated paint.Its salient features is see 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 DEG C, under stirring, by 96.1g phenyl-trichloro-silicane (PhSiCl
3), 28.1g dimethyldichlorosilane(DMCS) (Me
2siCl
2), 15.6g dichloromethyl phenylsilane (MePhSiCl
2), 34.8g methylvinyldichlorosilane (MeViSiCl
2) and 270g dimethylbenzene Homogeneous phase mixing liquid dropwise at 2h, continue to stir 1h, pour in 3000ml separating funnel leave standstill, layering, release lower floor acid solution.Be that the deionized water of 30 DEG C is repeatedly to neutral by the temperature of 1kg.Get gained silanol xylene solution, carrying out being condensed into solid content under temperature 85 ~ 95 DEG C, pressure-0.08MPa ~-0.096MPa is 50 ± 2%(mass concentration) silanol xylene solution.
(2) the silanol xylene solution 200g that above-mentioned gained solid content is 50 ± 2%, is got, add the potassium hydroxide of 0.2g, in 500ml reaction flask at 80 ~ 100 DEG C reflux water-dividing polycondensation 2h, be cooled to 60 DEG C, add 5g tetramethyl divinyl disiloxane (［ ViMe
2si ］
2o), continue stirring reaction 2h at 60 ~ 80 DEG C, neutrality is washed till with deionized water, stratification removing water layer, then at 100 DEG C, underpressure distillation (pressure-0.08MPa ~-0.096MPa) is carried out to remove the water that in system, solvent and reaction are formed, 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 see table 1.
Further calculating is known, the R/Si=1.55 of thing in the vinyl silicon of this example, Ph/R=0.35, Vi mass fraction %=7.7.
Get thing 100g phenyl-vinyl silicon oil 25g, dicumyl peroxide 1.5g in vinyl silicon, mixing can obtain high reactivity vinyl organosilicon solvent-free insulated paint.Its salient features is see 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 (composition: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 DEG C, under stirring, by 66.8g phenyl-trichloro-silicane (PhSiCl
3), 48.9g dimethyldichlorosilane(DMCS) (Me
2siCl
2), 43.1g methylvinyldichlorosilane (MeViSiCl
2) and 270g dimethylbenzene Homogeneous phase mixing liquid dropwise at 2h, continue to stir 1h, pour in 3000ml separating funnel leave standstill, layering, release lower floor acid solution.Be that the deionized water of 30 DEG C is repeatedly to neutral by the temperature of 1kg.Get gained silanol xylene solution, carrying out being condensed into solid content under temperature 85 ~ 95 DEG C, pressure-0.08MPa ~-0.096MPa is 50 ± 2%(mass concentration) silanol xylene solution.
(2) the silanol xylene solution 200g of solid content 50 ± 2%, is got, add the 2 ethyl hexanoic acid zinc (Zn content is 9%) of 0.02g, in 500ml reaction flask at 80 ~ 100 DEG C reflux water-dividing polycondensation 2h, be cooled to 60 DEG C, add 5g tetramethyl divinyl disiloxane (［ ViMe
2si ］
2o), continue stirring reaction 2h at 60 ~ 80 DEG C, then at 100 DEG C, carry out underpressure distillation (pressure-0.08MPa ~-0.096MPa) to remove the water that in system, solvent and reaction are formed, 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 see table 1.
The R/Si=1.68 of thing in the vinyl silicon of this example, 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 obtain high reactivity vinyl organosilicon solvent-free insulated paint.Its salient features is see 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 (composition: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 DEG C, under stirring, by 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 270g dimethylbenzene Homogeneous phase mixing liquid dropwise at 2h, continue to stir 1h, pour in 3000ml separating funnel leave standstill, layering, release lower floor acid solution.Repeatedly extremely neutral with the deionized water of 1kg.Get gained silanol xylene solution, carrying out being condensed into solid content under temperature 85 ~ 95 DEG C, pressure-0.08MPa ~-0.096MPa is 50 ± 2%(mass concentration) silanol xylene solution.
(2) the silanol xylene solution 200g of solid content 50 ± 2%, is got, add the Tetramethylammonium hydroxide of 0.2g, in 500ml reaction flask at 80 ~ 100 DEG C reflux water-dividing polycondensation 2h, be cooled to 60 DEG C, add 5g tetramethyl divinyl disiloxane (［ ViMe
2si ］
2o), continue stirring reaction 2h at 60 ~ 80 DEG C, neutrality is washed till with deionized water, stratification removing water layer, then at 100 DEG C, underpressure distillation (pressure-0.08MPa ~-0.096MPa) is carried out to remove the water that in system, solvent and reaction are formed, 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 see table 1.
Further calculating is known, the R/Si=1.58 of thing in the vinyl silicon of this example, 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 isopropanol complex 0.5g, Platinic chloride one diethyl phthalate complex compound 0.5g, mixing can obtain vinyl Si―H addition reaction organosilicon solvent-free insullac.Its salient features is see 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 (composition: dimethylbenzene 40g, toluene 128g and propyl carbinol 12g) and 720g water are housed, at 40 ± 5 DEG C, under stirring, by 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 270g dimethylbenzene Homogeneous phase mixing liquid dropwise at 2h, continue to stir 1h, pour in 3000ml separating funnel leave standstill, layering, release lower floor acid solution.Repeatedly extremely neutral with the deionized water of 1kg.Get gained silanol xylene solution, carrying out being condensed into solid content under temperature 85 ~ 95 DEG C, pressure-0.08MPa ~-0.096MPa is 50 ± 2%(mass concentration) silanol xylene solution.
(2) the silanol xylene solution 200g of solid content 50 ± 2%, is got, add the 2 ethyl hexanoic acid zinc (Zn content is 9%) of 0.02g, in 500ml reaction flask at 80 ~ 100 DEG C reflux water-dividing polycondensation 2h, be cooled to 60 DEG C, add 5g tri-phenyl chloride (Ph
3siCl), continue stirring reaction 2h at 60 ~ 80 DEG C, then at 100 DEG C, carry out underpressure distillation (pressure-0.08MPa ~-0.096MPa) to remove the water that in system, solvent and reaction are formed, 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 see table 1.
The R/Si=1.50 of thing in the vinyl silicon of this example, Ph/R=0.35, Vi mass fraction %=3.2.
Get thing 100g, E51 epoxy resin 20g in vinyl silicon, phenyl-vinyl silicon oil 5g, peroxidized t-butyl perbenzoate 2g, 2 ethyl hexanoic acid zinc (Zn content is 9%) 1g, mixing can obtain epoxy modified silicone solvent-free insulated paint.Its salient features is see table 2.
Thing salient features and structural parameter in table 1 vinyl silicon
Table 2 embodiment 1 ~ 8 join the salient features of insullac
Above-described embodiment is only for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (5)
1. the preparation method of thing in the vinyl silicon that represents of general formula (I),
It is characterized in that: in formula (I), x, y, m, n, q are the number between 0 ~ 20 independently, and when x, m and n three is different be 0, x, y and z three different time be 0, z be 0, q be not 0; R
1, R
2, R
3independently for being selected from methyl, the one in vinyl and phenyl;
The total mole number of the phenyl in thing, Si atom connected 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 phenyl, methyl and the vinyl that Si atom connects is 18% ~ 50%; The mass content of vinyl in silicon in thing is 0.5% ~ 10%;
In vinyl silicon, thing is 180 DEG C ~ 220 DEG C according to the humidity index that secant method is surveyed, and described vinyl silicon is 500 ~ 8000 according to the molecular weight measured by GPC method;
Described preparation method comprises the steps:
(1), make chlorosilane non-polar organic solvent and polar organic solvent composition mixed solvent in, in the presence of water, issue raw hydrolysis reaction in temperature 20 ~ 50 DEG C and stirring and generate silanol, hydrolysis time is 2 ~ 8 hours, after hydrolysis reaction terminates, be separated, obtain the solution of the non-polar solvent of silanol, wherein: described chlorosilane is by dichloromethyl phenylsilane, dimethyldichlorosilane(DMCS), methylvinyldichlorosilane, phenyl-trichloro-silicane, diphenyl dichlorosilane, vinyl trichloro silane is according to the ratio composition needed for formula (I), the mole dosage of water is 1 ~ 20 times of the molar weight of chlorine in chlorosilane,
(2), in the solution of the non-polar solvent of step (1) gained silanol, catalyzer is added, make to carry out backflow polycondensation at temperature 80 ~ 150 DEG C, when to temperature of reaction, institute's viscosimetric reaches 500 ~ 5000mPas, be cooled to 55 ~ 62 DEG C, add end-capping reagent, continue at 55 ~ 120 DEG C after stirring reaction 0.5 ~ 3h, be washed with water to neutrality, divide and remove upper water, concentrated, the water that distillation generates except desolventizing and reaction, obtain thing in vinyl silicon, 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
3independently for being selected from methyl, the one in vinyl and phenyl, add that quality is the quality of silanol 0.1% ~ 5% of end-capping reagent; Described catalyzer is be selected from the combination into one or more in 2 ethyl hexanoic acid zinc, potassium hydroxide and Tetramethylammonium hydroxide.
2. the preparation method of thing in vinyl silicon according to claim 1, it is characterized in that: in step (1), non-polar organic solvent in described mixed solvent is be selected from one or more the combination in 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 be 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.
3. the preparation method of thing in vinyl silicon according to claim 1 and 2, it is characterized in that: the implementation process of step (1) is as follows: chlorosilane is dissolved in the described non-polar organic solvent of part and obtains chlorosilane solution, then this chlorosilane solution is added drop-wise to 20 DEG C ~ 50 DEG C by dropping funnel, by the non-polar organic solvent of remainder, in the mixture of polar organic solvent and water, under agitation be hydrolyzed reaction, after hydrolysis reaction terminates, leave standstill, layering, release lower floor's liquid, with 30 DEG C ~ 65 DEG C deionized waters, supernatant liquid washing is extremely neutral, obtain the solution that mass concentration is the non-polar solvent of the silanol of 20% ~ 30%, continue temperature 60 ~ 100 DEG C, concentrate under pressure-0.08MPa ~-0.096MPa, the mass concentration of silanol in solution is made to be increased to 50% ~ 60%.
4. the preparation method of thing in vinyl silicon according to claim 1, is characterized in that: be concentrated in temperature 80 ~ 100 DEG C described in step (2), carry out under pressure-0.08MPa ~-0.096MPa.
5. the preparation method of thing in vinyl silicon according to claim 1, is characterized in that: in general formula (I), R
1, R
2, R
3be methyl or phenyl; Or, R
1, R
2, R
3in have two for methyl, have one for vinyl.
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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 |
| CN105349034B (en) * | 2015-11-30 | 2017-06-20 | 苏州太湖电工新材料股份有限公司 | A kind of low viscosity, fire resistant Inverter fed motor environmental protection insulated paint and preparation method thereof |
| CN105348534B (en) * | 2015-11-30 | 2017-02-08 | 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 |
| CN107731492B (en) * | 2016-07-30 | 2019-01-18 | 宁波甬嘉变压器有限公司 | A kind of power transformer |
| CN109943191A (en) * | 2019-03-14 | 2019-06-28 | 珠海市横琴新区贝格特实业有限公司 | Solvent-free heat-conducting resin preparation and coating processes |
| 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 |
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