CN117924945A - Silicon rubber for cable accessories and preparation method thereof - Google Patents
Silicon rubber for cable accessories and preparation method thereof Download PDFInfo
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- CN117924945A CN117924945A CN202410111410.7A CN202410111410A CN117924945A CN 117924945 A CN117924945 A CN 117924945A CN 202410111410 A CN202410111410 A CN 202410111410A CN 117924945 A CN117924945 A CN 117924945A
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000004945 silicone rubber Substances 0.000 claims abstract description 87
- 239000000463 material Substances 0.000 claims abstract description 62
- 229920002545 silicone oil Polymers 0.000 claims abstract description 55
- 239000006185 dispersion Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 239000005060 rubber Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 238000004898 kneading Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 16
- 229910052726 zirconium Inorganic materials 0.000 description 16
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 15
- 229910021485 fumed silica Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 6
- -1 polysiloxane Polymers 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 241000276425 Xiphophorus maculatus Species 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010303 mechanochemical reaction Methods 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 238000012805 post-processing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a silicone rubber for a cable accessory and a preparation method thereof, wherein the silicone rubber for the cable accessory comprises, by weight, 100 parts of raw rubber, 30-40 parts of white carbon black, 3-8 parts of first silicone oil, 0.1-20 parts of dispersing materials, 0.1-0.5 part of release agent and 0.8-1.3 parts of vulcanizing agent, wherein the dispersing materials are prepared by mixing second silicone oil and modified two-dimensional nano titanium dioxide and then performing high-temperature ball milling treatment, and the modified two-dimensional nano titanium dioxide is prepared by reacting two-dimensional nano titanium dioxide with a silane coupling agent. The dispersion material is prepared by mixing the second silicone oil and the modified two-dimensional nano titanium dioxide and then performing high-temperature ball milling treatment, the dispersion material has better dispersibility in the silicone rubber so as not to influence the mechanical properties of the silicone rubber, and the flaky nano titanium dioxide with good dispersion state forms a tortuous path in the silicone rubber so as to effectively prevent electric branch expansion and improve the electrical properties, so that the silicone rubber for the cable accessories can take both the electrical properties and the mechanical properties into consideration.
Description
Technical Field
The invention belongs to the technical field of power insulating materials, and particularly relates to silicone rubber for a cable accessory and a preparation method thereof.
Background
With the development of the electric power industry scale and the diversification of power generation and power transmission modes, urban power utilization, submarine power transmission and resource environment protection are required, and various cables are increasingly applied. Compared with the traditional insulating material, the silicon rubber has the characteristics of organic and inorganic materials and has good hydrophobicity, weather resistance, insulativity and the like, so that the silicon rubber becomes the most ideal insulating material for the high-voltage cable accessories at present. However, the cable accessory is inevitably affected by the combined action of various factors such as moisture, salt fog, oxidation, thermal stress, mechanical stress and the like in the long-term use process, so that higher requirements are placed on the electrical performance and mechanical performance of the silicone rubber for the cable accessory.
At present, sufficient filler auxiliary agent is often added to improve the electrical performance of the silicone rubber for the cable accessories, however, the compatibility of the filler auxiliary agent and the silicone rubber is poor, so that the sufficient filler auxiliary agent also easily reduces the processability and mechanical properties of the rubber material, influences the post-processing and the service life of the cable accessories, and has relatively high cost, and the electrical performance and the mechanical performance of the silicone rubber for the cable accessories cannot be simultaneously achieved.
Therefore, there is a need for a silicone rubber for cable accessories and a preparation method thereof to solve the shortcomings of the prior art.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a silicone rubber for a cable accessory that can achieve both electrical properties and mechanical properties, and a method for producing the same.
In order to achieve the above purpose, the first aspect of the invention provides a silicone rubber for cable accessories, which comprises, by weight, 100 parts of raw rubber, 30-40 parts of white carbon black, 3-8 parts of first silicone oil, 0.1-20 parts of dispersing materials, 0.1-0.5 part of release agent and 0.8-1.3 parts of vulcanizing agent, wherein the dispersing materials are prepared by mixing second silicone oil and modified two-dimensional nano titanium dioxide and then performing high-temperature ball milling treatment, and the modified two-dimensional nano titanium dioxide is prepared by reacting two-dimensional nano titanium dioxide with a silane coupling agent.
Compared with the prior art, the modified two-dimensional nano titanium dioxide is formed by reacting the two-dimensional nano titanium dioxide with the silane coupling agent, so that the wettability of the modified two-dimensional nano titanium dioxide and the second silicone oil can be effectively increased, the modified two-dimensional nano titanium dioxide and the second silicone oil can be better subjected to high-temperature ball milling treatment after being mixed, in the high-temperature ball milling treatment, the modified two-dimensional nano titanium dioxide and the second silicone oil can undergo mechanochemical reaction to graft polysiloxane on the two-dimensional nano titanium dioxide, and because the two-dimensional nano titanium dioxide is in a sheet-shaped structure, the special geometric structure can enable the polysiloxane to be more uniformly grafted on the surface of the two-dimensional nano titanium dioxide material, so that the polysiloxane has better compatibility with the silicone rubber, namely the dispersed material has better dispersibility in the silicone rubber, so that the mechanical property of the silicone rubber is not influenced, and the sheet-shaped nano titanium dioxide with a good dispersion state can form a tortuous path in the silicone rubber, so that the electric branch expansion can be effectively prevented to improve the electrical property; therefore, the silicone rubber for the cable accessory can be used for combining electrical performance and mechanical performance.
Further, the first silicone oil of the present invention includes a hydroxyl silicone oil, and the second silicone oil includes at least one of a vinyl silicone oil and a methyl silicone oil.
Further, the mass percentage of the modified two-dimensional nano titanium dioxide in the dispersion material is 20-60%.
Further, the silane coupling agent of the present invention is at least one of gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and hexadecyl triethoxysilane.
Further, the release agent of the present invention includes at least one of calcium stearate, zinc stearate, and magnesium stearate.
Further, the preparation of the two-dimensional nano titanium dioxide of the invention comprises the following steps: under the protection of nitrogen, adding titanium tetrachloride into ethylene glycol, heating to reflux, and adding water for reaction to obtain the two-dimensional nano titanium dioxide. Specifically, the volume ratio of the glycol to the titanium tetrachloride is 5-100:1, the volume ratio of the titanium tetrachloride to the water is 1-4:1, and the time for adding water for reflux reaction is 0.5-4 h.
Further, the preparation of the modified two-dimensional nano titanium dioxide of the invention comprises the following steps: adding two-dimensional nano titanium dioxide into a mixed solution of ethanol and water, adjusting the pH of the system, adding a silane coupling agent, and heating to reflux for reaction to obtain the modified two-dimensional nano titanium dioxide. Specifically, the dosage of the two-dimensional nano titanium dioxide is 10-15% of the mass of a mixed solution consisting of ethanol and water, the volume ratio of the ethanol to the water is 5-10:1, the PH of the system is regulated to 3-5 by adopting hydrochloric acid, the dosage of the silane coupling agent is 0.1-5% of the mass of the two-dimensional nano titanium dioxide, and the reaction is carried out for 1-4 hours after the heating to reflux. Specifically, the two-dimensional nano titanium dioxide can be uniformly dispersed in the mixed solution of ethanol and water through ultrasonic treatment and electromagnetic stirring. More specifically, the organic group in the silane coupling agent reacts with the hydroxyl group on the surface of the two-dimensional nano titanium dioxide to firmly bond the silane coupling agent with the two-dimensional nano titanium dioxide, which can improve the compatibility and dispersion stability of the two-dimensional nano titanium dioxide in the polymer material.
Further, the preparation of the dispersion material of the present invention comprises: uniformly mixing the second silicone oil and the modified two-dimensional nano titanium dioxide to obtain a paste, placing the paste into a planetary ball mill, adding grinding balls, starting the planetary ball mill until the temperature in the planetary ball mill reaches 165-185 ℃ and the pressure reaches 0.45-0.75 MPa, starting timing, and closing the planetary ball mill after 12-24 hours to obtain the dispersed material. Specifically, the mass ratio of the grinding ball to the paste is 5-7:2; specifically, the grinding ball consists of zirconium balls with three particle sizes of phi 15mm, phi 10mm and phi 5mm, wherein the mass ratio of phi 15mm, phi 10mm and phi 5mm is 45-55:25-35:15-25. Preferably, ball milling is carried out at 180℃and 0.6MPa for 18h.
Further, the raw rubber is 110 methyl vinyl silicone rubber, the molecular weight is 55-65 ten thousand, and the vinyl molar content is 0.03-1.0%.
Further, the white carbon black of the invention is a gas phase white carbon black with a specific surface area of 150-450 m 2/g.
Further, the kinematic viscosity of the hydroxyl silicone oil is 30-40 cst, and the hydroxyl content is 5-10%.
Further, the vulcanizing agent of the present invention includes 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
In order to achieve the above object, a second aspect of the present invention provides a method for preparing silicone rubber for a cable accessory, comprising the steps of:
(1) Adding raw rubber, white carbon black, first silicone oil and a release agent with the formula amount into an internal mixer for kneading and agglomerating;
(2) Adding a formula amount of dispersion materials into the mixture after the step (1), kneading the mixture, performing vacuum heat treatment after the mixture is agglomerated, and discharging the mixture for open mill;
(3) And (3) adding a formula amount of vulcanizing agent to carry out vulcanization treatment after the step (2) to obtain the silicone rubber for the cable accessories.
Compared with the prior art, the polysiloxane in the dispersion material is grafted on the surface of the two-dimensional nano titanium dioxide material more uniformly, so that the dispersion material, raw rubber, white carbon black, first silicone oil, the dispersion material and a release agent can be better dispersed after being mixed, the influence on the processability of the sizing material is small, the later processing and forming are facilitated, the mechanical property of the silicone rubber is not influenced, and the flaky nano titanium dioxide with good dispersion state forms a tortuous path in the silicone rubber, so that the expansion of an electric branch can be effectively prevented to improve the electrical property, and the silicone rubber for the cable accessories, which is prepared by the preparation method, can be compatible with the electrical property and the mechanical property.
Further, the vulcanization treatment of the invention comprises vulcanization for 3-5 min at 160-180 ℃.
Further, the temperature of the vacuum heat treatment is 150-170 ℃, the vacuum degree is 0.07-0.1 MPa, and the time is 180-240 min.
Detailed Description
For a better description of the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention.
Specifically, the planetary ball mill used in examples and comparative examples was of the type QM-1SP04 manufactured by Nanjing university mechanical factory.
The preparation of two-dimensional nano titania used in examples and comparative examples can be obtained by referring to the following methods:
And (3) taking 3L of ethylene glycol, slowly dropwise adding 200mL of titanium tetrachloride into the ethylene glycol under the protection of nitrogen, heating until the mixture flows back, slowly dropwise adding 200mL of deionized water into the mixture, flowing back for 3 hours, centrifuging, drying and grinding the product after the reaction is finished, and thus obtaining the two-dimensional nano titanium dioxide with the size of 213nm x 213nm.
Example 1
The embodiment provides a silicone rubber for cable accessories, which comprises, by weight, 100 parts of 110 methyl vinyl silicone rubber (with a molecular weight of 60 ten thousand and a vinyl molar content of 0.08%), 35 parts of fumed silica with a specific surface area of 200m 2/g, 4 parts of hydroxyl silicone oil (with a hydroxyl content of 8%, a kinematic viscosity of 30 cst), 3 parts of dispersed materials, 0.1 part of zinc stearate and 1 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, wherein the dispersed materials are prepared by mixing vinyl silicone oil and modified two-dimensional nano titanium dioxide and then performing high-temperature ball milling treatment, and the modified two-dimensional nano titanium dioxide is prepared by reacting two-dimensional nano titanium dioxide with gamma-aminopropyl triethoxysilane;
wherein the preparation of the dispersion material comprises the following steps: uniformly mixing 100g of vinyl silicone oil with viscosity of 10000 mPas with 100g of modified two-dimensional nano titanium dioxide to obtain a paste, placing the paste in a planetary ball mill, adding grinding balls (consisting of phi 15mm zirconium balls, phi 10mm zirconium balls and phi 5mm zirconium balls with the mass ratio of 50:30:20), starting the planetary ball mill until the temperature in the planetary ball mill reaches 180 ℃ and the pressure reaches 0.6MPa, closing the planetary ball mill after 18h, naturally cooling to normal temperature, filtering out the grinding balls to obtain a dispersion material, and enabling the mass percentage of the modified two-dimensional nano titanium dioxide in the dispersion material to be 50%;
The preparation of the modified two-dimensional nano titanium dioxide comprises the following steps: uniformly dispersing 10g of two-dimensional nano titanium dioxide with the size of 213nm and 213nm in 100g of mixed solution consisting of ethanol and water with the volume ratio of 5:1, regulating the pH value of the system to 3 by using hydrochloric acid, slowly dropwise adding 0.01g of gamma-aminopropyl triethoxysilane into the mixed solution, heating the mixed solution until reflux and reacting for 3 hours to obtain the modified two-dimensional nano titanium dioxide.
The embodiment provides a preparation method of silicone rubber for cable accessories, which comprises the following steps:
(1) 110 methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and zinc stearate are put into an internal mixer to be kneaded into a group;
(2) Adding the dispersion material into the mixture and kneading the mixture for 20min after the step (1), slowly heating the mixture to 150 ℃ after kneading the mixture into a mass, vacuumizing the mixture, carrying out vacuum heat treatment for 180min at 150 ℃ under the condition of 0.07MPa, and discharging the mixture for open mill;
(3) And (3) adding 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane after the step (2), and vulcanizing at 175 ℃ for 5min to obtain the silicone rubber for the cable accessories.
Example 2
The embodiment provides a silicone rubber for cable accessories, which comprises, by weight, 100 parts of 110 methyl vinyl silicone rubber (with a molecular weight of 60 ten thousand and a vinyl molar content of 0.08%), 35 parts of fumed silica with a specific surface area of 200m 2/g, 4 parts of hydroxyl silicone oil (with a hydroxyl content of 8%, a kinematic viscosity of 30 cst), 5 parts of dispersed materials, 0.1 part of zinc stearate and 1 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, wherein the dispersed materials are prepared by mixing vinyl silicone oil and modified two-dimensional nano titanium dioxide and then performing high-temperature ball milling treatment, and the modified two-dimensional nano titanium dioxide is prepared by reacting two-dimensional nano titanium dioxide with gamma-aminopropyl triethoxysilane;
wherein the preparation of the dispersion material comprises the following steps: uniformly mixing 100g of vinyl silicone oil with viscosity of 10000 mPas with 100g of modified two-dimensional nano titanium dioxide to obtain a paste, placing the paste in a planetary ball mill, adding grinding balls (consisting of phi 15mm zirconium balls, phi 10mm zirconium balls and phi 5mm zirconium balls with the mass ratio of 50:30:20), starting the planetary ball mill until the temperature in the planetary ball mill reaches 180 ℃ and the pressure reaches 0.6MPa, closing the planetary ball mill after 18h, naturally cooling to normal temperature, filtering out the grinding balls to obtain a dispersion material, and enabling the mass percentage of the modified two-dimensional nano titanium dioxide in the dispersion material to be 50%;
The preparation of the modified two-dimensional nano titanium dioxide comprises the following steps: uniformly dispersing 10g of two-dimensional nano titanium dioxide with the size of 213nm and 213nm in 100g of mixed solution consisting of ethanol and water with the volume ratio of 5:1, regulating the pH value of the system to 3 by using hydrochloric acid, slowly dropwise adding 0.01g of gamma-aminopropyl triethoxysilane into the mixed solution, heating the mixed solution until reflux and reacting for 3 hours to obtain the modified two-dimensional nano titanium dioxide.
The embodiment provides a preparation method of silicone rubber for cable accessories, which comprises the following steps:
(1) 110 methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and zinc stearate are put into an internal mixer to be kneaded into a group;
(2) Adding the dispersion material into the mixture and kneading the mixture for 20min after the step (1), slowly heating the mixture to 150 ℃ after kneading the mixture into a mass, vacuumizing the mixture, carrying out vacuum heat treatment for 180min at 150 ℃ under the condition of 0.07MPa, and discharging the mixture for open mill;
(3) And (3) adding 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane after the step (2), and vulcanizing at 175 ℃ for 5min to obtain the silicone rubber for the cable accessories.
Example 3
The embodiment provides a silicone rubber for cable accessories, which comprises, by weight, 100 parts of 110 methyl vinyl silicone rubber (with a molecular weight of 60 ten thousand and a vinyl molar content of 0.08%), 40 parts of fumed silica with a specific surface area of 200m 2/g, 8 parts of hydroxyl silicone oil (with a hydroxyl content of 8%, a kinematic viscosity of 30 cst), 10 parts of dispersed materials, 0.3 part of zinc stearate and 0.96 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, wherein the dispersed materials are prepared by mixing vinyl silicone oil and modified two-dimensional nano titanium dioxide and performing high-temperature ball milling treatment, and the modified two-dimensional nano titanium dioxide is prepared by reacting two-dimensional nano titanium dioxide with hexadecyl triethoxysilane;
Wherein the preparation of the dispersion material comprises the following steps: uniformly mixing 100g of vinyl silicone oil with viscosity of 10000 mPas with 67g of modified two-dimensional nano titanium dioxide to obtain a paste, placing the paste in a planetary ball mill, adding grinding balls (consisting of phi 15mm zirconium balls, phi 10mm zirconium balls and phi 5mm zirconium balls with mass ratio of 45:30:25), starting the planetary ball mill until the mass ratio of the paste to the grinding balls is 2:6, starting timing when the temperature in the planetary ball mill reaches 175 ℃ and the pressure reaches 0.7MPa, closing the planetary ball mill after 20h, naturally cooling to normal temperature, filtering out the grinding balls to obtain a dispersion material, and obtaining the modified two-dimensional nano titanium dioxide with mass ratio of 40.1% in the dispersion material;
The preparation of the modified two-dimensional nano titanium dioxide comprises the following steps: uniformly dispersing 10g of two-dimensional nano titanium dioxide with the size of 213nm and 213nm in 100g of mixed solution consisting of ethanol and water with the volume ratio of 6:1, regulating the pH value of the system to 4 by using hydrochloric acid, slowly dropwise adding 0.01g of hexadecyltriethoxysilane into the mixed solution, heating the mixture until reflux and reacting for 4 hours to obtain the modified two-dimensional nano titanium dioxide.
The embodiment provides a preparation method of silicone rubber for cable accessories, which comprises the following steps:
(1) 110 methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and zinc stearate are put into an internal mixer to be kneaded into a group;
(2) Adding the dispersion material into the mixture and kneading the mixture for 30min after the step (1), slowly heating the mixture to 160 ℃ after kneading the mixture into a mass, vacuumizing the mixture, performing vacuum heat treatment for 200min at 160 ℃ under the condition of 0.07MPa, and discharging the mixture for open mill;
(3) And (3) adding 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane after the step (2), and vulcanizing at 172 ℃ for 5min to obtain the silicone rubber for the cable accessories.
Example 4
The embodiment provides a silicone rubber for cable accessories, which comprises, by weight, 100 parts of 110 methyl vinyl silicone rubber (with a molecular weight of 55 ten thousand and a vinyl molar content of 0.08%), 30 parts of fumed silica with a specific surface area of 200m 2/g, 3 parts of hydroxyl silicone oil (with a hydroxyl content of 10%, a kinematic viscosity of 40 cst), 5 parts of dispersed materials, 0.1 part of magnesium stearate and 0.92 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, wherein the dispersed materials are prepared by mixing vinyl silicone oil and modified two-dimensional nano titanium dioxide through high-temperature ball milling treatment, and the modified two-dimensional nano titanium dioxide is prepared by reacting two-dimensional nano titanium dioxide with gamma-aminopropyl triethoxysilane;
Wherein the preparation of the dispersion material comprises the following steps: uniformly mixing 100g of vinyl silicone oil with viscosity of 10000 mPas with 42.9g of modified two-dimensional nano titanium dioxide to obtain a paste, placing the paste in a planetary ball mill, adding grinding balls (consisting of phi 15mm zirconium balls, phi 10mm zirconium balls and phi 5mm zirconium balls with mass ratio of 50:30:20), starting the planetary ball mill until the temperature in the planetary ball mill reaches 182 ℃ and the pressure reaches 0.5MPa, starting timing, closing the planetary ball mill after 15h, naturally cooling to normal temperature, filtering out the grinding balls to obtain a dispersion material, and obtaining 30% of modified two-dimensional nano titanium dioxide in the dispersion material;
the preparation of the modified two-dimensional nano titanium dioxide comprises the following steps: uniformly dispersing 10g of two-dimensional nano titanium dioxide with the size of 213nm and 213nm in 100g of mixed solution consisting of ethanol and water with the volume ratio of 8:1, regulating the pH value of the system to 3 by using hydrochloric acid, slowly dropwise adding 0.01g of gamma-aminopropyl triethoxysilane into the mixed solution, heating the mixed solution until reflux and reacting for 2.5 hours to obtain the modified two-dimensional nano titanium dioxide.
The embodiment provides a preparation method of silicone rubber for cable accessories, which comprises the following steps:
(1) 110 methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and magnesium stearate are put into an internal mixer to be kneaded into a group;
(2) Adding the dispersion material into the mixture and kneading the mixture for 20min after the step (1), slowly heating the mixture to 168 ℃ after kneading the mixture into a mass, vacuumizing the mixture, carrying out vacuum heat treatment for 220min at the temperature of 168 ℃ under the pressure of 0.07MPa, and discharging the mixture for open mill;
(3) And (3) adding 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane after the step (2), and vulcanizing at 170 ℃ for 5min to obtain the silicone rubber for the cable accessories.
Comparative example 1
The comparative example provides a silicone rubber for cable accessories, which comprises, by weight, 100 parts of 110 methyl vinyl silicone rubber (with a molecular weight of 60 ten thousand and a vinyl molar content of 0.08%), 35 parts of fumed silica with a specific surface area of 200m 2/g, 4 parts of hydroxyl silicone oil (with a hydroxyl content of 8% and a kinematic viscosity of 30 cst), 0.1 part of zinc stearate, and 1 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane;
the comparative example provides a preparation method of silicone rubber for cable accessories, which comprises the following steps:
(1) 110 methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and zinc stearate are put into an internal mixer to be kneaded into a group;
(2) Slowly heating to 150 ℃ after the step (1), vacuumizing, carrying out vacuum heat treatment for 180min at 150 ℃ and 0.07MPa, and discharging and open refining;
(3) And (3) adding 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane after the step (2), and vulcanizing at 175 ℃ for 5min to obtain the silicone rubber for the cable accessories.
Comparative example 2
The comparative example provides a silicone rubber for cable accessories, which comprises, by weight, 100 parts of 110 methyl vinyl silicone rubber (with a molecular weight of 60 ten thousand and a vinyl molar content of 0.08%), 35 parts of fumed silica with a specific surface area of 200m 2/g, 4 parts of hydroxyl silicone oil (with a hydroxyl content of 8%, a kinematic viscosity of 30 cst), 3 parts of dispersed materials, 0.1 part of zinc stearate and 1 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, wherein the dispersed materials are prepared by mixing vinyl silicone oil and modified two-dimensional nano titanium dioxide, and the modified two-dimensional nano titanium dioxide is prepared by reacting two-dimensional nano titanium dioxide with gamma-aminopropyl triethoxysilane;
Wherein the preparation of the dispersion material comprises the following steps: uniformly mixing 100g of vinyl silicone oil with viscosity of 10000 mPas with 100g of modified two-dimensional nano titanium dioxide to obtain a dispersion material, wherein the mass percentage of the modified two-dimensional nano titanium dioxide in the dispersion material is 50%;
The preparation of the modified two-dimensional nano titanium dioxide comprises the following steps: uniformly dispersing 10g of two-dimensional nano titanium dioxide with the size of 213nm and 213nm in 100g of mixed solution consisting of ethanol and water with the volume ratio of 5:1, regulating the pH value of the system to 3 by using hydrochloric acid, slowly dropwise adding 0.01g of gamma-aminopropyl triethoxysilane into the mixed solution, heating the mixed solution until reflux and reacting for 3 hours to obtain the modified two-dimensional nano titanium dioxide.
The comparative example provides a preparation method of silicone rubber for cable accessories, which comprises the following steps:
(1) 110 methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and zinc stearate are put into an internal mixer to be kneaded into a group;
(2) Adding the dispersion material into the mixture and kneading the mixture for 20min after the step (1), slowly heating the mixture to 150 ℃ after kneading the mixture into a mass, vacuumizing the mixture, carrying out vacuum heat treatment for 180min at 150 ℃ under the condition of 0.07MPa, and discharging the mixture for open mill;
(3) And (3) adding 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane after the step (2), and vulcanizing at 175 ℃ for 5min to obtain the silicone rubber for the cable accessories.
Comparative example 3
The comparative example provides a silicone rubber for cable accessories, which comprises, by weight, 100 parts of 110 methyl vinyl silicone rubber (with a molecular weight of 60 ten thousand and a vinyl molar content of 0.08%), 35 parts of fumed silica with a specific surface area of 200m 2/g, 4 parts of hydroxyl silicone oil (with a hydroxyl content of 8%, a kinematic viscosity of 30 cst), 3 parts of dispersed materials, 0.1 part of zinc stearate and 1 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, wherein the dispersed materials are prepared by mixing vinyl silicone oil and two-dimensional nano titanium dioxide and then performing high-temperature ball milling treatment;
Wherein the preparation of the dispersion material comprises the following steps: uniformly mixing 100g of vinyl silicone oil with viscosity of 10000 mPas and 100g of two-dimensional nano titanium dioxide with size of 213nm or 213nm to obtain a paste, placing the paste in a planetary ball mill, adding grinding balls (consisting of phi 15mm zirconium balls, phi 10mm zirconium balls and phi 5mm zirconium balls with mass ratio of 50:30:20), wherein the mass ratio of the paste to the grinding balls is 2:5, starting the planetary ball mill until the temperature in the planetary ball mill reaches 180 ℃ and the pressure reaches 0.6MPa, starting timing, closing the planetary ball mill after 18 hours, naturally cooling to normal temperature, filtering out the grinding balls to obtain a dispersion material, and obtaining 50 percent of the two-dimensional nano titanium dioxide in the dispersion material;
the comparative example provides a preparation method of silicone rubber for cable accessories, which comprises the following steps:
(1) 110 methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and zinc stearate are put into an internal mixer to be kneaded into a group;
(2) Adding the dispersion material into the mixture and kneading the mixture for 20min after the step (1), slowly heating the mixture to 150 ℃ after kneading the mixture into a mass, vacuumizing the mixture, carrying out vacuum heat treatment for 180min at 150 ℃ under the condition of 0.07MPa, and discharging the mixture for open mill;
(3) And (3) adding 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane after the step (2), and vulcanizing at 175 ℃ for 5min to obtain the silicone rubber for the cable accessories.
The silicone rubbers for cable accessories of examples 1 to 4 and comparative examples 1 to 3 were subjected to various performance tests according to the following test standards, and the test results are shown in table 1.
Plasticity test is referred to GB/T12828-2006; hardness testing is referred to GB/T531.1-2008; tensile strength, elongation test reference GB/T528-2009; tear strength test reference GB/T529-2008; breakdown strength test reference IEC 60243; volume resistivity tests were referenced to IEC 60093.
TABLE 1
From table 1, it can be seen that the silicone rubber for cable accessories of examples 1 to 4 can give consideration to both electrical performance and mechanical performance, which indicates that the modified two-dimensional nano titanium dioxide is formed by reacting two-dimensional nano titanium dioxide with a silane coupling agent, so that wettability of the modified two-dimensional nano titanium dioxide with the second silicone oil can be effectively increased, and thus, after the modified two-dimensional nano titanium dioxide is mixed with the second silicone oil, high-temperature ball milling treatment can be better performed, and in the high-temperature ball milling treatment, mechanochemical reaction can be performed on the modified two-dimensional nano titanium dioxide and the second silicone oil, so that polysiloxane is grafted on the two-dimensional nano titanium dioxide, and because the two-dimensional nano titanium dioxide has a sheet structure, the special geometric structure can enable polysiloxane to be grafted on the surface of the two-dimensional nano titanium dioxide material more uniformly, so that the modified two-dimensional nano titanium dioxide has better compatibility with silicone rubber, namely, the dispersion material has better dispersibility in silicone rubber, so that the mechanical performance of the silicone rubber is not affected, and the sheet-like nano titanium dioxide with good dispersion state forms a tortuous path in the silicone rubber, so that electrical branch expansion can be effectively prevented, so as to improve electrical performance.
Comparing example 1 with example 2, it is seen that the silicone rubber for cable accessories of example 2 has relatively better electrical properties, which indicates that the increase in the content of the dispersion is advantageous for further improving the electrical properties of the silicone rubber for cable accessories without causing a decrease in the mechanical properties of the silicone rubber for cable accessories.
Comparing example 1 with comparative example 1, it is known that the silicone rubber for cable accessories of example 1 has better electrical and mechanical properties, which indicates that the dispersion material has better dispersibility in the silicone rubber so as not to affect the mechanical properties of the silicone rubber, and the platy nano titanium dioxide in a well dispersed state forms a tortuous path in the silicone rubber so as to effectively prevent the electrical branch from expanding to improve the electrical properties.
Comparing example 1 with comparative example 2, it is known that the silicone rubber for cable accessories of example 1 has better electrical and mechanical properties because the high-temperature ball milling treatment can obtain the platy nano titanium dioxide in a good dispersion state, the well-dispersed platy nano titanium dioxide can form a laminated cover so as to effectively prevent the expansion of electric wires to improve the electrical properties, and meanwhile, the well-dispersed platy titanium dioxide has better dispersibility in the silicone rubber so as not to influence the mechanical properties of the silicone rubber.
Comparing example 1 with comparative example 3, it is shown that the silicone rubber for cable accessories of example 1 has better electrical performance, which indicates that the modified two-dimensional nano titanium dioxide can effectively increase wettability of the modified two-dimensional nano titanium dioxide and the second silicone oil by modifying the two-dimensional nano titanium dioxide, so that the modified two-dimensional nano titanium dioxide and the second silicone oil can be better subjected to high-temperature ball milling treatment after being mixed, and the electrical performance and mechanical performance can be improved to a certain extent by improving ball milling efficiency.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The silicone rubber for the cable accessories is characterized by comprising, by weight, 100 parts of raw rubber, 30-40 parts of white carbon black, 3-8 parts of first silicone oil, 0.1-20 parts of dispersing materials, 0.1-0.5 part of release agent and 0.8-1.3 parts of vulcanizing agent, wherein the dispersing materials are prepared by mixing second silicone oil and modified two-dimensional nano titanium dioxide and then performing high-temperature ball milling treatment, and the modified two-dimensional nano titanium dioxide is prepared by reacting two-dimensional nano titanium dioxide with a silane coupling agent.
2. The silicone rubber for cable accessories according to claim 1, wherein the first silicone oil comprises a hydroxyl silicone oil and the second silicone oil comprises at least one of a vinyl silicone oil and a methyl silicone oil.
3. The silicone rubber for cable accessories according to claim 1, wherein the mass percentage of the modified two-dimensional nano titanium dioxide in the dispersion material is 20-60%.
4. The silicone rubber for cable accessories according to claim 1, wherein the silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and hexadecyl triethoxysilane.
5. The silicone rubber for a cable accessory according to claim 1, wherein the mold release agent comprises at least one of calcium stearate, zinc stearate, and magnesium stearate.
6. The silicone rubber for cable accessories of claim 1, wherein the preparation of the two-dimensional nano-titanium dioxide comprises: and adding titanium tetrachloride into ethylene glycol under the protection of nitrogen, heating to reflux, and adding water for reaction to obtain the two-dimensional nano titanium dioxide.
7. The silicone rubber for cable accessories of claim 1, wherein the preparation of the modified two-dimensional nano-titanium dioxide comprises: and adding the two-dimensional nano titanium dioxide into a mixed solution of ethanol and water, adjusting the pH of a system, adding the silane coupling agent, and heating to reflux for reaction to obtain the modified two-dimensional nano titanium dioxide.
8. The silicone rubber for cable accessories of claim 1, wherein the preparation of the dispersion comprises: uniformly mixing the second silicone oil and the modified two-dimensional nano titanium dioxide to obtain a paste, placing the paste into a planetary ball mill, adding grinding balls, starting the planetary ball mill until the temperature in the planetary ball mill reaches 165-185 ℃ and the pressure reaches 0.45-0.75 MPa, starting timing, and closing the planetary ball mill after 12-24 hours to obtain the dispersion material.
9. A method for producing the silicone rubber for cable accessories according to any one of claims 1 to 8, characterized by comprising the steps of:
(1) Adding raw rubber, white carbon black, first silicone oil and a release agent with the formula amount into an internal mixer for kneading and agglomerating;
(2) Adding a formula amount of dispersion materials into the mixture after the step (1), kneading the mixture, performing vacuum heat treatment after the mixture is agglomerated, and discharging the mixture for open mill;
(3) And (3) adding a formula amount of vulcanizing agent to carry out vulcanization treatment after the step (2) to obtain the silicone rubber for the cable accessories.
10. The method for preparing silicone rubber for cable accessories according to claim 9, wherein the temperature of the vacuum heat treatment is 150-170 ℃, the vacuum degree is 0.07-0.1 MPa, and the time is 180-240 min.
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