CN102938279B - Preparation method of heat-resistant epoxy resin insulator - Google Patents
Preparation method of heat-resistant epoxy resin insulator Download PDFInfo
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- CN102938279B CN102938279B CN201210483759.0A CN201210483759A CN102938279B CN 102938279 B CN102938279 B CN 102938279B CN 201210483759 A CN201210483759 A CN 201210483759A CN 102938279 B CN102938279 B CN 102938279B
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Abstract
The invention discloses a preparation method of a heat-resistant epoxy resin insulator, which comprises the following steps: performing surface treatment on silicon micropowder with epoxy resin curing agent and gamma-(2,3-epoxy propoxy)propyltrimethoxysilicane; heating the silicon micropowder subjected to surface treatment at 40-50 DEG C for 1-2 hours, and drying for 1-2 hours under the condition of heating to 105-120 DEG C; and then, naturally cooling, mechanically separating bonded silicon micropowder particles, compounding with epoxy resin, and curing to obtain the heat-resistant epoxy resin insulator, wherein the glass transition temperature of the heat-resistant epoxy resin insulator is increased by more than 10 DEG C in comparison with the common epoxy insulator. The invention has the advantages of simple process and mild reaction conditions, and can effectively improve the heat resistance of the epoxy resin insulator. Compared with the conventional silicon micropowder filled epoxy resin composite material, the glass transition temperature of the epoxy resin insulator prepared by the invention is increased by more than 15 DEG C when the silicon micropowder particle content is 30%.
Description
Technical field
The present invention relates to the preparation method of heat proof material, particularly relate to a kind of preparation method of heat resistant epoxide resin insulator.
Background technology
Epoxy resin has good electrical insulating property, chemical stability, corrosion resistance, cohesiveness and good mechanical performance and machinability, be the important thermoset macromolecule material of a class, have a wide range of applications in fields such as electric, chemical industry, light industry, machinery, electronics, water conservancy, traffic, automobile, building and Aero-Space.At present, the yearly productive capacity of epoxy resin has exceeded 1,500,000 tons in the world, and has ever-increasing trend.Along with the development of Chinese national economy, to epoxy resin range of application also in continuous expansion, thereby the heat resistance of epoxy resin has been proposed to new requirement." heat resistance " of material refers to that material is in the short time or for a long time under high temperature and temperature change fast, the in fact injury-free or indeclinable ability of its main performance.Because the impacts such as electric property, mechanical performance, globality, operational reliability and the useful life of environment serviceability temperature on epoxy resin are very large, therefore, the heat resistance of epoxy resin enjoys product designer, producer and user's concern.Epoxy resin insulator is aspect epoxy resin apply in electric material one, and mechanical strength, insulating properties thermal endurance are had to higher requirement.In order to improve insulation property, the mechanical performance of epoxy resin insulator and to reduce production costs, be often filled in epoxy resin the silicon powder of 30% left and right as filler in process of production, prepare epoxy resin insulator.The epoxy resin insulator that silicon powder is filled uses at normal temperatures and can greatly improve mechanical property, the insulation property of epoxy resin and reduce production costs.But when this material is during for the occasion of the higher occasion of temperature or variations in temperature, often easily produce interfacial failure, thereby affect its hot serviceability.This is on the one hand because silicon powder is inorganic material, and adhesion between organic epoxy resin a little less than; The thermal coefficient of expansion that is on the other hand silicon powder and epoxy resin there are differences, and when variations in temperature, often, due to the mismatch of thermal coefficient of expansion, produces interfacial failure; The 3rd, because the main component of silicon powder is silicon dioxide, there is hydrophily, there is certain combination water in surface, and in the time that temperature is elevated to a certain degree, the combination water vapor on surface forms air film, to generation of interfaces destruction between silicon powder and epoxy resin.Thereby the hot property of epoxy composite material is affected.
Summary of the invention
In order to overcome epoxy insulation affected problem of serviceability under hot conditions of silicon powder filling, the object of the present invention is to provide a kind of preparation method of heat resistant epoxide resin insulator.Can, in improving the insulator mechanical strength of epoxy resin, improve the heat resistance of material by the method.
In order to achieve the above object, the step of the technical solution used in the present invention is as follows:
(1) by γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane coupling agent and epoxy curing agent be worth in mass ratio for after the ratio of 1:10 ~ 30 mixes, add and γ-(2,3-epoxy the third oxygen) ethanolic solution that the content of hydrochloric acid of propyl trimethoxy silicane equivalent is 2%, the mixed liquor after stirring is stand-by;
(2) mixed liquor of being prepared by step (1) joins in the container that is placed with silicon powder silicon powder is carried out to surface treatment;
(3) silicon powder behind surface is heated 1 ~ 2 hour in the temperature of 40 ~ 50 degree, after described coupling agent is reacted with silicon powder and epoxy curing agent, heat 1 ~ 2 hour 105 ~ 120 degree are lower, to remove remnants in silicon powder in conjunction with water, hydrochloric acid and ethanol.
(4) after dried silicon powder is naturally cooling, after with mechanical lapping, the silicon powder of adhesion being separated, carry out compoundly with epoxy resin, then pass through epoxy curing agent curing molding, obtain required heat resistant epoxide resin insulator.
Epoxy curing agent in described step (1) is identical with the epoxy curing agent in described step (4), is diaminodiphenyl-methane or methyl tetrahydrochysene liquid phthalic anhydride.
Epoxy resin corresponding to described diaminodiphenyl-methane curing agent is E-44 bisphenol A type epoxy resin; Epoxy resin corresponding to methyl tetrahydrochysene liquid phthalic anhydride curing agent is E-39-D type bisphenol A type epoxy resin.
Mixed liquor in described step (2) and silicon powder mass ratio are 0.2 ~ 0.5:1.
In described step (4), the ratio of epoxy resin and curing agent is 1:0.5～0.8.
The beneficial effect that the present invention has is:
1, the surface conditioning agent of the present invention using the curing agent of epoxy resin as filler, not only technique is simple, and is conducive to reduce dissimilar materials.
2, owing to having added γ-(2 in curing agent, 3-epoxy the third oxygen) propyl trimethoxy silicane, can make γ-(2,3-epoxy the third oxygen) epoxide group in propyl trimethoxy silicane is when reacting with curing agent, silane can react with hydrogen bond condensation mode and silicon powder, has increased the binding strength of silicon powder and matrix.
3, because the curing agent in surface conditioning agent mates with epoxy resin, can react with epoxy resin, make the processing layer on silicon powder surface and epoxy resin-base have very good compatibility.
4,, in dry run, can effectively remove contained ethanol in the combination water, surface conditioning agent on silicon powder surface; When cooling, because surface is with the curing agent of oiliness, stops moisture to be combined with silicon powder, thereby avoided in recombination process, moisture is brought in composite material with silicon powder.
5,, owing to having increased one deck transition zone on differential surface, osmanthus, be conducive to reduce between matrix and filler because the mismatch that linear expansion coefficient difference is brought.
Compared with the epoxy resin composite material of 6, filling with conventional silicon differential, epoxy resin insulator prepared by the present invention is in the time that silicon powder granule content is 30%, more than the vitrification point of its material has improved 15 degree.
Brief description of the drawings
Accompanying drawing is the vitrification point comparison diagram of sample.
Sample 1 for silicon powder content be 30%, silicon powder does not pass through conventional epoxy insulation of this method processing; Sample 2 for silicon powder content be 30%, silicon powder surface is through epoxy insulation of the present embodiment method processing.
Embodiment
Be embodiments of the invention below, make object effect of the present invention will become more obvious by the description of embodiment.
embodiment 1:
By γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) with the curing agent diaminodiphenyl-methane of E-44 bisphenol A type epoxy resin in mass ratio for after the ratio of 1:10 mixes, add and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) content of hydrochloric acid of the equivalent ethanolic solution that is 2% is (wherein, concentration of hydrochloric acid used is 37%, ethanol used is absolute ethyl alcohol, concentration according to 2% is formulated after calculating), after stirring, become surface conditioning agent, joined to be placed with in the container that fineness is 1000 object silicon powder particles it is carried out to surface treatment, wherein the ratio of silicon differential and surface conditioning agent is 1:0.2, stir after 20 minutes, silicon powder after surface treatment is heated 2 hours in the temperature of 40 degree left and right, γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) react with silicon powder and curing agent after, under 120 degree, heat 1 hour, to remove the moisture on silicon powder surface, ethanol and hydrochloric acid, naturally after cooling, after the silicon powder of adhesion being separated by mechanical system, the silicon powder that takes amount of calculation joins (ratio of E-44 bisphenol A type epoxy resin and diaminodiphenyl-methane is 1:08) in E-44 bisphenol A type epoxy resin and diaminodiphenyl-methane resin, after stirring, technique is cured moulding routinely, obtain silicon powder content and be 30% epoxy insulation.In addition, in order to contrast, by compound to not surface treated silicon powder and E-44 bisphenol A type epoxy resin (wherein curing agent is diaminodiphenyl-methane) moulding, prepare silicon powder content and be the epoxy resin insulator that 30% conventional silicon powder is filled.In addition, utilize above-mentioned two kinds of techniques, prepare respectively the sample of DSC test, carry out glass transition temperature mensuration.The data demonstration obtaining, the vitrification point that obtains sample with common process is 141.7 degree, the vitrification point obtaining with the sample of technique of the present invention is 160.3 degree.As shown in drawings, sample 1 for silicon powder content be 30%, silicon powder does not pass through epoxy insulation of this method processing; Sample 2 for silicon powder content be 30%, silicon powder surface is through epoxy insulation of the present embodiment method processing.
embodiment 2:
Just γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) with the curing agent methyl tetrahydrochysene liquid phthalic anhydride of E-39-D type bisphenol A type epoxy resin in mass ratio for after the ratio of 1:30 mixes, add and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) content of hydrochloric acid of the equivalent ethanolic solution that is 2% is (wherein, concentration of hydrochloric acid used is 37%, ethanol used is absolute ethyl alcohol, concentration according to 2% is formulated after calculating), after stirring, become surface conditioning agent, joined to be placed with in the container that fineness is 1000 object silicon powder particles silicon powder is carried out to surface treatment, wherein the ratio of silicon differential and surface conditioning agent is 1:0.3, stir after 20 minutes, silicon powder after surface treatment is heated 1 hour in the temperature of 45 degree left and right, make γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) react with silicon powder and curing agent methyl tetrahydrochysene liquid phthalic anhydride after, under 105 degree, heat 2 hours, to remove the moisture on silicon powder surface, ethanol and hydrochloric acid, naturally after cooling, after the silicon powder of adhesion being separated by mechanical system, the silicon powder that takes amount of calculation joins E-39-D type bisphenol A type epoxy resin and methyl tetrahydrochysene liquid phthalic anhydride (ratio of E-39-D type bisphenol A type epoxy resin and methyl tetrahydrochysene liquid phthalic anhydride is 1:0.6), after stirring, technique is cured process moulding routinely, obtain silicon powder content and be 30% epoxy insulation.In addition, in order to contrast, compound to not surface treated silicon powder and E-39-D type bisphenol A type epoxy resin (wherein curing agent is methyl tetrahydrochysene liquid phthalic anhydride) prepared to silicon powder content is the epoxy resin insulator that 32% conventional silicon powder is filled.In addition, utilize above-mentioned two kinds of techniques, prepare respectively DSC test sample, carry out glass transition temperature mensuration.The data demonstration obtaining, the vitrification point that obtains sample with common process is 151.5 degree, the vitrification point obtaining with the sample of technique of the present invention is 168.7 degree.
embodiment 3:
Just γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) with the curing agent methyl tetrahydrochysene liquid phthalic anhydride of E-39-D type bisphenol A type epoxy resin in mass ratio for after the ratio of 1:20 mixes, add and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) content of hydrochloric acid of the equivalent ethanolic solution that is 2% is (wherein, concentration of hydrochloric acid used is 37%, ethanol used is absolute ethyl alcohol, concentration according to 2% is formulated after calculating), after stirring, become surface conditioning agent, joined to be placed with in the container that fineness is 800 object silicon powder particles silicon powder is carried out to surface treatment, wherein the ratio of silicon differential and surface conditioning agent is 1:0.5, stir after 20 minutes, silicon powder after surface treatment is heated 1.5 hours in the temperature of 42 degree left and right, make γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane) react with silicon powder and curing agent methyl tetrahydrochysene liquid phthalic anhydride after, under 105 degree, heat 2 hours, to remove the moisture on silicon powder surface, ethanol and hydrochloric acid, naturally after cooling, after the silicon powder of adhesion being separated by mechanical system, the silicon powder that takes amount of calculation joins E-39-D type bisphenol A type epoxy resin and methyl tetrahydrochysene liquid phthalic anhydride (ratio of E-39-D type bisphenol A type epoxy resin and methyl tetrahydrochysene liquid phthalic anhydride is 1:0.5), after stirring, technique is cured process moulding routinely, obtain silicon powder content and be 26% epoxy insulation.In addition, in order to contrast, compound to not surface treated silicon powder and E-39-D type bisphenol A type epoxy resin (wherein curing agent is methyl tetrahydrochysene liquid phthalic anhydride) prepared to silicon powder content is the epoxy resin insulator that 25% conventional silicon powder is filled.In addition, utilize above-mentioned two kinds of techniques, prepare respectively DSC test sample, carry out glass transition temperature mensuration.The data demonstration obtaining, the vitrification point that obtains sample with common process is 151.8 degree, the vitrification point obtaining with the sample of technique of the present invention is 167.9 degree.
Claims (5)
1. a preparation method for heat resistant epoxide resin insulator, is characterized in that the step of the method is as follows:
(1) by γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and epoxy curing agent be worth in mass ratio for after the ratio of 1:10 ~ 30 mixes, add and γ-(2,3-epoxy the third oxygen) ethanolic solution that the content of hydrochloric acid of propyl trimethoxy silicane equivalent is 2%, the mixed liquor after stirring is stand-by;
(2) mixed liquor of being prepared by step (1) joins in the container that is placed with silicon powder silicon powder is carried out to surface treatment;
(3) silicon powder behind surface is heated 1 ~ 2 hour in the temperature of 40 ~ 50 degree, after described coupling agent is reacted with silicon powder and epoxy curing agent, heat 1 ~ 2 hour 105 ~ 120 degree are lower, to remove remnants in silicon powder in conjunction with water, hydrochloric acid and ethanol;
(4) after dried silicon powder is naturally cooling, after with mechanical lapping, the silicon powder of adhesion being separated, carry out compoundly with epoxy resin, then pass through epoxy curing agent curing molding, obtain required heat resistant epoxide resin insulator.
2. the preparation method of a kind of heat resistant epoxide resin insulator according to claim 1, it is characterized in that: the epoxy curing agent in described step (1) is identical with the epoxy curing agent in described step (4), be diaminodiphenyl-methane or methyl tetrahydrochysene liquid phthalic anhydride.
3. the preparation method of a kind of heat resistant epoxide resin insulator according to claim 2, is characterized in that: epoxy resin corresponding to described diaminodiphenyl-methane curing agent is E-44 bisphenol A type epoxy resin; Epoxy resin corresponding to methyl tetrahydrochysene liquid phthalic anhydride curing agent is E-39-D type bisphenol A type epoxy resin.
4. the preparation method of a kind of heat resistant epoxide resin insulator according to claim 1, is characterized in that: the mixed liquor in described step (2) and silicon powder mass ratio are 0.2 ~ 0.5:1.
5. the preparation method of a kind of heat resistant epoxide resin insulator according to claim 1, is characterized in that: in described step (4), the ratio of epoxy resin and curing agent is 1:0.5～0.8.
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| CN201210483759.0A CN102938279B (en) | 2012-11-26 | 2012-11-26 | Preparation method of heat-resistant epoxy resin insulator |
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| CN201210483759.0A CN102938279B (en) | 2012-11-26 | 2012-11-26 | Preparation method of heat-resistant epoxy resin insulator |
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| CN102938279B true CN102938279B (en) | 2014-11-05 |
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| CN107064754A (en) * | 2017-03-28 | 2017-08-18 | 国网上海市电力公司 | A kind of variable pulse voltage triggers the device of epoxy resin insulation material electric branch |
| CN111393797A (en) * | 2020-03-26 | 2020-07-10 | 上海稳优实业有限公司 | Preparation method of epoxy resin premix for improving anti-settling performance of filler |
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| CN101840757A (en) * | 2010-05-21 | 2010-09-22 | 扬州东宇电气有限公司 | Manufacturing method for environment-friendly type insulator shell |
| CN101958166A (en) * | 2010-09-02 | 2011-01-26 | 广西银河迪康电气有限公司 | Manufacture method of solid insulating circuit device |
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Patent Citations (5)
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| EP0676448A1 (en) * | 1994-04-08 | 1995-10-11 | Kabushiki Kaisha Toshiba | Epoxy resin composition and resin molding using the same |
| CN1828784A (en) * | 2006-03-27 | 2006-09-06 | 三门尔格科技有限公司 | Outdoor insulative supporting terminal |
| CN101800100A (en) * | 2010-04-23 | 2010-08-11 | 广西银河迪康电气有限公司 | Manufacture technology of middle pressure solid insulating sleeve |
| CN101840757A (en) * | 2010-05-21 | 2010-09-22 | 扬州东宇电气有限公司 | Manufacturing method for environment-friendly type insulator shell |
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