CN111073057B - Heat-resistant additive, silicone rubber material and preparation method of silicone rubber material - Google Patents
Heat-resistant additive, silicone rubber material and preparation method of silicone rubber material Download PDFInfo
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- CN111073057B CN111073057B CN201911338005.4A CN201911338005A CN111073057B CN 111073057 B CN111073057 B CN 111073057B CN 201911338005 A CN201911338005 A CN 201911338005A CN 111073057 B CN111073057 B CN 111073057B
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000000654 additive Substances 0.000 title claims abstract description 39
- 230000000996 additive effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004945 silicone rubber Substances 0.000 title claims description 37
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 57
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 29
- SHWQWXGIWFEYTA-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-triazatrisilinane Chemical compound N1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)N[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)N[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 SHWQWXGIWFEYTA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920002545 silicone oil Polymers 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 23
- 238000004073 vulcanization Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000005060 rubber Substances 0.000 claims description 21
- 239000006229 carbon black Substances 0.000 claims description 18
- -1 methyl vinyl Chemical group 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 16
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 16
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 16
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005642 Oleic acid Substances 0.000 claims description 16
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 16
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 5
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical group ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 230000032683 aging Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a heat-resistant additive, a silicon rubber material and a preparation method of the silicon rubber material. The heat-resistant additive comprises 1-10 parts of nano zirconium hydroxide, 1-5 parts of nano yttrium oxide and 0.1-0.9 part of hexaphenylcyclotrisilazane. According to the invention, nano zirconium hydroxide, nano yttrium oxide and hexaphenylcyclotrisilazane are matched and combined in proper dosage to form a specific heat-resistant additive formula. The components in the formula of the heat-resistant additive act synergistically, and when the heat-resistant additive is used for preparing a silicon rubber material, the obtained silicon rubber material keeps good mechanical properties at a higher temperature.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a heat-resistant additive, a silicone rubber material and a preparation method of the silicone rubber material.
Background
The silicone rubber belongs to special synthetic rubber, is different from the C-C bond of common rubber, has an inorganic structure of Si-O as a main chain, and belongs to a semi-inorganic, saturated, miscellaneous-chain and nonpolar elastomer. The elastomer with the side group being an organic group has the characteristics of excellent high and low temperature resistance, weather aging resistance, electric insulation, physiological inertia and the like, is widely applied to the fields of electronic and electric appliances, aerospace, machinery manufacturing, medical health and the like, and also has wide application in daily life. The service temperature range of the common silicon rubber is-50-200 ℃. With the continuous development of science and technology, the application field of the silicon rubber is wider and wider, and higher requirements are provided for the high temperature resistance and the aging resistance of the silicon rubber. The traditional silicon rubber cannot be used under the condition of higher temperature, and becomes brittle quickly under the condition of exceeding 250 ℃, so that the physical properties of the traditional silicon rubber are reduced sharply.
The methods for improving the heat resistance of the silicone rubber mainly comprise the following steps: changing the side chain group of silicon rubber, adding heat-resistant additive, introducing hetero atom, etc. The improvement of the high temperature resistance of the silicone rubber by adding the high temperature resistant additive is a hot point of research. Most of the heat-resistant additives commonly used at present are metal oxides and soluble transition metal compounds, among which metal oxides are most commonly used. However, the addition of some heat-resistant additives has limited improvement on the performance of the silicone rubber, and the mechanical properties of the silicone rubber cannot be maintained in a larger temperature range; the other high-temperature resistant additives can effectively inhibit the oxidative degradation of the silicone rubber within a certain temperature range, but when the temperature exceeds the temperature range, the degradation speed is increased, and certain limitations still exist. Overall, the heat resistance of the traditional heat-resistant additive to silicone rubber is not ideal.
Disclosure of Invention
Based on the above, the main object of the present invention is to provide a heat-resistant additive, and a silicone rubber material prepared by using the heat-resistant additive has good high temperature resistance.
The purpose of the invention is realized by the following technical scheme:
the invention mainly aims to provide a heat-resistant additive which comprises 1-10 parts of zirconium hydroxide, 1-5 parts of yttrium oxide and 0.1-0.9 part of hexaphenylcyclotrisilazane.
In one embodiment, the heat-resistant additive comprises 5.5-6.5 parts of zirconium hydroxide, 2.5-3.5 parts of yttrium oxide, and 0.35-0.45 part of hexaphenylcyclotrisilazane.
In one embodiment, the yttria is treated by the following method:
s1, putting the yttrium oxide into absolute ethyl alcohol for ultrasonic treatment;
s2, adding the yttrium oxide treated in the step S1 into oleic acid diluted by absolute ethyl alcohol, performing ultrasonic treatment, heating and stirring, cooling and standing, washing, centrifuging and drying.
In one embodiment, in step S2, the volume ratio of the volume of oleic acid to the volume of absolute ethanol is (0.5-1.5): 1.
in one embodiment, in step S2, the heating temperature is 55-65 ℃, and the heating time is 0.5-1.5 h; or/and the drying temperature is 80-110 ℃, and the drying time is 2.5-3.5 h.
In one embodiment, the particle size of the zirconium hydroxide is between 50-100 nm; or/and the yttrium oxide has a grain diameter of 30-50nm and a specific surface area of more than 50m2/g。
The invention also aims to provide the application of the heat-resistant additive in preparing high-temperature-resistant silicon rubber.
The invention also aims to provide high-temperature-resistant silicon rubber, and the preparation raw material of the high-temperature-resistant silicon rubber comprises the following components in parts by mass: 100-130 parts of methyl vinyl crude rubber, 30-60 parts of white carbon black, 3-10 parts of hydroxyl silicone oil, 0.1-3 parts of vulcanizing agent, 0-0.3 part of phenyl silicone oil, 0-0.3 part of zinc stearate and the heat-resistant additive.
In one embodiment, the raw materials for preparing the silicone rubber material comprise the following components in parts by mass: 125 portions of methyl vinyl crude rubber 115-45 portions, white carbon black 35-45 portions, hydroxyl silicone oil 4-5.5 portions, vulcanizing agent 1-2.5 portions, phenyl silicone oil 0-0.3 portion, zinc stearate 0-0.3 portion, zirconium hydroxide 5.5-6.5 portions, and the heat-resistant additive.
In one embodiment, the molar content of vinyl in the methyl vinyl raw rubber is 0.15-0.35%; or/and the white carbon black is fumed silica with the specific surface area of more than or equal to 100m2(ii)/g; or/and the vulcanizing agent is 2, 4-dichlorobenzoyl peroxide.
The invention also aims to provide a preparation method of the high-temperature-resistant silicon rubber, which comprises the following steps:
firstly, mixing the methyl vinyl raw rubber, the white carbon black, the hydroxyl silicone oil, the phenyl silicone oil and the zinc stearate;
secondly, adding the zirconium hydroxide, yttrium oxide and hexaphenylcyclotrisilazane into the product obtained in the first step, and mixing;
and thirdly, adding the vulcanizing agent into the product obtained in the second step, and carrying out primary vulcanization and secondary vulcanization.
In one embodiment, the conditions for the primary vulcanization are 130-150 ℃ and 8-12 min.
In one embodiment, the secondary vulcanization is carried out at 220 ℃ for 3.5-4.5 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention combines zirconium hydroxide, yttrium oxide and hexaphenylcyclotrisilazane in proper dosage to form a specific heat-resistant additive formula. The components in the formula of the heat-resistant additive act synergistically, and when the heat-resistant additive is used for preparing a silicon rubber material, the obtained silicon rubber material keeps good mechanical property at a higher temperature, so that the silicon rubber can be used at a higher temperature.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment of the invention provides a heat-resistant additive, which comprises 1-10 parts of zirconium hydroxide, 1-5 parts of yttrium oxide and 0.1-0.9 part of hexaphenylcyclotrisilazane.
The invention researches the proper addition ratio of zirconium hydroxide, yttrium oxide and hexaphenylcyclotrisilazane, and the synergistic effect of the three substances greatly increases the high temperature resistance of the silicone rubber.
Preferably, the heat resistant additive comprises 5.5-6.5 parts of zirconium hydroxide, 2.5-3.5 parts of yttrium oxide, and 0.35-0.45 part of hexaphenylcyclotrisilazane.
Preferably, the yttria is treated by the following method:
s1, putting the yttrium oxide into absolute ethyl alcohol for ultrasonic treatment;
s2, adding the yttrium oxide treated in the step S1 into oleic acid diluted by absolute ethyl alcohol, performing ultrasonic treatment, heating and stirring, cooling and standing, washing, centrifuging and drying.
Preferably, in step S2, the volume ratio of the volume of the oleic acid to the volume of the absolute ethanol is (0.5-1.5): 1.
preferably, in step S2, the heating temperature is 55-65 ℃, and the heating time is 0.5-1.5 h; or/and the drying temperature is 80-110 ℃, and the drying time is 2.5-3.5 h.
Preferably, the particle size of the zirconium hydroxide is between 50 and 100 nm; or/and the yttrium oxide has a grain diameter of 30-50nm and a specific surface area of more than 50m2/g。
The yttrium oxide of the embodiment of the invention, particularly the processed yttrium oxide, is subjected to the processing, so that the dispersibility and the compatibility with silicon rubber are improved, the rubber mixing is more convenient, the mechanical property of the silicon rubber is improved, the decomposition temperature of raw rubber is improved, and the service life of a silicon rubber product in the air is prolonged.
Hydroxyl groups on the lower end of silicon rubber molecules under a high-temperature condition can cause a tripping reaction, so that the thermal stability of the silicon rubber is seriously influenced, and the zirconium hydroxide surface contains more abundant active silicon hydroxyl groups and reacts with hydroxyl groups at the chain ends of the silicon rubber molecules, so that the number of the hydroxyl groups at the ends is reduced to a greater extent, and the tripping reaction is inhibited.
The hexaphenylcyclotrisilazane can effectively inhibit the degradation problem of the main chain and improve the heat resistance.
The synergistic effect of the three substances keeps the mechanical property of the silicon rubber material under the high-temperature condition in a larger range, and improves the initial decomposition temperature of the silicon rubber.
The embodiment of the invention also provides application of the heat-resistant additive in preparation of a silicone rubber material.
The embodiment of the invention also provides a silicon rubber material, and the preparation raw material of the silicon rubber material comprises the following components in parts by mass: 100-130 parts of methyl vinyl crude rubber, 30-60 parts of white carbon black, 3-10 parts of hydroxyl silicone oil, 0.1-3 parts of vulcanizing agent, 0-0.3 part of phenyl silicone oil, 0-0.3 part of zinc stearate, 1-10 parts of zirconium hydroxide, 1-5 parts of yttrium oxide and 0.1-0.9 part of hexaphenyl cyclotrisilazane.
In the embodiment of the invention, the phenyl silicone oil is used as a compounding agent of the high-temperature resistant agent, so that the occurrence of structuring is reduced; the zinc stearate is used as an internal release agent, and the sample is effectively prevented from being torn when being released.
Preferably, the raw materials for preparing the silicon rubber material comprise the following components in parts by mass: 122 parts of methyl vinyl crude rubber, 39-41 parts of white carbon black, 4.5-5.5 parts of hydroxyl silicone oil, 1-2.5 parts of vulcanizing agent, 0-0.3 part of phenyl silicone oil, 0-0.3 part of zinc stearate, 5.5-6.5 parts of zirconium hydroxide, 2.5-3.5 parts of yttrium oxide and 0.35-0.45 part of hexaphenyl cyclotrisilazane.
Preferably, the molar content of vinyl in the methyl vinyl raw rubber is 0.15-0.35%; or/and the white carbon black is fumed silica with the specific surface area of more than or equal to 100m2(ii)/g; or/and the vulcanizing agent is 2, 4-dichlorobenzoyl peroxide.
The embodiment of the invention also provides a preparation method of the silicon rubber material, which comprises the following steps:
firstly, mixing the methyl vinyl raw rubber, the white carbon black, the hydroxyl silicone oil, the phenyl silicone oil and the zinc stearate;
secondly, adding the zirconium hydroxide, yttrium oxide and hexaphenylcyclotrisilazane into the product obtained in the first step, and mixing;
and thirdly, adding the vulcanizing agent into the product obtained in the second step, and carrying out primary vulcanization and secondary vulcanization.
Preferably, the conditions adopted by the primary vulcanization are 130-150 ℃ and 8-12 min; or/and the secondary vulcanization adopts the conditions of 180-220 ℃ and 3.5-4.5 h.
Preferably, the mixing temperature is 145-155 ℃, and the mixing time is 0.8-1.2 h.
The raw materials of the embodiment of the invention are as follows:
methyl vinyl raw rubber, wherein the molar content of vinyl is 0.15-0.35%, Zhejiang Hengchang organosilicon 110 methyl vinyl silicone rubber; the white carbon black is fumed silica with specific surface area of 100m or more2(iv) HN-300, a chemical company Limited of Haoneng of Jiangsu; the particle size of zirconium hydroxide is 50-100nm, DK-417-3 of Beijing Deke island gold science and technology Limited; the yttrium oxide has a particle size of 30-50nm and a specific surface area of more than 50m2(ii)/g, DK-Y2O3-20, available from Ishikaki technologies, Inc., Beijing Germany; the vulcanizing agent is 2, 4-dichlorobenzoyl peroxide, Aksu PerkadoxOPC-50S-PS-LM.
Example 1
The method comprises the following steps: the nano yttrium oxide is treated by the following method
(S1) putting the nano yttrium oxide into absolute ethyl alcohol for ultrasonic treatment for 20 min;
(S2) adding absolute ethyl alcohol diluted oleic acid (the volume ratio of the oleic acid to the absolute ethyl alcohol is 1:1) into the nano yttrium oxide treated in the step S1, and then carrying out ultrasonic treatment for 30 min;
(S3) stirring for a period of time at a certain temperature (specifically stirring for 1h at 60 ℃), then cooling and standing to room temperature, washing and centrifugally separating the mixture, and drying for 3h at 100 ℃ to obtain the processed nano yttrium oxide.
Step two: according to the weight portion, 115 portions of methyl vinyl raw rubber, 38 portions of white carbon black, 4 portions of hydroxyl silicone oil, 0.2 portion of phenyl silicone oil and 0.2 portion of zinc stearate are weighed and mixed under the condition of 25 ℃.
Step three: and (3) adding 4 parts of nano zirconium hydroxide, 2.5 parts of nano yttrium oxide and 0.3 part of hexaphenylcyclotrisilazane into the product obtained in the second step, stirring for 1 hour under the condition of keeping the temperature at 150 ℃, and cooling to obtain the heat-resistant silicone rubber compound.
Step four: and (3) adding 1.5 parts of vulcanizing agent into the product obtained in the third step according to the parts by weight, wherein the conditions of primary vulcanization are 130 ℃ and 10min, and the conditions of secondary vulcanization are 200 ℃ and 4h, so as to obtain the high-temperature-resistant silicon rubber material. The raw material formulation of the silicone rubber material is shown in table 1.
Example 2
The procedure of example 1 was repeated with the component contents specified in table 1 below, and the test results before and after aging are shown in tables 2 to 4.
The method comprises the following steps: the nano yttrium oxide is treated by the following method
(S1) putting the nano yttrium oxide into absolute ethyl alcohol for ultrasonic treatment for 20 min;
(S2) adding absolute ethyl alcohol diluted oleic acid (the volume ratio of the oleic acid to the absolute ethyl alcohol is 1:1) into the nano yttrium oxide treated in the step S1, and then carrying out ultrasonic treatment for 30 min;
(S3) stirring for a period of time at a certain temperature (specifically stirring for 1h at 60 ℃), then cooling and standing to room temperature, washing and centrifugally separating the mixture, and drying for 3h at 100 ℃ to obtain the processed nano yttrium oxide.
Step two: according to the parts by weight, 120 parts of methyl vinyl raw rubber, 40 parts of white carbon black, 5 parts of hydroxyl silicone oil, 0.2 part of phenyl silicone oil and 0.2 part of zinc stearate are weighed and mixed under the condition of 25 ℃.
Step three: and (3) adding 6 parts of nano zirconium hydroxide, 3 parts of nano yttrium oxide and 0.4 part of hexaphenylcyclotrisilazane into the product obtained in the second step, stirring for 1 hour under the condition of keeping the temperature at 150 ℃, and cooling to obtain the heat-resistant silicone rubber compound.
Step four: and (3) adding 1.5 parts of vulcanizing agent into the product obtained in the third step according to the parts by weight, wherein the conditions of primary vulcanization are 135 ℃ and 8min, and the conditions of secondary vulcanization are 180 ℃ and 4.5h, so as to obtain the high-temperature-resistant silicon rubber material. The raw material formulation of the silicone rubber material is shown in table 1.
Example 3
The procedure of example 1 was repeated with the component contents specified in table 1 below, and the test results before and after aging are shown in tables 2 to 4.
The method comprises the following steps: the nano yttrium oxide is treated by the following method
(S1) putting the nano yttrium oxide into absolute ethyl alcohol for ultrasonic treatment for 20 min;
(S2) adding absolute ethyl alcohol diluted oleic acid (the volume ratio of the oleic acid to the absolute ethyl alcohol is 1:1) into the nano yttrium oxide treated in the step S1, and then carrying out ultrasonic treatment for 30 min;
(S3) stirring for a period of time at a certain temperature (specifically stirring for 1h at 60 ℃), then cooling and standing to room temperature, washing and centrifugally separating the mixture, and drying for 3h at 100 ℃ to obtain the processed nano yttrium oxide.
Step two: according to the weight portion, 125 portions of methyl vinyl raw rubber, 42 portions of white carbon black, 6 portions of hydroxyl silicone oil, 0.2 portion of phenyl silicone oil and 0.2 portion of zinc stearate are weighed and mixed under the condition of 25 ℃.
Step three: and (3) adding 7 parts by weight of nano zirconium hydroxide, 1.5 parts by weight of nano yttrium oxide and 0.5 part by weight of hexaphenylcyclotrisilazane into the product obtained in the second step, stirring for 0.8h under the condition of keeping the temperature at 145 ℃, and cooling to obtain the heat-resistant silicone rubber compound.
Step four: and (3) adding 1.5 parts of vulcanizing agent into the product obtained in the third step according to the parts by weight, wherein the conditions of primary vulcanization are 140 ℃ and 12min, and the conditions of secondary vulcanization are 210 ℃ and 3.5h, so as to obtain the high-temperature-resistant silicon rubber material. The raw material formulation of the silicone rubber material is shown in table 1.
Example 4
The procedure of example 1 was repeated with the component contents specified in table 1 below, and the test results before and after aging are shown in tables 2 to 4.
The method comprises the following steps: the nano yttrium oxide is treated by the following method
(S1) putting the nano yttrium oxide into absolute ethyl alcohol for ultrasonic treatment for 20 min;
(S2) adding absolute ethyl alcohol diluted oleic acid (the volume ratio of the oleic acid to the absolute ethyl alcohol is 1:1) into the nano yttrium oxide treated in the step S1, and then carrying out ultrasonic treatment for 30 min;
(S3) stirring for a period of time at a certain temperature (specifically stirring for 1h at 60 ℃), then cooling and standing to room temperature, washing and centrifugally separating the mixture, and drying for 3h at 100 ℃ to obtain the processed nano yttrium oxide.
Step two: according to the parts by weight, 120 parts of methyl vinyl raw rubber, 39 parts of white carbon black, 5.5 parts of hydroxyl silicone oil, 0.2 part of phenyl silicone oil and 0.3 part of zinc stearate are weighed and mixed and stirred at the temperature of 25 ℃.
Step three: and (3) adding 7 parts by weight of nano zirconium hydroxide, 1.3 parts by weight of nano yttrium oxide and 0.4 part by weight of hexaphenylcyclotrisilazane into the product obtained in the second step, stirring for 0.8h under the condition of keeping at 155 ℃, and cooling to obtain the heat-resistant silicone rubber compound.
Step four: and adding 1.6 parts of vulcanizing agent into the finished product obtained in the third step according to the parts by weight, wherein the conditions of primary vulcanization are 140 ℃ and 11min, and the conditions of secondary vulcanization are 190 ℃ and 4.5h, so as to obtain the high-temperature-resistant silicon rubber material. The raw material formulation of the silicone rubber material is shown in table 1.
Example 5
The procedure of example 1 was repeated with the component contents specified in table 1 below, and the test results before and after aging are shown in tables 2 to 4.
The method comprises the following steps: the nano yttrium oxide is treated by the following method
(S1) putting the nano yttrium oxide into absolute ethyl alcohol for ultrasonic treatment for 20 min;
(S2) adding absolute ethyl alcohol diluted oleic acid (the volume ratio of the oleic acid to the absolute ethyl alcohol is 1.5:1) into the nano yttrium oxide treated in the step S1, and then carrying out ultrasonic treatment for 30 min;
(S3) stirring for a period of time at a certain temperature (specifically stirring for 1.5h at 55 ℃), then cooling and standing to room temperature, washing and centrifugally separating the mixture, and drying for 3h at 100 ℃ to obtain the processed nano yttrium oxide.
Step two: according to the weight portion, under the condition of 25 ℃, 125 portions of methyl vinyl raw rubber, 41 portions of white carbon black, 4 portions of hydroxyl silicone oil, 0.3 portion of phenyl silicone oil and 0.2 portion of zinc stearate are weighed, mixed and stirred.
Step three: and (3) adding 5 parts of nano zirconium hydroxide, 2.0 parts of nano yttrium oxide and 0.6 part of hexaphenylcyclotrisilazane into the product obtained in the second step, stirring for 1h under the condition of keeping the temperature at 150 ℃, and cooling to obtain the heat-resistant silicone rubber compound.
Step four: and (3) adding 1.3 parts of vulcanizing agent into the product obtained in the third step according to the parts by weight, wherein the conditions of primary vulcanization are 150 ℃ and 8min, and the conditions of secondary vulcanization are 220 ℃ and 3.5h, so as to obtain the high-temperature-resistant silicon rubber material. The raw material formulation of the silicone rubber material is shown in table 1.
Example 6
This example is a modification of example 5, and is different from example 5 mainly in that the nano yttrium oxide is used without being subjected to the processes of steps (S1), (S2) and (S3).
Comparative example 1
This comparative example is a comparative example to example 5, the difference with respect to example 5 being mainly: nano yttrium oxide and hexaphenylcyclotrisilazane were not added. The procedure of example 5 was repeated with the component contents specified in Table 1 below, and the test results before and after aging are shown in tables 2 to 4.
Comparative example 2
This comparative example is a comparative example to example 5, the difference with respect to example 5 being mainly: the nanometer zirconium hydroxide and the nanometer yttrium oxide are not added. The procedure of example 5 was repeated with the component contents specified in Table 1 below, and the test results before and after aging are shown in tables 2 to 4.
Comparative example 3
This comparative example is a comparative example to example 5, the difference with respect to example 5 being mainly: nano zirconium hydroxide and hexaphenylcyclotrisilazane were not added. The procedure of example 5 was repeated with the component contents specified in Table 1 below, and the test results before and after aging are shown in tables 2 to 4.
Feed compositions for Table 1, examples 1-6 and comparative examples 1-3
Performance testing
The silica gel sheets prepared from the samples of examples 1 to 6 and comparative examples 1 to 3 were baked at 300 ℃ for 48 hours, respectively, and mechanical properties before and after aging were evaluated.
Evaluation index and test method:
hardness: GB/T531.1-2008
Tensile strength: GB/T528-
Elongation percentage: GB/T528-
Mass loss rate: weighing, placing in a muffle furnace at 330 ℃ for 24h at constant temperature, taking out the aged mass, and calculating the mass loss rate.
Initial decomposition temperature: the test was carried out using a thermogravimetric analyzer type TGA 4000 of PerkinElmer, USA.
Examples 1-6 the results of the performance tests of comparative examples 1-3 are shown in tables 2-4 below.
Table 2, results of initial mechanical property test of silicone rubber materials of examples and comparative examples
Table 3, test results of aging of silicone rubber materials of examples and comparative examples at 300 ℃ for 48h
| Content of test | Hardness (Shao A) | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 1 | 62 | 7.04 | 786.2 |
| Example 2 | 57 | 7.34 | 795.3 |
| Example 3 | 60 | 7.11 | 761.5 |
| Example 4 | 61 | 7.04 | 726.5 |
| Example 5 | 60 | 6.98 | 736.4 |
| Example 6 | 64 | 5.45 | 574.2 |
| Comparative example 1 | 67 | 4.62 | 392.5 |
| Comparative example 2 | 68 | 4.71 | 278.2 |
| Comparative example 3 | 78 | 4.01 | 395.5 |
Table 4, examples and comparative examples 330 ℃ aging 24h performance test results
As can be seen from tables 2-4: the performances of the silica gel sheets prepared by the samples of examples 1 to 6 of the invention are superior to those of the silica gel sheets prepared by the samples of comparative examples 1 to 3, which shows that the matching of the nano zirconium hydroxide, the hexaphenylcyclotrisilazane and the nano yttrium oxide is adopted by the invention, and the improvement of the performances of the silica gel sheets is very important. In the examples, the performance of the silica gel sheets prepared from the samples of examples 1 to 5 is better than that of example 6, which shows that the specific treatment of the nano yttrium oxide in the heat-resistant additive of the invention can further improve the performance of the silica gel sheets. In examples 1-5, the silicone sheet prepared from the sample of example 2 has the best performance, which indicates that there are preferred embodiments for the heat resistant additive and silicone rubber material of the present invention.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. The heat-resistant additive is characterized by comprising 1-10 parts by weight of zirconium hydroxide, 1-5 parts by weight of yttrium oxide and 0.1-0.9 part by weight of hexaphenylcyclotrisilazane.
2. The heat resistant additive according to claim 1, wherein the heat resistant additive comprises 5.5-6.5 parts of zirconium hydroxide, 2.5-3.5 parts of yttrium oxide, and 0.35-0.45 part of hexaphenylcyclotrisilazane.
3. A heat resistant additive according to claim 1 or 2, wherein the yttria is treated by:
s1, putting the yttrium oxide into absolute ethyl alcohol for ultrasonic treatment;
s2, adding the yttrium oxide treated in the step S1 into oleic acid diluted by absolute ethyl alcohol, performing ultrasonic treatment, heating and stirring, cooling and standing, washing, centrifuging and drying.
4. The heat-resistant additive according to claim 3, wherein in step S2, the volume ratio of the oleic acid to the absolute ethyl alcohol is (0.5-1.5): 1.
5. the heat-resistant additive according to claim 3, wherein in step S2, the heating temperature is 55-65 ℃, and the heating time is 0.5-1.5 h; or/and the drying temperature is 80-110 ℃, and the drying time is 2.5-3.5 h.
6. A heat resistant additive according to claim 1, 2, 4 or 5 wherein the particle size of the zirconium hydroxide is between 50-100 nm; or/and the yttrium oxide has the grain diameter of 30-50nm and the specific surface area of more than 50m2/g。
7. Use of the heat resistant additive of any one of claims 1 to 6 in the preparation of a silicone rubber material.
8. The silicon rubber material is characterized in that the preparation raw material of the silicon rubber material comprises the following components in parts by mass: 100-130 parts of methyl vinyl crude rubber, 30-60 parts of white carbon black, 3-10 parts of hydroxyl silicone oil, 0.1-3 parts of vulcanizing agent, 0-0.3 part of phenyl silicone oil, 0-0.3 part of zinc stearate and the heat-resistant additive disclosed in any one of claims 1 to 6.
9. The silicone rubber material of claim 8, wherein the raw materials for preparing the silicone rubber material comprise the following components in parts by mass: 122 portions of methyl vinyl crude rubber 118-122 portions, 39-41 portions of white carbon black, 4.5-5.5 portions of hydroxyl silicone oil, 1-2.5 portions of vulcanizing agent, 0-0.3 portion of phenyl silicone oil, 0-0.3 portion of zinc stearate and the heat-resistant additive.
10. The silicone rubber material according to claim 8 or 9, wherein the molar content of vinyl groups in the methyl vinyl raw rubber is 0.15-0.35%; or/and the white carbon black is fumed silica with the specific surface area of more than or equal to 100m2(ii)/g; or/and the vulcanizing agent is 2, 4-dichlorobenzoyl peroxide.
11. A method for preparing the silicone rubber material according to any one of claims 8 to 10, comprising the steps of:
firstly, mixing the methyl vinyl raw rubber, the white carbon black, the hydroxyl silicone oil, the phenyl silicone oil and the zinc stearate;
secondly, adding the zirconium hydroxide, yttrium oxide and hexaphenylcyclotrisilazane into the product obtained in the first step, and mixing;
and thirdly, adding the vulcanizing agent into the product obtained in the second step, and vulcanizing.
12. The method for producing a silicone rubber material according to claim 11, wherein the vulcanization includes a primary vulcanization and a secondary vulcanization: the conditions adopted by the primary vulcanization are 130-150 ℃ and 8-12 min; or/and the secondary vulcanization adopts the conditions of 180-220 ℃ and 3.5-4.5 h.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209789A (en) * | 1996-11-18 | 1999-03-03 | 康涅狄格州立大学 | Nanostructured oxides and hydroxides and methods for their synthesis |
| CN102174220A (en) * | 2011-01-06 | 2011-09-07 | 包头稀土研究院 | Application of rare earth hydroxide as flame-retardant synergist in high molecular materials |
| CN106751889A (en) * | 2016-12-02 | 2017-05-31 | 东爵有机硅(南京)有限公司 | A kind of high temperature resistance and high strength rubber composition and preparation method thereof |
| JP2017179210A (en) * | 2016-03-31 | 2017-10-05 | ニチアス株式会社 | Fluorine elastomer composition, molded article, sealant, and plasma treatment device and semiconductor manufacturing device containing sealant |
| CN109535595A (en) * | 2018-11-22 | 2019-03-29 | 慈溪赛洁日用品有限公司 | A kind of multi-functional PVC foam cushion and preparation method thereof |
| CN109867965A (en) * | 2019-03-26 | 2019-06-11 | 华东理工大学 | A kind of high-temperature-resisting silicon rubber material and the preparation method and application thereof |
| CN110330795A (en) * | 2019-05-31 | 2019-10-15 | 东莞市天桉硅胶科技有限公司 | A kind of high-temperature-resisting silicon rubber and preparation method thereof |
-
2019
- 2019-12-23 CN CN201911338005.4A patent/CN111073057B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209789A (en) * | 1996-11-18 | 1999-03-03 | 康涅狄格州立大学 | Nanostructured oxides and hydroxides and methods for their synthesis |
| CN102174220A (en) * | 2011-01-06 | 2011-09-07 | 包头稀土研究院 | Application of rare earth hydroxide as flame-retardant synergist in high molecular materials |
| JP2017179210A (en) * | 2016-03-31 | 2017-10-05 | ニチアス株式会社 | Fluorine elastomer composition, molded article, sealant, and plasma treatment device and semiconductor manufacturing device containing sealant |
| CN106751889A (en) * | 2016-12-02 | 2017-05-31 | 东爵有机硅(南京)有限公司 | A kind of high temperature resistance and high strength rubber composition and preparation method thereof |
| CN109535595A (en) * | 2018-11-22 | 2019-03-29 | 慈溪赛洁日用品有限公司 | A kind of multi-functional PVC foam cushion and preparation method thereof |
| CN109867965A (en) * | 2019-03-26 | 2019-06-11 | 华东理工大学 | A kind of high-temperature-resisting silicon rubber material and the preparation method and application thereof |
| CN110330795A (en) * | 2019-05-31 | 2019-10-15 | 东莞市天桉硅胶科技有限公司 | A kind of high-temperature-resisting silicon rubber and preparation method thereof |
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