CN113667162A - Method for improving high-temperature resistance of silicone resin and composite material thereof - Google Patents
Method for improving high-temperature resistance of silicone resin and composite material thereof Download PDFInfo
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000805 composite resin Substances 0.000 claims abstract description 22
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims abstract description 15
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004744 fabric Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 230000002787 reinforcement Effects 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 9
- 230000004580 weight loss Effects 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- 238000012360 testing method Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000007769 metal material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Abstract
The invention discloses a method for improving high-temperature resistance of silicone resin and a composite material thereof, which comprises the following steps: firstly, synthesizing methyl phenyl silicone resin by using methyl triethoxysilane, phenyl trimethoxysilane and methyl diethoxy silane as raw materials; secondly, coating methyl phenyl silicone resin on the reinforcement, pretreating to obtain prepreg cloth, cutting the prepreg cloth, and forming to obtain a silicone resin-based composite material; and thirdly, carrying out high-temperature heat treatment on the methyl phenyl silicone resin and the composite material thereof. After high-temperature heat treatment, the residual weight fraction of the silicone resin at high temperature is increased from 51-69% to 57-84%, the temperature at 5% weight loss is increased from 442.5-533.3 ℃ to 533.8-629.8 ℃, and the bending strength of the composite material after high-temperature heat treatment at 500 ℃ can reach 40-130 MPa, thereby solving the problems of large weight loss fraction, poor mechanical property, poor high-temperature resistance and the like of the conventional silicone resin and the composite material thereof at high temperature.
Description
Technical Field
The invention relates to a method for improving high-temperature resistance of silicone resin and a composite material thereof.
Background
The silicone resin and the composite material thereof have excellent heat insulation, low dielectric, low tangent loss and other properties, are widely applied to the fields of electronic instruments, aerospace, national defense and military industry and the like, are especially hot materials for manufacturing the radome at present, but with the requirements of modern war and the development of missile technology, the Mach number of an aircraft is continuously improved, the missile warhead flying at high speed generates a large amount of heat due to severe friction with air, and the requirement on the high temperature resistance of the radome is increasingly improved.
At present, there is no systematic research on the performance improvement of the polymer composite material by adopting a heat treatment process at home and abroad, and the heat treatment process is mostly applied to metal materials and inorganic non-metal materials. Heat treatment refers to a material processing technique in which after a material is formed, the material is heated, kept warm, and cooled to obtain a desired structure, and properties. The heat treatment of the polymer composite material generally selects a certain heating rate to heat to a certain temperature, keeps the temperature for a period of time, and then cools to room temperature at a certain rate to improve the performance of the composite material.
At present, most of silicone resin can lose weight by 30-40% at 450-500 ℃, the research on improving the high-temperature resistance of the silicone resin and the composite material thereof by adopting a high-temperature heat treatment method is limited, the bending strength of the methyl phenyl silicone resin composite material which is not subjected to high-temperature treatment is 5-10 MPa at 800 ℃, and the performance at high temperature is poor.
Disclosure of Invention
The invention provides a method for improving the high-temperature resistance of silicone resin and a composite material thereof, aiming at solving the problems of great loss and poor performance at high temperature of the conventional silicone resin and the composite material thereof.
The purpose of the invention is realized by the following technical scheme:
a method for improving high-temperature resistance of silicone resin comprises the following steps:
step one, using methyltriethoxysilane, phenyltrimethoxysilane and methyldiethoxysilane as raw materials, and controlling the molar ratio of the methyltriethoxysilane to the phenyltrimethoxysilane to the methyldiethoxysilane to be 2-5: 0.1-2: 0.5-2, synthesizing the methyl phenyl silicone resin with the R/Si ratio of 1.1-1.3 and the Ph/Si of 0.1-0.8, and specifically comprising the following steps:
(1) the method comprises the following steps of taking methyltriethoxysilane, phenyltrimethoxysilane and methyldiethoxysilane as raw materials, taking ethanol as a solvent, adding the raw materials into a three-neck flask, placing the three-neck flask into an oil bath kettle at the temperature of 60-90 ℃ for heating, mixing a proper amount of catalyst and deionized water, adding the mixture into the three-neck flask, carrying out condensation reflux reaction for 10-15 hours, and preparing a methylphenylsilicone resin prepolymer through hydrolytic condensation, wherein: the catalyst is an acidic catalyst or a basic catalyst, and the acidic catalyst is one or more of hydrochloric acid, acetic acid and propionic acid; the alkaline catalyst is one or more of organic alkali and inorganic alkali such as ammonia water, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the amount of the catalyst is 1-5% of the total mole of the silane;
(2) distilling the prepolymer of the methyl phenyl silicone resin at 140-160 ℃ under reduced pressure to remove ethanol, methanol and water, distilling at 110-130 ℃ under reduced pressure for 0.5-2 h when the temperature of a reaction system rises, and cooling to room temperature to obtain methyl phenyl silicone resin;
and secondly, placing the methyl phenyl silicone resin composite material in a tubular furnace for high-temperature heat treatment, wherein the heat treatment temperature is controlled to be 350-600 ℃, and the heat treatment time is 0.5-2 h.
A method for improving the high temperature resistance of a silicone resin composite material comprises the following steps:
step one, using methyltriethoxysilane, phenyltrimethoxysilane and methyldiethoxysilane as raw materials, and controlling the molar ratio of the methyltriethoxysilane to the phenyltrimethoxysilane to the methyldiethoxysilane to be 2-5: 0-2: 0.5-2, synthesizing the methyl phenyl silicone resin with the R/Si ratio of 1.1-1.3 and the Ph/Si of 0.1-0.8, and specifically comprising the following steps:
(1) the method comprises the following steps of taking methyltriethoxysilane, phenyltrimethoxysilane and methyldiethoxysilane as raw materials, taking ethanol as a solvent, adding the raw materials into a three-neck flask, placing the three-neck flask into an oil bath kettle at the temperature of 60-90 ℃ for heating, mixing a proper amount of catalyst and deionized water, adding the mixture into the three-neck flask, carrying out condensation reflux reaction for 10-15 hours, and preparing a methylphenylsilicone resin prepolymer through hydrolytic condensation, wherein: the catalyst is an acidic catalyst or a basic catalyst, and the acidic catalyst is one or more of hydrochloric acid, acetic acid and propionic acid; the alkaline catalyst is one or more of organic alkali and inorganic alkali such as ammonia water, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the amount of the catalyst is 1-5% of the total mole of the silane;
(2) distilling the prepolymer of the methyl phenyl silicone resin at 140-160 ℃ under reduced pressure to remove ethanol, methanol and water, distilling at 110-130 ℃ under reduced pressure for 0.5-2 h when the temperature of a reaction system rises, and cooling to room temperature to obtain methyl phenyl silicone resin;
step two, coating the methyl phenyl silicone resin in the step one on the reinforcement by adopting a brush coating method, a blade coating method, a dry method or a wet method, pretreating to obtain a prepreg cloth, cutting the prepreg cloth, and molding by adopting a hot press molding process, an autoclave molding process or a vacuum bag molding method and the like to obtain the silicone resin-based composite material, wherein: the reinforcement is quartz fiber fabric, quartz fiber, high silica fiber or high silica fiber fabric; the pressure of hot-press molding is 5-10 MPa, the temperature is 200-350 ℃, and the time is 2-18 h; the silicone resin content in the silicone resin-based composite material is 10-60 wt%;
and step three, putting the methyl phenyl silicone resin composite material into a mold, applying a certain pressure, placing the mold in a muffle furnace for high-temperature heat treatment, controlling the heat treatment temperature to be 350-600 ℃, and controlling the heat treatment time to be 0.5-2 h.
Compared with the prior art, the invention has the following advantages:
the high-temperature heat treatment method adopts a tubular furnace and a muffle furnace as instruments, after high-temperature heat treatment, the residual weight fraction of the silicone resin at high temperature is increased from 51-69% to 57-84%, the temperature at 5% weight loss is increased from 442.5-533.3 ℃ to 533.8-629.8 ℃, and the bending strength of the composite material after high-temperature heat treatment at 500 ℃ can reach 40-130 MPa, thereby solving the problems of large weight loss fraction, poor mechanical property, poor high-temperature resistance and the like of the existing silicone resin and the composite material thereof at high temperature.
Drawings
FIG. 1 is a TGA test plot of a non-heat treated silicone;
FIG. 2 is a TGA test chart of silicone resin with 0.2 phenyl content after high temperature heat treatment;
FIG. 3 is a TGA test chart of a silicone resin with a phenyl content of 0.3 after high temperature heat treatment;
FIG. 4 is a TGA test chart of a silicone resin with 0.4 phenyl content after high temperature heat treatment;
FIG. 5 is a TGA test chart of a silicone resin with 0.5 phenyl content after high temperature heat treatment;
FIG. 6 is a TGA test chart of a silicone resin with 0.6 phenyl content after high temperature heat treatment;
FIG. 7 is a graph of bending properties of the silicone resin composite material with a phenyl content of 0.2-0.6 after heat treatment at 500 ℃.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
The invention provides a method for improving high-temperature resistance of silicone resin and a composite material thereof, which comprises the following steps:
step one, synthesizing methyl phenyl silicone resin with R/Si ratio of 1.2, Ph/Si of 0.2 (silane molar ratio of 4:0.5: 1), 0.3 (silane molar ratio of 3.5: 0.5: 1), 0.4 (silane molar ratio of 3: 1: 1), 0.5 (silane molar ratio of 2.5:1.5: 1) and 0.6 (silane molar ratio of 2:2: 1) by using methyl triethoxysilane, phenyl trimethoxysilane and methyl diethoxysilane as raw materials, and specifically comprising the following steps:
(1) methyl triethoxysilane, phenyl trimethoxysilane and methyl diethoxy silane are used as raw materials, ethanol is used as a solvent, the raw materials are added into a three-neck flask, the three-neck flask is placed into a 75 ℃ oil bath pot for heating, 1% hydrochloric acid of the total mole number of silane is added as a catalyst, the mixture is mixed with deionized water and then added into the three-neck flask, and the mixture is condensed and refluxed for 12 hours to prepare a methyl phenyl silicone resin prepolymer through hydrolysis and condensation;
(2) distilling the prepolymer of the methyl phenyl silicone resin at 150 ℃ under reduced pressure to remove ethanol, methanol and water, distilling the prepolymer under reduced pressure for 1h when the temperature of a reaction system is raised to 120 ℃, and cooling the prepolymer to room temperature to obtain methyl phenyl silicone resin;
preparing methyl phenyl silicone resin into a solution with the mass fraction of 50%, brushing the solution on a high silica fiber fabric, pretreating to obtain a prepreg cloth, cutting the prepreg cloth, placing the cut prepreg cloth in a mold, and curing at the high temperature of 250 ℃ for 12 hours to obtain a silicone resin-based composite material with the silicone resin content of 25 wt%;
and step three, performing high-temperature heat treatment on the methyl phenyl silicone resin with different phenyl contents and the composite material thereof, wherein the heat treatment temperature is controlled to be 350 ℃, 400 ℃, 450 ℃ and 500 ℃, and the heat treatment time is 1 h.
As can be seen from FIGS. 1-6, the residual weight of the silicone resin obtained by the above method is 74.1%, 75.3%, 80.0% and 84.2% when the phenyl content is 0.2 after the silicone resin with different phenyl contents is subjected to high-temperature treatment at 350 ℃, 400 ℃, 450 ℃ and 500 ℃ through tests; when the content of the phenyl is 0.3, the residual weight is 70.5 percent, 71.5 percent, 75.5 percent and 78.3 percent respectively; when the content of the phenyl is 0.4, the residual weight is respectively 64.9 percent, 65.9 percent, 69.6 percent and 73.5 percent; when the content of the phenyl is 0.5, the residual weight is respectively 60.3%, 61.6%, 64.1% and 68.7%; when the content of phenyl groups was 0.6, the residual weight percentages were 56.7%, 57.6%, 59.6% and 64.9%, respectively.
As can be seen from FIG. 7, after the silicone resin composite material obtained by the above method is subjected to high-temperature heat treatment at 500 ℃, the bending strength of the silicone resin composite material with the phenyl content of 0.2 at 500 ℃ can reach 100-130 MPa; the bending strength of the silicone resin composite material with the phenyl content of 0.3 at 500 ℃ can reach 70-90 MPa; the bending strength of the silicone resin composite material with the phenyl content of 0.4 at 500 ℃ can reach 60-90 MPa; the bending strength of the silicone resin composite material with the phenyl content of 0.5 at 500 ℃ can reach 55-90 MPa; the bending strength of the silicone resin composite material with the phenyl content of 0.6 at 500 ℃ can reach 40-70 MPa.
Claims (10)
1. A method for improving high temperature resistance of silicone resin is characterized by comprising the following steps:
step one, using methyltriethoxysilane, phenyltrimethoxysilane and methyldiethoxysilane as raw materials, and controlling the molar ratio of the methyltriethoxysilane to the phenyltrimethoxysilane to the methyldiethoxysilane to be 2-5: 0.1-2: 0.5-2, synthesizing methyl phenyl silicone resin with the R/Si ratio of 1.1-1.3 and the Ph/Si of 0.1-0.8;
and secondly, placing the methyl phenyl silicone resin composite material in a tubular furnace for high-temperature heat treatment, wherein the heat treatment temperature is controlled to be 350-600 ℃, and the heat treatment time is 0.5-2 h.
2. The method for improving high temperature resistance of silicone resin according to claim 1, wherein the methyl phenyl silicone resin is prepared by the following steps:
(1) adding methyl triethoxysilane, phenyl trimethoxysilane and methyl diethoxy silane which serve as raw materials and ethanol which serves as a solvent into a three-neck flask, heating the three-neck flask in an oil bath kettle at the temperature of 60-90 ℃, mixing a catalyst and deionized water, adding the mixture into the three-neck flask, performing condensation reflux reaction for 10-15 hours, and preparing a methyl phenyl silicone resin prepolymer through hydrolytic condensation;
(2) and distilling the prepolymer of the methyl phenyl silicone resin at 140-160 ℃ under reduced pressure to remove ethanol, methanol and water, distilling at 110-130 ℃ under reduced pressure for 0.5-2 h when the temperature of the reaction system rises, and cooling to room temperature to obtain the methyl phenyl silicone resin.
3. The method of claim 2, wherein the catalyst is an acidic catalyst or a basic catalyst, and the amount of the catalyst is 1-5% of the total molar number of the silane.
4. The method for improving the high temperature resistance of the silicone resin according to claim 3, wherein the acidic catalyst is one or more of hydrochloric acid, acetic acid and propionic acid; the alkaline catalyst is one or more of ammonia water, potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide.
5. A method for improving the high temperature resistance of a silicone resin composite material is characterized by comprising the following steps:
step one, using methyltriethoxysilane, phenyltrimethoxysilane and methyldiethoxysilane as raw materials, and controlling the molar ratio of the methyltriethoxysilane to the phenyltrimethoxysilane to the methyldiethoxysilane to be 2-5: 0.1-2: 0.5-2, synthesizing methyl phenyl silicone resin with the R/Si ratio of 1.1-1.3 and the Ph/Si of 0.1-0.8;
step two, coating the methyl phenyl silicone resin obtained in the step one on the reinforcement by adopting a brush coating method, a blade coating method, a dry method or a wet method, pretreating to obtain a prepreg cloth, cutting the prepreg cloth, and forming by adopting a hot press forming process, an autoclave forming process or a vacuum bag forming method to obtain a silicone resin-based composite material with the silicone resin content of 10-60 wt%;
and step three, putting the methyl phenyl silicone resin composite material into a mold, applying pressure, placing the mold in a muffle furnace, and performing high-temperature heat treatment, wherein the heat treatment temperature is controlled to be 350-600 ℃, and the heat treatment time is 0.5-2 h.
6. The method for improving the high temperature resistance of the silicone resin composite material according to claim 5, wherein the methyl phenyl silicone resin is prepared by the following steps:
(1) adding methyl triethoxysilane, phenyl trimethoxysilane and methyl diethoxy silane which serve as raw materials and ethanol which serves as a solvent into a three-neck flask, heating the three-neck flask in an oil bath kettle at the temperature of 60-90 ℃, mixing a catalyst and deionized water, adding the mixture into the three-neck flask, performing condensation reflux reaction for 10-15 hours, and preparing a methyl phenyl silicone resin prepolymer through hydrolytic condensation;
(2) and distilling the prepolymer of the methyl phenyl silicone resin at 140-160 ℃ under reduced pressure to remove ethanol, methanol and water, distilling at 110-130 ℃ under reduced pressure for 0.5-2 h when the temperature of the reaction system rises, and cooling to room temperature to obtain the methyl phenyl silicone resin.
7. The method of claim 6, wherein the catalyst is an acidic catalyst or a basic catalyst, and the amount of the catalyst is 1-5% of the total mole of the silane.
8. The method for improving the high temperature resistance of the silicone resin composite material according to claim 7, wherein the acidic catalyst is one or more of hydrochloric acid, acetic acid and propionic acid; the alkaline catalyst is one or more of ammonia water, potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide.
9. The method for improving the high temperature resistance of the silicone composite material according to claim 5, wherein the reinforcement is a quartz fiber fabric, a quartz fiber, a high silica fiber or a high silica fiber fabric.
10. The method for improving the high temperature resistance of the silicone resin composite material according to claim 5, wherein the hot press forming pressure is 5-10 MPa, the temperature is 200-350 ℃, and the time is 2-18 h.
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| CN116589682A (en) * | 2023-07-13 | 2023-08-15 | 哈尔滨工业大学 | Preparation method and application of silicone resin suitable for hot-melt presoaking |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381515A (en) * | 2008-09-26 | 2009-03-11 | 哈尔滨工业大学 | Process for preparing silicon resin base composite material |
| CN104151558A (en) * | 2014-08-08 | 2014-11-19 | 广东省工业技术研究院(广州有色金属研究院) | Preparation method for MDTQ type methyl phenyl vinyl silicone resin |
| CN104211964A (en) * | 2014-09-13 | 2014-12-17 | 哈尔滨工业大学 | Method for preparing organic silicon resin heat-resisting material by utilizing modified alumina |
| WO2016101534A1 (en) * | 2014-12-25 | 2016-06-30 | 广东生益科技股份有限公司 | Ceramized silicone resin composition and pre-preg and laminate that use the composition |
| CN105778506A (en) * | 2014-12-25 | 2016-07-20 | 广东生益科技股份有限公司 | Organic silicon resin composition and prepreg, laminated board, copper-clad plate and aluminum-based plate adopting same |
| CN107698269A (en) * | 2017-09-18 | 2018-02-16 | 上海大学 | Infiltrate the method for silicones intensified ceramic core |
-
2021
- 2021-09-18 CN CN202111096256.3A patent/CN113667162B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381515A (en) * | 2008-09-26 | 2009-03-11 | 哈尔滨工业大学 | Process for preparing silicon resin base composite material |
| CN104151558A (en) * | 2014-08-08 | 2014-11-19 | 广东省工业技术研究院(广州有色金属研究院) | Preparation method for MDTQ type methyl phenyl vinyl silicone resin |
| CN104211964A (en) * | 2014-09-13 | 2014-12-17 | 哈尔滨工业大学 | Method for preparing organic silicon resin heat-resisting material by utilizing modified alumina |
| WO2016101534A1 (en) * | 2014-12-25 | 2016-06-30 | 广东生益科技股份有限公司 | Ceramized silicone resin composition and pre-preg and laminate that use the composition |
| CN105778506A (en) * | 2014-12-25 | 2016-07-20 | 广东生益科技股份有限公司 | Organic silicon resin composition and prepreg, laminated board, copper-clad plate and aluminum-based plate adopting same |
| CN107698269A (en) * | 2017-09-18 | 2018-02-16 | 上海大学 | Infiltrate the method for silicones intensified ceramic core |
Non-Patent Citations (2)
| Title |
|---|
| 胡春平;刘丽;姜波;黄玉东;: "高硅氧/有机硅复合材料高温弯曲性能研究", 航空材料学报, no. 05, pages 66 - 69 * |
| 黎春阳;李国军;樊欣;张炳;任瑞铭;: "耐高温甲基苯基硅树脂的合成", 有机硅材料, no. 01, pages 5 - 9 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116589682A (en) * | 2023-07-13 | 2023-08-15 | 哈尔滨工业大学 | Preparation method and application of silicone resin suitable for hot-melt presoaking |
| CN116589682B (en) * | 2023-07-13 | 2023-10-03 | 哈尔滨工业大学 | Preparation method and application of silicone resin suitable for hot-melt presoaking |
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