CN117327352A - Insulating rubber material and preparation method and application thereof - Google Patents
Insulating rubber material and preparation method and application thereof Download PDFInfo
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- CN117327352A CN117327352A CN202311248607.7A CN202311248607A CN117327352A CN 117327352 A CN117327352 A CN 117327352A CN 202311248607 A CN202311248607 A CN 202311248607A CN 117327352 A CN117327352 A CN 117327352A
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- rubber material
- insulating rubber
- calcined kaolin
- ethylene
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 111
- 239000005060 rubber Substances 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 57
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 57
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 57
- -1 polyethylene Polymers 0.000 claims abstract description 49
- 229920001577 copolymer Polymers 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 239000004698 Polyethylene Substances 0.000 claims abstract description 41
- 229920000573 polyethylene Polymers 0.000 claims abstract description 41
- 239000001993 wax Substances 0.000 claims abstract description 41
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 40
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 239000004200 microcrystalline wax Substances 0.000 claims abstract description 24
- 235000019808 microcrystalline wax Nutrition 0.000 claims abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008117 stearic acid Substances 0.000 claims abstract description 15
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 14
- 238000012360 testing method Methods 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 239000000155 melt Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 5
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 5
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 5
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 5
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 claims description 2
- 238000010292 electrical insulation Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 16
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 14
- 230000032683 aging Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001125 extrusion Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- GFGMEONGUFFOID-UHFFFAOYSA-N 1-tert-butyl-4-(2,3,3-trimethylbutan-2-yl)benzene Chemical compound CC(C)(C)C1=CC=C(C(C)(C)C(C)(C)C)C=C1 GFGMEONGUFFOID-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention provides an insulating rubber material, and a preparation method and application thereof. The insulating rubber material comprises the following preparation raw materials in parts by mass: 50-80 parts of ethylene propylene diene monomer, 20-50 parts of ethylene octene copolymer, 5-10 parts of indirect zinc oxide, 1-2 parts of stearic acid, 30-60 parts of modified calcined kaolin, 20-30 parts of calcined kaolin, 0.2-0.5 part of coupling agent, 3-4 parts of microcrystalline wax, 6-10 parts of polyethylene wax, 10-16 parts of liquid polybutadiene, 2.5-3.5 parts of anti-aging agent, 1-2 parts of sulfur aid and 3-6 parts of vulcanizing agent. The insulating rubber material has excellent electrical insulation performance, dielectric property, breakdown strength, mechanical property and high temperature resistance.
Description
Technical Field
The invention relates to the technical field of insulating materials, in particular to an insulating rubber material and a preparation method and application thereof.
Background
Ethylene propylene rubber has excellent heat resistance, aging resistance, electrical insulation property and the like, and is widely applied to the preparation of wire and cable insulation products. For wire and cable products of different voltage classes, different types of ethylene propylene rubbers are generally selected.
In order to match the high-voltage cable with the increasingly high transmission power, the performance requirement of the cable insulation rubber material is correspondingly improved. At present, researchers usually add a certain amount of lead or lead master batch into the preparation raw materials to achieve the purpose of improving the heat resistance of the ethylene propylene rubber insulating material and the electrical stability in a humid environment, but lead ions are precipitated into the ecological environment and possibly cause harm to human health.
The high-temperature-resistant high-strength ethylene propylene rubber insulating adhesive for wires and cables in the traditional technology has low voltage resistance level and dielectric property which cannot meet the requirements of wire and cable products with high voltage level. Accordingly, there is a need for improvements in insulating rubber materials for cables.
Disclosure of Invention
Based on the above, the invention provides an environment-friendly insulating rubber material with excellent insulating property, dielectric property, mechanical property and high-temperature aging resistance. The specific technical scheme is as follows:
according to one aspect of the invention, there is provided an insulating rubber material comprising the following preparation raw materials in parts by mass:
50-80 parts of ethylene propylene diene monomer,
20-50 parts of ethylene octene copolymer,
5-10 parts of indirect zinc oxide,
1-2 parts of stearic acid,
30-60 parts of modified calcined kaolin,
20-30 parts of calcined kaolin,
0.2 to 0.5 part of coupling agent,
3-4 parts of microcrystalline wax,
6-10 parts of polyethylene wax,
10-16 parts of liquid polybutadiene,
2.5-3.5 parts of an anti-aging agent,
1-2 parts of sulfur-assisting agent
3-6 parts of vulcanizing agent.
In one embodiment, the preparation method comprises the following preparation raw materials in parts by weight:
60-80 parts of ethylene propylene diene monomer,
20-40 parts of ethylene octene copolymer,
7-10 parts of indirect zinc oxide,
4~2 portions of stearic acid,
35-50 parts of modified calcined kaolin,
20-30 parts of calcined kaolin,
0.4 to 0.5 part of coupling agent,
3.5-4 parts of microcrystalline wax,
8-10 parts of polyethylene wax,
10-15 parts of liquid polybutadiene,
3-3.5 parts of an anti-aging agent,
1.5-26 parts of sulfur-assisting agent
4-6 parts of vulcanizing agent.
In one embodiment, the insulating rubber material satisfies at least one of the following conditions (1) - (3):
(1) The ethylene structural unit content in the ethylene propylene diene monomer is 60-77 wt%;
(2) The Mooney viscosity of the ethylene propylene diene monomer is 20-50 under the testing condition of ML1+4125 ℃;
(3) The content of the third monomer structural unit in the ethylene propylene diene monomer is 4-8wt%.
In one embodiment, the insulating rubber material satisfies at least one of the following conditions (4) - (6):
(4) The melt index of the ethylene octene copolymer is 1 g/min-3 g/min under the test condition of 2.16kg and 190 ℃;
(5) The melting temperature of the ethylene octene copolymer is 60-70 ℃;
(6) The Mooney viscosity of the ethylene octene copolymer under the test condition of ML1+4121 ℃ is 10-30.
In one embodiment, the insulating rubber material satisfies at least one of the following conditions (7) - (11):
(7) The coupling agent comprises one or more of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane and aluminate coupling agent;
(8) The melting point of the microcrystalline wax is 67-82 ℃, and the kinematic viscosity of the microcrystalline wax under the test condition of 100 ℃ is 6mm 2 /s~20mm 2 /s；
(9) The anti-aging agent comprises one or more of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2-mercaptobenzimidazole;
(10) The auxiliary vulcanizing agent comprises one or more of trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, triallyl isocyanurate and triallyl cyanurate;
(11) The vulcanizing agent comprises one or more of dicumyl peroxide, 1, 4-di-tert-butyl cumene peroxide and dibenzoyl peroxide.
In one embodiment, the insulating rubber material satisfies at least one of the following conditions (12) - (13):
(12) The particle size of the modified calcined kaolin is 5000-8000 meshes;
(13) The modifying agent used to form the modified calcined kaolin comprises a silane coupling agent.
In one embodiment, the calcined kaolin has a particle size of 5000 mesh to 6000 mesh.
In one embodiment, the insulating rubber material satisfies at least one of the following conditions (14) - (16):
(14) The melting point of the polyethylene wax is 105-110 ℃;
(15) The brookfield viscosity of the polyethylene wax at 140 ℃ under the test condition is 20cps to 30cps;
(16) The weight average molecular weight of the polyethylene wax is 1000-2000.
In one embodiment, the insulating rubber material satisfies at least one of the following conditions (17) - (19):
(17) The dynamic viscosity of the liquid polybutadiene is 50P-200P under the test condition of 45 ℃;
(18) The weight average molecular weight of the liquid polybutadiene is 2200-3300;
(19) The liquid polybutadiene is hydrogenated modified liquid 1,2 polybutadiene.
According to another aspect of the present invention, there is provided a method for preparing an insulating rubber material, comprising the steps of:
providing a preparation raw material according to the insulating rubber material, and mixing the preparation raw material to prepare the insulating rubber material.
According to still another aspect of the present invention, there is provided a cable comprising the above-mentioned insulating rubber material or the insulating rubber material prepared by the above-mentioned preparation method.
Compared with the prior art, the invention has the following beneficial effects:
according to the insulating rubber material, the mass parts of the preparation raw materials are limited within a specific range, so that different raw materials are matched and cooperate, and the insulating rubber material with excellent electrical insulation performance, dielectric property, breakdown strength, mechanical property and high temperature resistance is prepared. Specifically, the ethylene octene copolymer and the ethylene propylene rubber have good compatibility, and the combination of the ethylene octene copolymer and the ethylene propylene rubber can endow the insulating rubber material with excellent dielectric property and mechanical property; the modified calcined kaolin and the calcined kaolin are matched, so that excellent electrical insulation property and mechanical property can be given to the rubber material, and the aging resistance of the rubber material is also benefited; polyethylene wax is added into the raw materials to serve as a sizing material dielectric property modifier, so that the dielectric property and the electrical insulation property of the sizing material can be obviously improved; besides the function of plasticizer, the liquid polybutadiene can also participate in the vulcanization reaction of the rubber material, and can be crosslinked with ethylene propylene rubber and ethylene octene copolymer, so that the rubber material is endowed with excellent mechanical property and ageing resistance, and simultaneously, the dielectric property and insulating property of the rubber material can be obviously improved.
Detailed Description
The detailed description of the present invention will be provided to make the above objects, features and advantages of the present invention more obvious and understandable. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The invention provides an insulating rubber material, which comprises the following preparation raw materials in parts by mass:
50-80 parts of ethylene propylene diene monomer,
20-50 parts of ethylene octene copolymer,
5-10 parts of indirect zinc oxide,
1-2 parts of stearic acid,
30-60 parts of modified calcined kaolin,
20-30 parts of calcined kaolin,
0.2 to 0.5 part of coupling agent,
3-4 parts of microcrystalline wax,
6-10 parts of polyethylene wax,
10-16 parts of liquid polybutadiene,
2.5-3.5 parts of an anti-aging agent,
1-2 parts of sulfur-assisting agent
3-6 parts of vulcanizing agent.
According to the insulating rubber material, the polyethylene wax is used as a dielectric property modifier, and the ethylene-octene copolymer is used as a modified base material, so that the granulated rubber particles are not adhered to each other on the premise of not affecting the electrical property and the mechanical property, and therefore, an additional coating of a release agent is not required.
In some embodiments, the insulating rubber material comprises the following preparation raw materials in parts by weight:
60-80 parts of ethylene propylene diene monomer,
20-40 parts of ethylene octene copolymer,
7-10 parts of indirect zinc oxide,
1.4-2 parts of stearic acid,
35-50 parts of modified calcined kaolin,
20-30 parts of calcined kaolin,
0.4 to 0.5 part of coupling agent,
3.5-4 parts of microcrystalline wax,
8-10 parts of polyethylene wax,
10-15 parts of liquid polybutadiene,
3-3.5 parts of an anti-aging agent,
1.5-2 parts of sulfur-assisting agent
4-6 parts of vulcanizing agent.
In one preferred example, the insulating rubber material comprises the following preparation raw materials in parts by mass:
70 parts of ethylene propylene diene monomer,
30 parts of ethylene octene copolymer,
8 parts of indirect zinc oxide,
1.6 parts of stearic acid,
45 parts of modified calcined kaolin,
25 parts of calcined kaolin,
0.5 part of coupling agent,
4 parts of microcrystalline wax,
7 parts of polyethylene wax,
11 parts of liquid polybutadiene,
3.2 parts of anti-aging agent,
1.5 parts of sulfur-helping agent
5 parts of vulcanizing agent.
Understandably, with the mass fraction in the above preferred example, the prepared insulating rubber material has more excellent insulating properties.
In some specific examples, the ethylene structural unit content in the ethylene propylene diene monomer is 60-77 wt%; preferably, the ethylene structural unit content in the ethylene propylene diene monomer is 65-77 wt%; more preferably, the ethylene structural unit content in the ethylene propylene diene monomer is 65wt%.
In some specific examples, the Mooney viscosity of the ethylene propylene diene monomer rubber under the test condition of ML1+4125 ℃ is 20-50; preferably, the Mooney viscosity of the ethylene propylene diene monomer is 20-45; more preferably, the Mooney viscosity of the ethylene propylene diene monomer is 35.
In the invention, the Mooney viscosity reflects the quality of rubber processability, the molecular weight and the width of the distribution range. Wherein M represents Mooney, L1+4deg.C represents torsion value measured at 125 deg.C by preheating with a large rotor for 1min and rotating for 4 min.
In some specific examples, the content of the third monomer structural unit in the ethylene propylene diene monomer is 4-8wt%; preferably, the content of the third monomer structural unit in the ethylene propylene diene monomer is 4-6wt%; more preferably, the content of the third monomer structural unit in the ethylene propylene diene monomer is 6wt%.
Specifically, the third monomer refers to non-conjugated diene substances except ethylene and propylene in ethylene propylene diene monomer; the third monomer may be selected from Ethylidene Norbornene (ENB), dicyclopentadiene (DCPD) or 1, 4-Hexadiene (HD); more preferably, the third monomer is selected from Ethylidene Norbornene (ENB).
It is understood that excellent kneading and extrusion processability, electrical insulating properties and dielectric properties can be obtained with the ethylene propylene diene monomer rubber of the above specific parameters.
In some specific examples, the ethylene octene copolymer has a melt index of 1g/min to 3g/min at a test condition of 2.16kg and 190 ℃; preferably, the melt index of the ethylene octene copolymer is 2 g/min-3 g/min; more preferably, the ethylene octene copolymer has a melt index of 2.5g/min.
In some specific examples, the ethylene octene copolymer has a melting temperature of 60 ℃ to 70 ℃; preferably, the melting temperature of the ethylene octene copolymer is 64-70 ℃; more preferably, the ethylene octene copolymer has a melting temperature of 67 ℃.
In some specific examples, the ethylene octene copolymer has a mooney viscosity of 10 to 30 under ML1+4 ℃ test conditions; preferably, the Mooney viscosity of the ethylene octene copolymer is 20-30; more preferably, the ethylene octene copolymer has a mooney viscosity of 24.
The ethylene octene copolymer is a saturated copolymer and has excellent ageing resistance; the structure of the ethylene propylene rubber is similar to that of ethylene propylene rubber, and the ethylene propylene rubber has good electrical insulation performance and good compatibility. The ethylene-octene copolymer and ethylene propylene rubber can be used as a base material of a cable insulation rubber material, and can endow the rubber material with excellent dielectric property and mechanical property.
The applicant researches find that the ethylene octene copolymer has the dielectric property equivalent to that of ethylene propylene rubber, and can replace ethylene propylene diene monomer rubber to be used for preparing medium voltage cable insulating rubber materials; the ethylene-octene copolymer is added into the preparation raw material, the rubber matrix does not need to be sprayed with isolation powder after extrusion granulation, the phenomena of adhesion agglomeration, introduction of potential breakdown foreign matter impurities and the like are avoided, and the prepared insulating rubber material has high pressure resistance and excellent dielectric property.
It is understood that the ethylene-octene copolymer having the above specific parameters can impart excellent dielectric properties to the insulating rubber material on the one hand, and can sufficiently disperse and combine the respective production raw materials to form a uniform material because of its large fillable amount on the other hand.
Compared with other types of active zinc oxide, the purity of the indirect zinc oxide is 99.7%, the material purity is high, and the impurities are few.
In some specific examples thereof, the coupling agent includes one or more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane, and aluminate coupling agents. It is understood that the coupling agent may include any one of the above, may include any two or more of the above, and may include other substances than the above.
In some specific examples, the microcrystalline wax has a melting point of 67 ℃ to 82 ℃. It is understood that microcrystalline waxes having melting points of 67 to 82 ℃ may be included in addition to microcrystalline waxes having melting points.
In some specific examples, the microcrystalline wax has a kinematic viscosity of 6mm at 100 ℃ under test conditions 2 /s~20mm 2 /s。
In some specific examples thereof, the anti-aging agent includes one or more of n-stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and 2-mercaptobenzimidazole. It is understood that the antioxidant may include any one of the above, may include any two or more of the above, and may include other substances than the above.
Specifically, the anti-aging agent is compounded with other components, so that the insulating rubber material can be endowed with excellent high-temperature aging resistance, and the vulcanization performance of the insulating rubber material is not affected.
In some specific examples thereof, the co-vulcanizing agent includes one or more of trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, triallyl isocyanurate, and triallyl cyanurate.
In some specific examples thereof, the vulcanizing agent includes one or more of dicumyl peroxide, 1, 4-di-tert-butylperoxycumene, and dibenzoyl peroxide.
The specific types of indirect zinc oxide, coupling agent, microcrystalline wax, anti-aging agent, auxiliary vulcanizing agent and vulcanizing agent are selected, and the components can be matched and synergistic with the rubber base material, so that the insulating rubber material with excellent insulating property, dielectric property and mechanical property is prepared.
In some specific examples, the modified calcined kaolin has a particle size of 5000 mesh to 8000 mesh; preferably, the particle size of the modified calcined kaolin is 6000 mesh.
In some specific examples thereof, the modifying agent used to form the modified calcined kaolin comprises a silane coupling agent.
Specifically, the modified calcined kaolin is formed by the steps of: grinding kaolin to the required mesh number by a grinder, calcining for 50 minutes at 800+/-20 ℃, cooling the calcined material to room temperature, adding the calcined material into a high-speed stirrer, adding a coupling agent accounting for 0.8 percent of the weight of the calcined kaolin in a spray mode at 105 ℃, and treating for 10 minutes to obtain the required modified calcined kaolin.
In some specific examples, the calcined kaolin has a particle size of 5000 mesh to 6000 mesh; preferably, the calcined kaolin has a particle size of 6000 mesh.
In the invention, the modified calcined kaolin and the calcined kaolin are matched, so that the insulating rubber material can be endowed with excellent electrical insulation property and mechanical property, and the ageing resistance of the insulating rubber material can be improved. The particle sizes of the modified calcined kaolin and the calcined kaolin are controlled within a specific range, so that the modified calcined kaolin and the calcined kaolin can be uniformly dispersed in the rubber base material, the uniformity of the rubber insulating material is improved, and potential breakdown points are not formed.
In some specific examples, the polyethylene wax has a melting point of 105 ℃ to 110 ℃; preferably, the melting point of the polyethylene wax is 107-110 ℃; more preferably, the polyethylene wax has a melting point of 109 ℃.
In some specific examples, the polyethylene wax has a brookfield viscosity of 20cps to 30cps at 140 ℃ under test conditions; preferably, the polyethylene wax has a brookfield viscosity of 28cps.
In some specific examples, the polyethylene wax has a weight average molecular weight of 1000 to 2000; preferably, the weight average molecular weight of the polyethylene wax is 1100-2000; more preferably, the polyethylene wax has a weight average molecular weight of 1800.
Polyethylene waxes are commonly used in PVC materials as dispersants, lubricants and brighteners; the modified polypropylene can also be used as a processing aid in rubber, so that the dispersibility of the filler is improved, and the extrusion molding rate is improved; it has not been used as a dielectric property modifier in the conventional art. The applicant researches find that the polyethylene wax is added into the raw materials of the insulating rubber material, so that the dielectric property and the electrical insulation property of the insulating rubber material are obviously improved; thus being used as a dielectric property modifier.
In some specific examples, the dynamic viscosity of the liquid polybutadiene is 50P-200P under the test condition of 45 ℃; preferably, the dynamic viscosity of the liquid polybutadiene is 100P-200P; more preferably, the dynamic viscosity of the liquid polybutadiene is 180P.
In some specific examples, the liquid polybutadiene has a weight average molecular weight of 2200 to 3300; preferably, the weight average molecular weight of the liquid polybutadiene is 2700-3300; more preferably, the liquid polybutadiene has a weight average molecular weight of 2900.
In some specific examples, 1,2 vinyl groups in the liquid polybutadiene are hydrogenated and modified to enable unsaturated vinyl groups on branched chains to be hydrogenated and modified, and then the unsaturated vinyl groups are converted into saturated materials with better ageing resistance.
It is understandable that adding the liquid polybutadiene with the specific parameters into the preparation raw materials of the insulating rubber material can make the rubber material have excellent heat resistance, dielectric property and electrical insulation property, and can participate in the vulcanization reaction of the rubber material, and can be crosslinked with ethylene propylene rubber and ethylene octene copolymer to endow the rubber with excellent mechanical property.
The insulating rubber material of the invention has at least the following advantages: (1) The preparation raw materials are low-cost environment-friendly materials, and are suitable for large-scale production; (2) The cost performance of raw materials is high, the processability is good, no additional spraying of a release agent is needed after extrusion granulation, and the phenomenon of bonding and agglomeration can not occur; (3) The high-voltage cable has excellent insulating property, dielectric property, mechanical property and high-temperature aging resistance, and can meet the application requirements of 10kV high-voltage cables.
In a second aspect of the present invention, there is provided a method for producing an insulating rubber material, comprising the steps of:
providing the preparation raw materials, mixing the preparation raw materials, and preparing the insulating rubber material.
In some specific examples, the preparation method of the insulating rubber material comprises steps S10-S30.
S10: mixing and kneading an ethylene-octene copolymer, indirect zinc oxide, stearic acid, modified calcined kaolin, a coupling agent, microcrystalline wax, polyethylene wax, liquid polybutadiene and an anti-aging agent to obtain a first mixture;
s20: adding ethylene propylene rubber into the first mixture, and sequentially carrying out pressurized mixing, filtering and extrusion granulation to obtain a rubber matrix;
s30: adding a vulcanization aid and a vulcanizing agent into the rubber matrix, and sequentially carrying out pressurized mixing and extrusion granulation to prepare the insulating rubber material.
The invention provides an insulating rubber material or an application of the insulating rubber material prepared by the preparation method in preparation of power transmission articles.
A cable comprises the insulating rubber material or the insulating rubber material prepared by the preparation method.
In some of these specific examples, the cable is a 10kV cable. Understandably, the insulating rubber material provided by the invention has excellent insulating property, dielectric property, mechanical property and high-temperature-resistant and aging-resistant properties, and can meet the application requirements of 10kV wires and cables.
The present invention will be further described with reference to specific examples and comparative examples, which should not be construed as limiting the scope of the invention.
Example 1:
1. the preparation method comprises the following steps of: 50 parts of ethylene propylene diene monomer, 50 parts of ethylene octene copolymer, 5 parts of indirect zinc oxide, 1 part of stearic acid, 30 parts of modified calcined kaolin, 30 parts of calcined kaolin, 0.5 part of vinyltriethoxysilane, 3 parts of microcrystalline wax, 6 parts of polyethylene wax, 16 parts of liquid polybutadiene, 2.5 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, 2 parts of trimethylolpropane trimethacrylate and 6 parts of dicumyl peroxide.
Wherein the ethylene structural unit content in the ethylene propylene diene monomer is 60wt%, the Mooney viscosity (ML1+4125 ℃) is 50, and the third monomer structural unit content is 8wt%;
the ethylene octene copolymer had a melt index of 2.2g/min (test conditions of 2.16kg load, 190 ℃) and a melt temperature of 70℃and a Mooney viscosity of 10;
the melting point of the polyethylene wax is 105 ℃, the brookfield viscosity (140 ℃) is 20cps, and the weight average molecular weight is 1000;
the dynamic viscosity (45 ℃) of the liquid polybutadiene was 60P, and the weight-average molecular weight was 2400.
2. The specific preparation process is as follows:
(1) All raw materials except ethylene propylene diene monomer, a vulcanization aid and a vulcanizing agent are added into a first internal mixer and mixed for 1 minute.
(2) Adding ethylene propylene diene monomer into a first internal mixer, and pressurizing and mixing; raising the upper ram when the temperature of the first internal mixer is raised to 75 ℃, mixing for 30 seconds, falling the upper ram, and continuing to carry out pressurized mixing; and when the temperature of the first internal mixer is increased to 105 ℃, lifting the upper ram, mixing for 30 seconds, dropping the upper ram, and continuing to carry out pressurized mixing.
(3) And when the temperature of the first internal mixer is increased to 115 ℃, discharging the rubber material to a double-cone feeding port, conveying the rubber material through a single-screw extruder, filtering, granulating through a granulator, and cooling the rubber compound particles through a cyclone cooling device. Wherein the temperature of the extruder and the granulator is controlled below 125 ℃.
(4) Weighing the rubber compound particles, and putting the rubber compound particles into a second internal mixer for pressurized mixing; when the temperature of the second internal mixer is increased to 60 ℃, pressurizing and mixing the auxiliary vulcanizing agent and the vulcanizing agent; raising the upper ram when the temperature of the second internal mixer is raised to 70 ℃, mixing for 15 seconds, falling the upper ram, and continuing to carry out pressurized mixing; and when the temperature of the second internal mixer is increased to 90 ℃, lifting the upper ram, mixing for 30 seconds, dropping the upper ram, and continuing to carry out pressurized mixing.
(5) And when the temperature of the second internal mixer is increased to 100 ℃, discharging the rubber material to a double-cone feeding port, conveying the rubber material to a granulator for granulation through a single-screw extruder, conveying the rubber material to a vibrating screen through a fan, and then further cooling the rubber compound particles through a cyclone cooling device. Wherein the temperature of the extruder and the granulator is controlled below 105 ℃.
(6) And (3) conveying the cooled rubber compound particles to a storage bin through a fan to prepare the insulating rubber material.
Example 2:
1. the preparation method comprises the following steps of: 60 parts of ethylene propylene diene monomer, 40 parts of ethylene octene copolymer, 10 parts of indirect zinc oxide, 2 parts of stearic acid, 60 parts of modified calcined kaolin, 20 parts of calcined kaolin, 0.4 part of vinyltrimethoxysilane, 4 parts of microcrystalline wax, 10 parts of polyethylene wax, 10 parts of liquid polybutadiene, 2.5 parts of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1.5 parts of N, N' -m-phenylene bismaleimide and 4.5 parts of 1, 4-di-tert-butyl peroxyisopropyl benzene.
Wherein the ethylene structural unit content in the ethylene propylene diene monomer is 77wt%, the Mooney viscosity (ML1+4125 ℃) is 20, and the third monomer structural unit content is 4wt%;
the ethylene octene copolymer has a melt index of 2g/min (test conditions of 2.16kg load, 190 ℃) and a melt temperature of 65℃and a Mooney viscosity of 30;
the melting point of the polyethylene wax is 110 ℃, the brookfield viscosity (140 ℃) is 30cps, and the weight average molecular weight is 2000;
the dynamic viscosity (45 ℃) of the liquid polybutadiene was 180P, and the weight-average molecular weight was 3300.
2. The specific preparation process was the same as in example 1.
Example 3:
1. the preparation method comprises the following steps of: 80 parts of ethylene propylene diene monomer, 20 parts of ethylene octene copolymer, 7 parts of indirect zinc oxide, 1.4 parts of stearic acid, 40 parts of modified calcined kaolin, 30 parts of calcined kaolin, 0.2 part of vinyl tri (beta-methoxyethoxy) silane, 0.3 part of aluminate coupling agent, 3.5 parts of microcrystalline wax, 8 parts of polyethylene wax, 14 parts of liquid polybutadiene, 3.5 parts of 2-mercaptobenzimidazole, 2 parts of triallyl isocyanurate and 3.5 parts of dibenzoyl peroxide.
Wherein the ethylene structural unit content in the ethylene propylene diene monomer is 70wt%, the Mooney viscosity (ML1+4125 ℃) is 30, and the third monomer structural unit content is 5wt%;
the ethylene octene copolymer has a melt index of 3g/min (test conditions of 2.16kg load, 190 ℃) and a melt temperature of 70℃and a Mooney viscosity of 26;
the polyethylene wax has a melting point of 107 ℃, a brookfield viscosity (140 ℃) of 23cps, and a weight average molecular weight of 1400;
the dynamic viscosity (45 ℃) of the liquid polybutadiene was 80P, and the weight-average molecular weight was 2700.
2. The specific preparation process was the same as in example 1.
Example 4:
1. the preparation method comprises the following steps of: 70 parts of ethylene propylene diene monomer, 30 parts of ethylene octene copolymer, 8 parts of indirect zinc oxide, 1.6 parts of stearic acid, 45 parts of modified calcined kaolin, 25 parts of calcined kaolin, 0.2 part of vinyltriethoxysilane, 0.3 part of vinyltrimethoxysilane, 4 parts of microcrystalline wax, 7 parts of polyethylene wax, 11 parts of liquid polybutadiene, 3.2 parts of n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1.5 parts of triallyl cyanurate and 5 parts of 1, 4-di-tert-butyl peroxyisopropyl benzene.
Wherein the ethylene structural unit content in the ethylene propylene diene monomer is 65wt%, the Mooney viscosity (ML1+4125 ℃) is 35, and the third monomer structural unit content is 6wt%;
the ethylene octene copolymer had a melt index of 2.5g/min (test conditions of 2.16kg load, 190 ℃) and a melt temperature of 67℃and a Mooney viscosity of 24;
the melting point of the polyethylene wax is 109 ℃, the brookfield viscosity (140 ℃) is 28cps, and the weight average molecular weight is 1800;
the dynamic viscosity (45 ℃) of the liquid polybutadiene was 100P, and the weight-average molecular weight was 2900.
2. The specific preparation process was the same as in example 1.
Example 5:
1. the preparation method comprises the following steps of: 60 parts of ethylene propylene diene monomer, 40 parts of ethylene octene copolymer, 6 parts of indirect zinc oxide, 1.8 parts of stearic acid, 35 parts of modified calcined kaolin, 30 parts of calcined kaolin, 0.2 part of vinyltrimethoxysilane, 0.2 part of vinyltris (beta-methoxyethoxy) silane, 3.5 parts of microcrystalline wax, 9 parts of polyethylene wax, 15 parts of liquid polybutadiene, 3 parts of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 3 parts of N, N' -m-phenylene bismaleimide, 1 part of triallyl isocyanurate, 1 part of triallyl cyanurate, 3 parts of dicumyl peroxide and 3 parts of 1, 4-di-tert-butyl isopropyl benzene peroxide.
Wherein the ethylene structural unit content in the ethylene propylene diene monomer is 73wt%, the Mooney viscosity (ML1+4125 ℃) is 25, and the third monomer structural unit content is 4.5wt%;
the ethylene octene copolymer had a melt index of 1.5g/min (test conditions of 2.16kg load, 190 ℃) and a melt temperature of 64℃and a Mooney viscosity of 20;
the melting point of the polyethylene wax is 108 ℃, the brookfield viscosity (140 ℃) is 20cps, and the weight average molecular weight is 1100;
the dynamic viscosity (45 ℃) of the liquid polybutadiene was 140P, and the weight average molecular weight was 3000.
2. The specific preparation process was the same as in example 1.
Example 6:
1. the preparation method comprises the following steps of: 55 parts of ethylene propylene diene monomer, 45 parts of ethylene octene copolymer, 5 parts of indirect zinc oxide, 1 part of stearic acid, 30 parts of modified calcined kaolin, 30 parts of calcined kaolin, 0.3 part of vinyltriethoxysilane, 0.2 part of vinyltrimethoxysilane, 3.5 parts of microcrystalline wax, 8 parts of polyethylene wax, 14 parts of liquid polybutadiene, 3 parts of 2-mercaptobenzimidazole, 2 parts of trimethylolpropane trimethacrylate and 6 parts of dicumyl peroxide.
Wherein the ethylene structural unit content in the ethylene propylene diene monomer is 60wt%, the Mooney viscosity (ML1+4125 ℃) is 50, and the third monomer structural unit content is 8wt%;
the melt index of the ethylene octene copolymer is 1g/min (the test condition is 2.16kg load and 190 ℃), the melt temperature is 70 ℃ and the Mooney viscosity is 10;
the melting point of the polyethylene wax is 105 ℃, the brookfield viscosity (140 ℃) is 20cps, and the weight average molecular weight is 1000;
the dynamic viscosity (45 ℃) of the liquid polybutadiene was 60P, and the weight-average molecular weight was 2400.
2. The specific preparation process was the same as in example 1.
Comparative example 1:
the preparation raw materials do not contain modified calcined kaolin, and the calcined kaolin is replaced by equivalent calcined kaolin.
Comparative example 2:
the preparation raw material does not contain liquid polybutadiene.
Comparative example 3:
the preparation raw material adopts equivalent rubber-based paraffin oil to replace liquid polybutadiene.
Comparative example 4:
the preparation raw materials do not contain ethylene octene copolymer, and the ethylene propylene diene monomer is replaced by the same amount.
Comparative example 5:
the raw materials for preparation do not include polyethylene wax.
Specifically, the formulations of the insulating rubber materials of the above examples 1 to 6 and comparative examples 1 to 5 are shown in table 1 in terms of parts by mass.
TABLE 1
Performance testing
The mechanical property test is carried out by referring to GB/T2951.11-2008 standard; the air heat aging test is carried out according to the GB/T2951.12-2008 standard; the aeroelastic aging test is carried out according to the GB/T2951.12-2008 standard; the water absorption performance test is carried out according to the GB/T2951.13-2008 standard. The results of the performance tests of examples 1 to 6 and comparative examples 1 to 5 are shown in Table 2.
TABLE 2
From the above table, in examples 1 to 6, specific parts and specific types of preparation raw materials cooperate and cooperate with each other, and the prepared insulating rubber material has at least the following advantages: (1) has excellent insulating electrical properties: volume resistivity is more than or equal to 1.1 multiplied by 10 16 Omega cm; (2) has excellent dielectric properties: the dielectric constant is less than or equal to 2.8, and the dielectric loss is less than or equal to 0.0048; (3) has excellent mechanical properties: the tensile strength is more than or equal to 12.0MPa, and the elongation at break is more than or equal to 340%; (4) has excellent high-temperature aging resistance: after heat treatment at 135 ℃ for 240 hours, the change rate of the tensile strength and the change rate of the elongation at break are both within +/-15 percent.
Comparative example 1 is substantially the same as example 1 except that the modified calcined kaolin in the preparation raw material is replaced with calcined kaolin, and the volume resistivity and dielectric strength of the prepared insulating rubber material are reduced, and the dielectric constant and dielectric loss are remarkably increased; the dielectric properties are significantly inferior to those of examples 1 to 6.
Comparative example 2 is substantially the same as example 1 except that liquid polybutadiene is not added to the raw material for preparation, and the elongation at break, volume resistivity and dielectric strength of the prepared insulating rubber material are all reduced, the dielectric constant and dielectric loss are increased, and the water absorption property is lowered.
Comparative example 3 is substantially the same as example 1 except that an equal amount of rubber-based paraffin oil is used instead of liquid polybutadiene, and the dielectric loss of the prepared insulating rubber material is significantly increased.
Comparative example 4 is substantially the same as example 2 except that ethylene octene copolymer in the preparation raw material is replaced with ethylene propylene diene monomer in equal amount, the tensile strength of the prepared insulating rubber material is reduced, the dielectric loss is obviously increased, and a certain degree of adhesion phenomenon occurs between rubber particles after granulation.
Comparative example 5 is substantially the same as example 3 except that no polyethylene wax is added to the raw materials for preparation, and the volume resistivity of the prepared insulating rubber material is reduced, the dielectric loss is increased, and the water absorption performance is reduced.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (12)
1. The insulating rubber material is characterized by comprising the following preparation raw materials in parts by mass:
50-80 parts of ethylene propylene diene monomer,
20-50 parts of ethylene octene copolymer,
5-10 parts of indirect zinc oxide,
1-2 parts of stearic acid,
30-60 parts of modified calcined kaolin,
20-30 parts of calcined kaolin,
0.2 to 0.5 part of coupling agent,
3-4 parts of microcrystalline wax,
6-10 parts of polyethylene wax,
10-16 parts of liquid polybutadiene,
2.5-3.5 parts of an anti-aging agent,
1-2 parts of sulfur-assisting agent
3-6 parts of vulcanizing agent.
2. The insulating rubber material according to claim 1, which is characterized by comprising the following preparation raw materials in parts by mass:
60-80 parts of ethylene propylene diene monomer,
20-40 parts of ethylene octene copolymer,
7-10 parts of indirect zinc oxide,
1.4-2 parts of stearic acid,
35-50 parts of modified calcined kaolin,
20-30 parts of calcined kaolin,
0.4 to 0.5 part of coupling agent,
3.5-4 parts of microcrystalline wax,
8-10 parts of polyethylene wax,
10-15 parts of liquid polybutadiene,
3-3.5 parts of an anti-aging agent,
1.5-2 parts of sulfur-assisting agent
4-6 parts of vulcanizing agent.
3. The insulating rubber material according to any one of claims 1 to 2, characterized in that the insulating rubber material satisfies at least one of the following conditions (1) to (3):
(1) The ethylene structural unit content in the ethylene propylene diene monomer is 60-77 wt%;
(2) The Mooney viscosity of the ethylene propylene diene monomer is 20-50 under the testing condition of ML1+4125 ℃;
(3) The content of the third monomer structural unit in the ethylene propylene diene monomer is 4-8wt%.
4. The insulating rubber material according to any one of claims 1 to 2, characterized in that the insulating rubber material satisfies at least one of the following conditions (4) to (6):
(4) The melt index of the ethylene octene copolymer is 1 g/min-3 g/min under the test condition of 2.16kg and 190 ℃;
(5) The melting temperature of the ethylene octene copolymer is 60-70 ℃;
(6) The Mooney viscosity of the ethylene octene copolymer under the test condition of ML1+4121 ℃ is 10-30.
5. The insulating rubber material according to any one of claims 1 to 2, characterized in that the insulating rubber material satisfies at least one of the following conditions (7) to (11):
(7) The coupling agent comprises one or more of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane and aluminate coupling agent;
(8) The melting point of the microcrystalline wax is 67-82 ℃, and the kinematic viscosity of the microcrystalline wax under the test condition of 100 ℃ is 6mm 2 /s~20mm 2 /s；
(9) The anti-aging agent comprises one or more of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2-mercaptobenzimidazole;
(10) The auxiliary vulcanizing agent comprises one or more of trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, triallyl isocyanurate and triallyl cyanurate;
(11) The vulcanizing agent comprises one or more of dicumyl peroxide, 1, 4-di-tert-butyl cumene peroxide and dibenzoyl peroxide.
6. The insulating rubber material according to any one of claims 1 to 2, characterized in that the insulating rubber material satisfies at least one of the following conditions (12) to (13):
(12) The particle size of the modified calcined kaolin is 5000-8000 meshes;
(13) The modifying agent used to form the modified calcined kaolin comprises a silane coupling agent.
7. The insulating rubber material according to any one of claims 1 to 2, wherein the calcined kaolin has a particle size of 5000 to 6000 mesh.
8. The insulating rubber material according to any one of claims 1 to 2, characterized in that the insulating rubber material satisfies at least one of the following conditions (14) to (16):
(14) The melting point of the polyethylene wax is 105-110 ℃;
(15) The brookfield viscosity of the polyethylene wax at 140 ℃ under the test condition is 20cps to 30cps;
(16) The weight average molecular weight of the polyethylene wax is 1000-2000.
9. The insulating rubber material according to any one of claims 1 to 2, characterized in that the insulating rubber material satisfies at least one of the following conditions (17) to (19):
(17) The dynamic viscosity of the liquid polybutadiene is 50P-200P under the test condition of 45 ℃;
(18) The weight average molecular weight of the liquid polybutadiene is 2200-3300;
(19) The liquid polybutadiene is hydrogenated modified liquid 1,2 polybutadiene.
10. The preparation method of the insulating rubber material is characterized by comprising the following steps:
the insulating rubber material according to any one of claims 1 to 9, which is prepared by kneading a preparation raw material.
11. The insulating rubber material according to any one of claims 1 to 9 or the insulating rubber material prepared by the preparation method according to claim 10, and application thereof in preparation of power transmission articles.
12. A cable, characterized by comprising the insulating rubber material according to any one of claims 1 to 9 or the insulating rubber material prepared by the preparation method according to claim 10.
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