CN105255361A - Silicone impregnating varnish as well as preparation method and application thereof - Google Patents
Silicone impregnating varnish as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN105255361A CN105255361A CN201510734105.4A CN201510734105A CN105255361A CN 105255361 A CN105255361 A CN 105255361A CN 201510734105 A CN201510734105 A CN 201510734105A CN 105255361 A CN105255361 A CN 105255361A
- Authority
- CN
- China
- Prior art keywords
- group
- phenyl
- monomer
- viscosity
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to the field of oil varnish chemical engineering, in particular to silicone impregnating varnish as well as a preparation method and application thereof. The tensile strength of a curing product of the silicone impregnating varnish is 15MPa or over 15MPa, and the preferable range is 15 to 20MPa; the bending strength of the curing product of the silicone impregnating varnish is 25MPa or over 25MPa, and the preferable range is 25 to 35MPa. The mechanical strength of the silicone impregnating varnish disclosed by the invention is greatly improved.
Description
Technical field
The present invention relates to paint class chemical field, particularly a kind of silicone impregnating varnish and its preparation method and application.
Background technology
Organosilicon material is current a kind of general insulating material kind, and be widely used in the fields such as impregnating varnish, coating, mica tape adhesive, but organosilicon material has the defect of himself, the problem that its cured product physical strength is low enjoys blame always.
Organosilicon Si―H addition reaction class silicone paint product is the large series products of one in organosilicon systems, it obtains last cured product by there is addition reaction between silico ethylene base and silicon hydrogen, normally be made up of silico ethylene base component and silicon hydrogen component, for obtaining suitable paint viscosity, such as obtain the paint viscosity of 1000CP, general employing accomplishes the viscosity of about 1000CP respectively silico ethylene base component and silicon hydrogen component, the viscosity being obtained painting by their mixtures is then about 1000CP, but the product physical strength obtained like this is very general.
Therefore, the silicone paint product developed a kind of physical strength and improve is needed badly.
Summary of the invention
The invention provides a kind of silicone impregnating varnish, the tensile strength of the cured product of described silicone impregnating varnish is more than 15MPa, and be preferably 15-20MPa, the flexural strength of the cured product of described silicone impregnating varnish is more than 25MPa, is preferably 25-35MPa.
Wherein, the tensile strength of the cured product of above-mentioned silicone impregnating varnish obtains according to standard GB/T/T1040-1992 measurement; The flexural strength of the cured product of above-mentioned silicone impregnating varnish obtains according to standard GB/T/T9341-2000 measurement.
In a specific embodiment, described silicone impregnating varnish has and is more than or equal to 800CP under the condition of 23 ± 2 DEG C, and is less than or equal to the viscosity of 1400CP, preferably has and is more than or equal to 900CP, and be less than or equal to the viscosity of 1500CP.
Wherein, the viscosity of above-mentioned silicone impregnating varnish obtains according to standard GB/T 15022-2007 measurement.
In a specific embodiment, described silicone impregnating varnish is that the content solidifying fugitive constituent under the condition of 200 DEG C is no more than 2% in temperature.
Wherein, above-mentioned silicone impregnating varnish is that the content solidifying fugitive constituent under the condition of 200 DEG C obtains according to standard GB/T 15022-2007 measurement in temperature.
In a specific embodiment, described silicone impregnating varnish comprises silico ethylene base, silicon hydrogen base, methyl and phenyl, and the mol ratio of described silico ethylene base, silicon hydrogen base, methyl and phenyl is (20-80): (5-40): (5-40): (5-40), the mol ratio of preferred described silico ethylene base, silicon hydrogen base, methyl and phenyl is (30-70): (10-30): (5-20): (5-20).
Present invention also offers a kind of preparation method preparing as above any one silicone impregnating varnish, comprise the steps:
A) by silico ethylene base monomer and methyl-monosilane monomer and the cohydrolysis polycondensation in a solvent of phenyl silane monomer; By silicon hydrogen monomer, methyl-monosilane monomer and the cohydrolysis polycondensation in a solvent of phenyl silane monomer; Obtain the system of the polycondensate containing silico ethylene base group and the polycondensate containing silicon hydrogen group respectively;
C) distinguish the solvent in the system of the above-mentioned two kinds of polycondensates of extracting removing and low-boiling-point substance, then obtain the organosilicon preformed polymer of siliceous vinyl group and the organosilicon preformed polymer of hydrosilyl group-containing group respectively;
D) by the organosilicon preformed polymer of the organosilicon preformed polymer of described siliceous vinyl group and described hydrosilyl group-containing group and catalyzer and inhibitor mixed, after stirring, described silicone impregnating varnish has been obtained.
In a specific embodiment, described silico ethylene base monomer comprises one or more in methylvinyldichlorosilane, methyl ethylene dimethoxy, dimethylvinylmethoxysiiane, vinyl trichloro silane, vinyltrimethoxy silane and vinyl double-seal head;
Described silicon hydrogen monomer comprise in methyl hydrogen dichlorosilane, methyl hydrogen diethoxy silane, dimethyl hydrogen Ethoxysilane and hydrogeneous double-seal head one or more;
Described methyl-monosilane monomer comprise in dimethyldichlorosilane(DMCS), dimethyldiethoxysilane, dichloromethyl phenylsilane, aminomethyl phenyl diethoxy silane, Union carbide A-162, METHYL TRICHLORO SILANE, trimethylchlorosilane and hexamethyldisiloxane one or more;
Described phenyl silane monomer comprise in diphenyl diethoxy silane, diphenyl dichlorosilane, a phenyl-trichloro-silicane and a phenyl trimethoxy silane one or more.
Wherein, vinyl double-seal head is also called tetramethyl divinyl disiloxane; Hydrogeneous double-seal head is also called tetramethyldisiloxane, tetramethyldihydrogendisiloxane or 1,1,3,3-tetramethyl disiloxane etc.
In a specific embodiment, steps A) in solvent be weak polar solvent, one or more and the water preferably included in toluene, dimethylbenzene, acetone, naphthenic hydrocarbon, halohydrocarbon, vinyl acetic monomer and N-BUTYL ACETATE is mixed into emulsion, be preferably the emulsion of toluene and water, more preferably the proportional range of toluene and water presses massfraction proportioning for (50-100): (30-60).
In a specific embodiment, in cohydrolysis polycondensation process, the temperature range of solvent is 5-60 DEG C, and preferable range is 10-50 DEG C.
In a specific embodiment, in steps A) and step C) between also comprise step B-I), respectively the system of the described polycondensate containing silico ethylene base group and the polycondensate containing silicon hydrogen group is concentrated.
In a specific embodiment, in step B-I) and step C) between also comprise step B-II), respectively to step B-I) polycondensate containing silico ethylene base group that obtains and the system of polycondensate containing silicon hydrogen group wash until neutral.
The present invention utilizes the prepolymer at least containing silico ethylene base and the prepolymer two kinds of components containing silicon hydrogen base to synthesize and obtains silicone impregnating varnish of the present invention, and the viscosity of wherein a kind of prepolymer is done large especially, and the viscosity of another kind of prepolymer is done relatively little, the component of so large viscosity provides enough physical strengths, the component of little viscosity is then used for playing diluting effect when joining paint, is unlikely to make two kinds of components coordinate the paint viscosity obtained excessive.And the scheme that a kind of viscosity of component is greater than the viscosity of another kind of component adopts the scheme of basic identical viscosities to have very large improvement in physical strength compared with two kinds of components.Therefore, in a specific embodiment, at described step C) in the organosilicon preformed polymer of siliceous vinyl group that obtains and hydrosilyl group-containing group organosilicon preformed polymer in, a kind of prepolymer has the viscosity of 5000-10000CP under the condition of 60 ± 2 DEG C, and another kind of prepolymer has the viscosity of 20-100CP under the condition of 23 ± 2 DEG C.That is, the range of viscosities prepolymer that to be the prepolymer of 5000-10000CP/ (60 ± 2 DEG C) can be containing silico ethylene base also can be the prepolymer containing silicon hydrogen base; The range of viscosities prepolymer that to be the prepolymer of 20-100CP/ (23 ± 2 DEG C) can be containing silico ethylene base also can be the prepolymer containing silicon hydrogen base; But the range of viscosities of the prepolymer containing silico ethylene base and the prepolymer containing silicon hydrogen base can not be 5000-10000CP/ (60 ± 2 DEG C), can not be 20-100CP/ (23 ± 2 DEG C) simultaneously simultaneously.
In a specific embodiment, in step D) in, the mass ratio of the organosilicon preformed polymer of the organosilicon preformed polymer of described siliceous vinyl group and described hydrosilyl group-containing group is (30-50): (20-40), and the mass ratio of the organosilicon preformed polymer of the organosilicon preformed polymer of preferred described siliceous vinyl group and described hydrosilyl group-containing group is (35-45): (25-35).
In a specific embodiment, described catalyzer is selected from platinum catalyst, and described inhibitor is selected from containing at least one in the compound of the groups such as nitrogen phosphate and sulfur, thiazolinyl and alkynyl.
In a specific embodiment, the consumption of described catalyzer accounts for the 0.01-0.05% of mixture total mass; And/or the consumption of described inhibitor accounts for the 0.01-0.1% of mixture total mass.
Preparation technology's flow process that the present invention is concrete:
(1) synthesis of the prepolymer of silicone impregnating varnish, by end product, the i.e. molar fraction of silicone impregnating varnish, methyl wherein: phenyl: silico ethylene group: silicon hydrogen group=(20-80) %:(5-40) %:(5-40) %:(5-40) %, by silico ethylene base monomer and methyl-monosilane monomer and the cohydrolysis polycondensation in a solvent of phenyl silane monomer; By silicon hydrogen monomer, methyl-monosilane monomer and the cohydrolysis polycondensation in a solvent of phenyl silane monomer; Obtain the solution of the polycondensate A of siliceous vinyl group and the polycondensate B of hydrosilyl group-containing group respectively, then concentrate at the temperature of 80-140 DEG C respectively, then solvent and low-boiling-point substance is extracted, namely organosilicon preformed polymer A and B is obtained, wherein the range of viscosities of the component of in component A or B component is controlled at 5000-10000CP/60 DEG C, and the range of viscosities of another component controls at 20-100CP/23 DEG C accordingly.
(2) composite prepolymer, above-mentioned intermediate pre-polymer A and B component are pressed (35-45): (25-35) mass parts, and be mixed into platinum catalyst and the 0.01-0.1% inhibitor of the 0.01-0.05% of resin total amount, namely stir about obtains organosilicon solvent-free dip varnish product after half an hour.
The invention provides a kind of silicone impregnating varnish product and synthetic method thereof of high mechanical strength, the silicone impregnating varnish product of this high mechanical strength has following characteristic: (1) is not with the insullac kind that any organic solvent is medium, solvent-free pure varnished insulation paint, belongs to nuisanceless green environment-friendlyinsulation insulation material; (2) this paint has lower viscosity at normal temperatures; (3) deviate from without low-molecular material during this impregnating varnish film-forming, do not affect electric property, pollution-free, good combination property, application art performance is good, is applicable to the vacuum pressure varnished insulation process of the equipment such as motor, transformer.This product contains silico ethylene based component and silicon hydrogen composition, and the curing mechanism of the addition reaction of silicon with hydrogen that its solidification causes with platinum catalyst, its curing kinetics is such as formula (1).
Embodiment
Following examples further illustrate of the present invention, but the invention is not restricted to following embodiment.
Embodiment 1
Get a phenyl-trichloro-silicane 1mol, dimethyldichlorosilane(DMCS) 0.1mol, methylvinyldichlorosilane 0.5mol, diphenyl dichlorosilane 0.2mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, measuring component A viscosity through NDJ-79 rotational viscosimeter (Wuhan Ge Laimo test set company limited) is 8120CP/60 DEG C.
Get a phenyl-trichloro-silicane 0.5mol, dimethyldichlorosilane(DMCS) 0.1mol, methyl hydrogen dichlorosilane 0.4mol, dichloromethyl phenylsilane 0.1mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 50CP/23 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.52, add 0.015% platinum catalyst and the 0.05% inhibitor triethyl-phosphite of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 1100CP/23 DEG C.
Embodiment 2
Get a phenyl-trichloro-silicane 0.2mol, dimethyldichlorosilane(DMCS) 0.1mol, methylvinyldichlorosilane 0.4mol, diphenyl diethoxy silane 0.2mol, hexamethyldisiloxane 0.3mol, with the speed of 6L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 35CP/23 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 1.2mol, dimethyldichlorosilane(DMCS) 0.1mol, methyl hydrogen dichlorosilane 0.4mol, aminomethyl phenyl diethoxy silane 0.1mol, hexamethyldisiloxane 0.1mol, with the speed of 6L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 7550CP/60 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.35, add 0.02% platinum catalyst and the 0.08% inhibitor vinylcyclohexanol of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 1050CP/23 DEG C.
Embodiment 3
Get a phenyl-trichloro-silicane 1.2mol, dimethyldichlorosilane(DMCS) 0.1mol, methylvinyldichlorosilane 0.5mol, dichloromethyl phenylsilane 0.2mol, hexamethyldisiloxane 0.2mol, with the speed of 8L/min organosilane monomer being added drop-wise under the condition of 20 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 9050CP/60 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 0.3mol, dimethyldichlorosilane(DMCS) 0.2mol, methyl hydrogen dichlorosilane 0.5mol, dichloromethyl phenylsilane 0.2mol, hexamethyldisiloxane 0.3mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 15 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 40CP/23 DEG C through rotating NDJ-79 viscosity meter B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.23, add 0.018% platinum catalyst and the 0.04% inhibitor N,N-DIMETHYLACETAMIDE of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 920CP/23 DEG C.
Embodiment 4
Get a phenyl-trichloro-silicane 1mol, dimethyldichlorosilane(DMCS) 0.1mol, methylvinyldimethoxysilane 0.5mol, diphenyl dichlorosilane 0.2mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 9020CP/60 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 0.5mol, dimethyldichlorosilane(DMCS) 0.1mol, methyl hydrogen diethoxy silane 0.4mol, dichloromethyl phenylsilane 0.1mol, hexamethyldisiloxane 0.2mol, with the speed of 7L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 48CP/23 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.51, add 0.015% platinum catalyst and the 0.05% inhibitor ethyl-sulfide of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 1150CP/23 DEG C.
Embodiment 5
Get a phenyl-trichloro-silicane 0.2mol, dimethyldichlorosilane(DMCS) 0.1mol, dimethylvinylmethoxysiiane 0.4mol, diphenyl diethoxy silane 0.2mol, hexamethyldisiloxane 0.3mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 40CP/23 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 1.2mol, dimethyldichlorosilane(DMCS) 0.1mol, dimethyl hydrogen Ethoxysilane 0.4mol, aminomethyl phenyl diethoxy silane 0.1mol, hexamethyldisiloxane 0.1mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 6890CP/60 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.25, add 0.02% platinum catalyst and the 0.08% inhibitor vinylcyclohexanol of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 930CP/23 DEG C.
Embodiment 6
Get a phenyl-trichloro-silicane 1.2mol, dimethyldichlorosilane(DMCS) 0.1mol, vinyl trichloro silane 0.45mol, dichloromethyl phenylsilane 0.2mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 20 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 7950CP/60 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 0.3mol, dimethyldichlorosilane(DMCS) 0.2mol, hydrogeneous double-seal head 0.5mol, dichloromethyl phenylsilane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 15 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 35CP/23 DEG C through rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.35, add 0.018% platinum catalyst and the 0.04% inhibitor N,N-DIMETHYLACETAMIDE of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 980CP/23 DEG C.
Embodiment 7
Get a phenyl-trichloro-silicane 0.2mol, dimethyldichlorosilane(DMCS) 0.1mol, vinyl double-seal head 0.2mol, diphenyl diethoxy silane 0.2mol, hexamethyldisiloxane 0.1mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 45CP/23 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 1.2mol, dimethyldichlorosilane(DMCS) 0.1mol, methyl hydrogen dichlorosilane 0.4mol, aminomethyl phenyl diethoxy silane 0.1mol, hexamethyldisiloxane 0.1mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 8150CP/60 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.30, add 0.02% platinum catalyst and the 0.08% inhibitor vinylcyclohexanol of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 1010CP/23 DEG C.
Embodiment 8
Get a phenyl-trichloro-silicane 1mol, dimethyldichlorosilane(DMCS) 0.1mol, dimethylvinylmethoxysiiane 0.1mol, vinyl double-seal head 0.1mol and methylvinyldichlorosilane 0.2mol, diphenyl dichlorosilane 0.2mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 8520CP/60 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 0.5mol, dimethyldichlorosilane(DMCS) 0.1mol, dimethyl hydrogen Ethoxysilane 0.1mol, methyl hydrogen dichlorosilane 0.3mol, dichloromethyl phenylsilane 0.1mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 40CP/23 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.3, add 0.015% platinum catalyst and the 0.05% inhibitor ethyl-sulfide of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 1200CP/23 DEG C.
Comparative example 1
Get a phenyl-trichloro-silicane 0.6mol, dimethyldichlorosilane(DMCS) 0.1mol, methylvinyldichlorosilane 0.5mol, diphenyl dichlorosilane 0.2mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 1050CP/23 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 0.8mol, dimethyldichlorosilane(DMCS) 0.1mol, methyl hydrogen dichlorosilane 0.4mol, dichloromethyl phenylsilane 0.1mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 950CP/23 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.35, add 0.015% platinum catalyst and the 0.05% inhibitor triethyl-phosphite of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 1020CP/23 DEG C.
Comparative example 2
Get a phenyl-trichloro-silicane 0.6mol, dimethyldichlorosilane(DMCS) 0.1mol, methylvinyldichlorosilane 0.4mol, diphenyl diethoxy silane 0.2mol, hexamethyldisiloxane 0.3mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 1100CP/23 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 0.8mol, dimethyldichlorosilane(DMCS) 0.1mol, methyl hydrogen dichlorosilane 0.4mol, aminomethyl phenyl diethoxy silane 0.1mol, hexamethyldisiloxane 0.1mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 10 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 1000CP/23 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.45, add 0.02% platinum catalyst and the 0.08% inhibitor vinylcyclohexanol of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 1050CP/23 DEG C.
Comparative example 3
Get a phenyl-trichloro-silicane 0.7mol, dimethyldichlorosilane(DMCS) 0.1mol, methylvinyldichlorosilane 0.5mol, dichloromethyl phenylsilane 0.2mol, hexamethyldisiloxane 0.2mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 20 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and obtain component A with bottom discharge, be 1000CP/23 DEG C through NDJ-79 rotary viscosity measuring component A viscosity.
Get a phenyl-trichloro-silicane 0.6mol, dimethyldichlorosilane(DMCS) 0.2mol, methyl hydrogen dichlorosilane 0.5mol, dichloromethyl phenylsilane 0.2mol, hexamethyldisiloxane 0.3mol, with the speed of 5L/min organosilane monomer being added drop-wise under the condition of 15 DEG C has in the flask of rapid stirring, drip hydrolysis reaction and continue 4 hours, then at 120 DEG C of concentrated slaking reactions 4 hours of carrying out refluxing, carry out afterwards being washed to neutrality, upper strata enamelled coating is carried out vacuumizing desolventizing and de-low-boiling-point substance, and sample viscosimetric, when viscosity reaches target zone, namely heating is stopped, be cooled to 60 DEG C and draw B component with bottom discharge, be 1020CP/23 DEG C through NDJ-79 rotary viscosity measuring B component viscosity.
Obtain A, B two component respectively, mix by the mass ratio of A/B=1.4, add 0.018% platinum catalyst and the 0.04% inhibitor N,N-DIMETHYLACETAMIDE of formula ratio afterwards, stir, namely discharging obtains product, and the viscosity using NDJ-79 rotary viscosity measuring paint is 1010CP/23 DEG C.
Embodiment 9
Measure according to standard GB/T/T1040-1992 the product prepared in above-mentioned all embodiments and comparative example the tensile strength of cured product; The flexural strength of the cured product of the product prepared in above-mentioned all embodiments and comparative example is measured according to standard GB/T/T9341-2000; The content of the viscosity of product and the solidification fugitive constituent of product prepared in above-mentioned all embodiments and comparative example is measured according to standard GB/T 15022-2007.
As can be seen from Table 1, the tensile strength of the silicone impregnating varnish prepared in embodiments of the invention 1-8 and flexural strength are obviously better than the silicone impregnating varnish prepared in comparative example 1-3, thus the physical strength of silicone impregnating varnish is enhanced.Content not significant change compared with comparative example of the biological range of viscosities of the silicone impregnating varnish simultaneously prepared in embodiments of the invention 1-8 and solidification fugitive constituent.
Table 1 the performance test results
| Embodiment | Tensile strength (MPa) | Flexural strength (MPa) | Viscosity (CP) | The content (%) of solidification fugitive constituent |
| Embodiment 1 | 15.6 | 29.4 | 1100 | 1.2 |
| Embodiment 2 | 16.4 | 30.2 | 1050 | 1.5 |
| Embodiment 3 | 18.5 | 29.8 | 920 | 1.4 |
| Embodiment 4 | 17.8 | 32.9 | 1150 | 1.4 |
| Embodiment 5 | 18.2 | 33.5 | 930 | 1.8 |
| Embodiment 6 | 16.3 | 29.8 | 980 | 1.5 |
| Embodiment 7 | 17.5 | 34.0 | 1010 | 0.9 |
| Embodiment 8 | 18.8 | 32.9 | 1200 | 1.0 |
| Comparative example 1 | 12.6 | 23.7 | 1020 | 1.2 |
| Comparative example 2 | 13.5 | 24.2 | 1050 | 1.5 |
| Comparative example 3 | 12.2 | 20.9 | 1010 | 1.4 |
Claims (11)
1. a silicone impregnating varnish, the tensile strength of the cured product of described silicone impregnating varnish is more than 15MPa, and be preferably 15-20MPa, the flexural strength of the cured product of described silicone impregnating varnish is more than 25MPa, is preferably 25-35MPa.
2. silicone impregnating varnish according to claim 1, it is characterized in that, described silicone impregnating varnish comprises silico ethylene base, silicon hydrogen base, methyl and phenyl, and the mol ratio of described silico ethylene base, silicon hydrogen base, methyl and phenyl is (20-80): (5-40): (5-40): (5-40), the mol ratio of preferred described silico ethylene base, silicon hydrogen base, methyl and phenyl is (30-70): (10-30): (5-20): (5-20).
3. a preparation method for silicone impregnating varnish as claimed in claim 1 or 2, comprises the steps:
A) by silico ethylene base monomer and methyl-monosilane monomer and the cohydrolysis polycondensation in a solvent of phenyl silane monomer; By silicon hydrogen monomer, methyl-monosilane monomer and the cohydrolysis polycondensation in a solvent of phenyl silane monomer; Obtain the system of the polycondensate of siliceous vinyl group and the polycondensate of hydrosilyl group-containing group respectively;
C) distinguish the solvent in the system of the above-mentioned two kinds of polycondensates of extracting removing and low-boiling-point substance, then obtain the organosilicon preformed polymer of siliceous vinyl group and the organosilicon preformed polymer of hydrosilyl group-containing group respectively;
D) by the organosilicon preformed polymer of the organosilicon preformed polymer of described siliceous vinyl group and described hydrosilyl group-containing group and catalyzer and inhibitor mixed, after stirring, described silicone impregnating varnish has been obtained.
4. preparation method according to claim 3, it is characterized in that, described silico ethylene base monomer comprise in methylvinyldichlorosilane, methylvinyldimethoxysilane, dimethylvinylmethoxysiiane, vinyl trichloro silane, vinyltrimethoxy silane and vinyl double-seal head one or more;
Described silicon hydrogen monomer comprise in methyl hydrogen dichlorosilane, methyl hydrogen diethoxy silane, dimethyl hydrogen Ethoxysilane and hydrogeneous double-seal head one or more;
Described methyl-monosilane monomer comprise in dimethyldichlorosilane(DMCS), dimethyldiethoxysilane, dichloromethyl phenylsilane, aminomethyl phenyl diethoxy silane, Union carbide A-162, METHYL TRICHLORO SILANE, trimethylchlorosilane and hexamethyldisiloxane one or more;
Described phenyl silane monomer comprise in diphenyl diethoxy silane, diphenyl dichlorosilane, a phenyl-trichloro-silicane and a phenyl trimethoxy silane one or more.
5. the preparation method according to claim 3 or 4, it is characterized in that, steps A) in solvent be weak polar solvent, preferably include the emulsion that one or more and water in toluene, dimethylbenzene, acetone, naphthenic hydrocarbon, halohydrocarbon, vinyl acetic monomer and N-BUTYL ACETATE are mixed into, be preferably the emulsion of toluene and water, more preferably the proportional range of toluene and water presses massfraction proportioning for (50-100): (30-60).
6. the preparation method according to claim 3-5 any one, is characterized in that, in cohydrolysis polycondensation process, the temperature range of solvent is 5-60 DEG C, and preferable range is 10-50 DEG C.
7. the preparation method according to claim 3-6 any one, it is characterized in that, in steps A) and step C) between also comprise step B-I), respectively to step B-I) polycondensate containing silico ethylene base group that obtains and the system of polycondensate containing silicon hydrogen group carry out concentrated balance.
8. the preparation method according to claim 3-7 any one, it is characterized in that, at described step C) in the organosilicon preformed polymer of siliceous vinyl group that obtains and hydrosilyl group-containing group organosilicon preformed polymer in, a kind of prepolymer has the viscosity of 5000-10000CP under the condition of 60 ± 2 DEG C, and another kind of prepolymer has the viscosity of 20-100CP under the condition of 23 ± 2 DEG C.
9. the preparation method according to claim 3-8 any one, it is characterized in that, in step D) in, the mass ratio of the organosilicon preformed polymer of the organosilicon preformed polymer of described siliceous vinyl group and described hydrosilyl group-containing group is (30-50): (20-40), and the mass ratio of the organosilicon preformed polymer of the organosilicon preformed polymer of preferred described siliceous vinyl group and described hydrosilyl group-containing group is (35-45): (25-35).
10. the preparation method according to claim 3-9 any one, is characterized in that, described catalyzer is selected from platinum catalyst, and/or described inhibitor is selected from containing at least one in the compound of nitrogen phosphate and sulfur, thiazolinyl and alkynyl group.
11. preparation methods according to claim 3-10 any one, it is characterized in that, the consumption of described catalyzer accounts for the 0.01-0.05% of mixture total mass; And/or the consumption of described inhibitor accounts for the 0.01-0.1% of mixture total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510734105.4A CN105255361B (en) | 2015-11-03 | 2015-11-03 | A kind of silicone impregnating varnish and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510734105.4A CN105255361B (en) | 2015-11-03 | 2015-11-03 | A kind of silicone impregnating varnish and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105255361A true CN105255361A (en) | 2016-01-20 |
| CN105255361B CN105255361B (en) | 2017-12-12 |
Family
ID=55095312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510734105.4A Active CN105255361B (en) | 2015-11-03 | 2015-11-03 | A kind of silicone impregnating varnish and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105255361B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146850A (en) * | 2016-07-05 | 2016-11-23 | 山东省科学院新材料研究所 | A kind of additional organosilicon impregnating resin viscosifier and preparation method thereof |
| CN109355013A (en) * | 2018-09-06 | 2019-02-19 | 广州贝特新材料有限公司 | A kind of rail traffic high-low temperature resistant impact organosilicon impregnating resin and preparation method thereof |
| CN113845841A (en) * | 2021-11-09 | 2021-12-28 | 株洲时代电气绝缘有限责任公司 | Modified organic silicon solvent-free impregnating varnish and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121861A (en) * | 2007-08-01 | 2008-02-13 | 株洲时代新材料科技股份有限公司 | Low-viscosity solvent-free organic silicon insulation impregnating varnish and preparation method thereof |
| CN101381583A (en) * | 2008-10-20 | 2009-03-11 | 株洲时代新材料科技股份有限公司 | High heat conduction organosilicon dip varnish |
| CN103382366A (en) * | 2013-06-27 | 2013-11-06 | 马鞍山采石矶涂料有限公司 | High-temperature resistance organic silicon impregnating varnish and preparation method thereof |
-
2015
- 2015-11-03 CN CN201510734105.4A patent/CN105255361B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121861A (en) * | 2007-08-01 | 2008-02-13 | 株洲时代新材料科技股份有限公司 | Low-viscosity solvent-free organic silicon insulation impregnating varnish and preparation method thereof |
| CN101381583A (en) * | 2008-10-20 | 2009-03-11 | 株洲时代新材料科技股份有限公司 | High heat conduction organosilicon dip varnish |
| CN103382366A (en) * | 2013-06-27 | 2013-11-06 | 马鞍山采石矶涂料有限公司 | High-temperature resistance organic silicon impregnating varnish and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 蒋大伟: "无溶剂有机硅浸渍树脂的制备及其性能研究", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146850A (en) * | 2016-07-05 | 2016-11-23 | 山东省科学院新材料研究所 | A kind of additional organosilicon impregnating resin viscosifier and preparation method thereof |
| CN109355013A (en) * | 2018-09-06 | 2019-02-19 | 广州贝特新材料有限公司 | A kind of rail traffic high-low temperature resistant impact organosilicon impregnating resin and preparation method thereof |
| CN113845841A (en) * | 2021-11-09 | 2021-12-28 | 株洲时代电气绝缘有限责任公司 | Modified organic silicon solvent-free impregnating varnish and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105255361B (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104152104B (en) | A kind of autohension organic silicon pressure-sensitive adhesive and preparation method thereof | |
| CN105008432B (en) | Moisturecuring hot melt silicone adhesive composition comprising alkoxy-functional siloxanes reaction resin | |
| CN101696263B (en) | Epoxy resin curing agent, method for preparing same and application thereof | |
| BR112014012199B1 (en) | composition of olefinomically olefinically functionalized siloxanes based on alkoxysilanes, their preparation and use process | |
| CN104610753B (en) | A kind of silicones coating layer material and its preparation and application | |
| CN107353871A (en) | A kind of high temperature resistant adhering and sealing silicones and preparation method thereof | |
| CN105001422B (en) | A kind of addition-type silicon rubber tackifier and preparation method thereof and addition-type silicon rubber | |
| CN106146850B (en) | Tackifier for addition type organic silicon impregnating resin and preparation method thereof | |
| CN105295720B (en) | A kind of preparation method of silicone impregnating varnish | |
| CN103450797A (en) | Room-temperature cured epoxy polysiloxane resin | |
| CA2855993A1 (en) | Mixtures, particularly low in volatile organic compounds (voc), of olefinically functionalised siloxane oligomers based on alkoxy silanes | |
| CN109233627A (en) | A kind of insulator coating bi-component addition type liquid silastic and preparation method thereof | |
| CN105255438A (en) | Bisphenol a epoxy resin modified room temperature vulcanized silicone rubber and preparation method thereof | |
| CN105218825A (en) | A kind of organosilicon solvent-free solvent impregnated resin and synthetic method thereof | |
| EP2888327B1 (en) | Aqueous epoxy and organo-substituted branched organopolysiloxane emulsions | |
| CN109232894B (en) | Methoxy-terminated methylphenyl polysiloxane resin, organic silicon coating adhesive, preparation method and application | |
| CN101121861A (en) | Low-viscosity solvent-free organic silicon insulation impregnating varnish and preparation method thereof | |
| CN108676168A (en) | A kind of preparation method of heat resist modification organosilicon material | |
| CN104497579B (en) | One-component room temperature vulcanized organic silicon rubber with high adhesion and preparation method thereof | |
| CN110156997A (en) | It is a kind of can moisture solidification organic silicon block copolymer and preparation method thereof | |
| CN105255361A (en) | Silicone impregnating varnish as well as preparation method and application thereof | |
| CN110387128B (en) | Self-adhesive single-component addition type silicone rubber and preparation method thereof | |
| US20230086610A1 (en) | Curable silicone-acrylate compositions, conductive materials prepared therewith, and related methods | |
| CN106519238A (en) | Synthetic method for macromolecule silane coupling agent | |
| CN107641466B (en) | Organic silicon solvent-free impregnating varnish and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180724 Address after: 412199 Industrial Park, Lukou Economic Development Zone, Zhuzhou County, Zhuzhou, Hunan Patentee after: Zhuzhou Times Electric Insulation Co., Ltd. Address before: 412007 Haitian Road, Tianyuan District, Zhuzhou, Hunan Province, No. 18 Patentee before: Zhuzhou Shidai New Material Sci-Tech Co., Ltd. |