CN114516990A - Ethylene propylene diene monomer insulating material with high mechanical property and preparation method thereof - Google Patents
Ethylene propylene diene monomer insulating material with high mechanical property and preparation method thereof Download PDFInfo
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- CN114516990A CN114516990A CN202210260038.7A CN202210260038A CN114516990A CN 114516990 A CN114516990 A CN 114516990A CN 202210260038 A CN202210260038 A CN 202210260038A CN 114516990 A CN114516990 A CN 114516990A
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- diene monomer
- ethylene propylene
- propylene diene
- insulating material
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- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 71
- 239000011810 insulating material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 150000002978 peroxides Chemical class 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 di-tert-butylperoxy diisopropylbenzene Chemical compound 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 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 3
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 claims description 3
- YNSSPVZNXLACMW-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)-3-ethyl-5-methylphenyl]methyl]-2-ethyl-6-methylphenyl]pyrrole-2,5-dione Chemical compound C=1C(C)=C(N2C(C=CC2=O)=O)C(CC)=CC=1CC(C=C1CC)=CC(C)=C1N1C(=O)C=CC1=O YNSSPVZNXLACMW-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 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 3
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 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 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 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 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- JFCCVNTYPIUJDJ-UHFFFAOYSA-N methyl-tris(prop-2-enyl)silane Chemical compound C=CC[Si](C)(CC=C)CC=C JFCCVNTYPIUJDJ-UHFFFAOYSA-N 0.000 claims description 3
- QFCLQSLLAYLBCU-UHFFFAOYSA-N phenyl-tris(prop-2-enyl)silane Chemical compound C=CC[Si](CC=C)(CC=C)C1=CC=CC=C1 QFCLQSLLAYLBCU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011297 pine tar Substances 0.000 claims description 3
- 229940068124 pine tar Drugs 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- AKRQMTFHUVDMIL-UHFFFAOYSA-N tetrakis(prop-2-enyl)silane Chemical compound C=CC[Si](CC=C)(CC=C)CC=C AKRQMTFHUVDMIL-UHFFFAOYSA-N 0.000 claims description 3
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 8
- 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 8
- 239000000463 material Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000012812 general test Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Abstract
The invention relates to the technical field of high polymer insulating materials, in particular to an ethylene propylene diene monomer insulating material with high mechanical property and a preparation method thereof. The invention discloses a high-mechanical-property ethylene propylene diene monomer insulating material which comprises 60-95 parts of ethylene propylene diene monomer, 5-40 parts of metallocene polyethylene, 0.5-2 parts of peroxide vulcanizing agent, 0.5-2 parts of vulcanizing assistant, 30-50 parts of reinforcing filler, 0.8-1.2 parts of stearic acid, 4-6 parts of zinc oxide, 1-3 parts of plasticizer, 1-3 parts of anti-aging agent and 1-3 parts of coupling agent. The invention aims to provide a high-mechanical-performance ethylene propylene diene monomer insulating material which can be used for marine shore power cables, wind power anti-torsion cables and other cables bearing high mechanical stress for a long time and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of high polymer insulating materials, in particular to an ethylene propylene diene monomer insulating material with high mechanical property and a preparation method thereof.
Background
Ethylene-propylene-diene monomer (EPDM) is a generic name of synthetic rubbers obtained by copolymerizing ethylene, propylene, and a small amount of a third monomer as a base monomer, and has excellent chemical stability, chemical resistance, electrical insulation, and impact resilience, heat resistance, and water vapor resistance. The modification of the ethylene propylene diene monomer rubber material on the market at present mainly focuses on chemical modification and physical blending modification of a rubber matrix.
The chemical modification of the ethylene propylene diene monomer rubber material is to improve the affinity between rubber and other materials by carrying out chemical reaction on low molecular organic matters and EPDM under different conditions, thereby improving the comprehensive performance of the ethylene propylene diene monomer rubber mixture. The chemical modification of the ethylene propylene diene monomer rubber in the market at present mainly comprises three types of halogenation, sulfonation and reactive grafting modification. The physical blending modification of the ethylene propylene diene monomer material mainly comprises three aspects: 1) EPDM blends with other rubber or polymer molecules; 2) EPDM and inorganic filler are blended and modified; 3) and (3) reinforcing the EPDM formula.
The blending modification of the ethylene propylene diene monomer material and other polymer molecules means that other polymer matrixes are added and mixed with each other by means of mixing and the like, so that the molecular chain size is uniformly distributed, and the advantageous properties of each party are obtained. The inorganic filler is modified by reinforcing a matrix mainly by utilizing a nano-sized structure and a larger specific surface area characteristic of the filler, and can play a role generally when a larger amount of the filler is required to be added, and the inorganic filler has poorer compatibility with an organic matrix, so that the nano particles are easy to agglomerate and accumulate in the matrix. The formula reinforcement of the ethylene propylene diene monomer rubber needs to consider the action of each filler on a matrix and the interaction between the fillers, and in the process, a vulcanization system, a vulcanization active system, an anti-aging system, a plasticizer system and the like of the rubber need to be optimized and matched, so that the process is a complicated process.
Ethylene propylene diene monomer rubber has good insulating property and water resistance, so that the ethylene propylene diene monomer rubber is widely applied to the field of electric power insulation. However, in some special occasions subjected to moving use such as bending, dragging and stretching for a long time, the conventional ethylene propylene diene monomer insulating material has low mechanical strength, and the tensile strength is usually between 4.2MPa and 12.5MPa, so that the use requirement of the special occasions cannot be completely met. The ethylene propylene diene monomer insulating material has the advantages of excellent mechanical property, anti-aging property, electric insulating property and the like, and still needs further research.
Therefore, the technical personnel in the field are dedicated to develop the high-mechanical-property ethylene propylene diene monomer insulating material which has the advantages of easy processing and preparation process, smooth surface, low requirement on equipment, environmental protection and capability of being widely applied to marine shore power cables, wind power torsion-resistant cables and other cables needing to bear high mechanical stress for a long time, and the preparation method thereof.
Disclosure of Invention
In view of the defects in the prior art, the invention discloses an ethylene propylene diene monomer insulating material with high mechanical property and a preparation method thereof, and aims to solve the technical problem of providing an insulating material for marine shore power cables and wind power torsion-resistant cables which can bear high mechanical stress for a long time.
In order to achieve the purpose, the invention provides an ethylene propylene diene monomer insulating material with high mechanical property, which comprises 60-95 parts of ethylene propylene diene monomer, 5-40 parts of metallocene polyethylene, 0.5-2 parts of peroxide vulcanizing agent, 0.5-2 parts of vulcanizing assistant, 30-50 parts of reinforcing filler, 0.8-1.2 parts of stearic acid, 4-6 parts of zinc oxide, 1-3 parts of plasticizer, 1-3 parts of anti-aging agent and 1-3 parts of coupling agent.
Preferably, the ethylene propylene diene monomer is 75-90 parts, the ethylene propylene diene monomer is a polymer formed by copolymerizing ethylene, propylene and a third monomer ENB, the ethylene group content of the ethylene propylene diene monomer is 45-70%, the ethylidene norbornene group (the third monomer ENB) content is 4.0-8.0%, and the balance is the propylene group, so that the ethylene propylene diene monomer has relatively high mechanical property and electrical property, high filling property and moderate vulcanization speed.
Preferably, the metallocene polyethylene accounts for 10-40 parts, the metallocene polyethylene is copolymerized by ethylene and 1-hexene or 1-octene under the action of a metallocene catalyst, the relative molecular weight distribution of the metallocene polyethylene is 2.0-2.5, the density is 0.864-0.936 g/cm3, and the melt flow rate is 0.5-10.0 g/10 min. The melting point of the metallocene polyethylene selected by the invention is lower than that of common polyethylene, and the metallocene polyethylene has good processing fluidity and good flexibility.
Preferably, the peroxide curing agent is one of dicumyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and di-tert-butylperoxy diisopropylbenzene.
Preferably, the vulcanizing assistant is one or more of triallyl isocyanurate, trimethylallylisocyanate, N '- (1, 4-phenylene) bismaleimide, N' -m-phenylene bismaleimide, 1, 2-phenylene-bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, triallyl (phenyl) silane, tetraallylsilane, methyltriallylsilane, triallylamine.
Preferably, the reinforcing filler is non-conductive reinforcing filler and is one or more of fumed silica, alumina fiber, titanium dioxide and mica powder.
Preferably, the plasticizer is one or more of paraffin oil, pine tar, triethylene glycol and diisodecyl phthalate.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 6PPD, antioxidant UOP88, antioxidant SP, antioxidant 2246S and antioxidant 264.
Preferably, the coupling agent is any one of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, triisostearoylisopropyl titanate, sodium stearate and hexadecyltrimethylammonium bromide.
The invention also provides a preparation method of the ethylene propylene diene monomer insulating material with high mechanical property, which comprises the following steps:
(1) sequentially adding 60-95 parts of ethylene propylene diene monomer, 5-40 parts of metallocene polyethylene, 30-50 parts of reinforcing filler, 1-3 parts of coupling agent, 1 part of stearic acid, 5 parts of zinc oxide, 1-3 parts of plasticizer and 1-3 parts of anti-aging agent into an internal mixer, melting and blending for 10-30 min at 50-150 ℃, then adding 0.5-2 parts of peroxide vulcanizing agent and 0.5-2 parts of vulcanizing assistant, uniformly mixing, and taking out a primary mixture;
(2) placing the primary mixture in a mold, preheating the primary mixture for 3-7 min on a flat vulcanizing machine at the temperature of 115 +/-5 ℃ without pressurizing, then hot-pressing the primary mixture for 25-35 min under the conditions that the temperature is 170 +/-5 ℃ and the pressurizing pressure is 15-20 Mpa, and finally pressurizing and cooling the primary mixture to room temperature and taking the primary mixture out to obtain the ethylene propylene diene monomer insulating material with high mechanical property.
The beneficial effects of the invention are:
the ethylene propylene diene monomer rubber and the metallocene polyethylene are adopted, the matrix is physically reinforced by the inorganic filler, the inorganic filler is uniformly dispersed in the matrix under the action of the coupling agent, and meanwhile, the linear polymer is fully crosslinked under the action of the high-efficiency peroxide vulcanizing agent and the high-efficiency vulcanizing assistant, so that the ethylene propylene diene monomer rubber insulating material with excellent mechanical property and electric insulating property is obtained. Meanwhile, the ENB type ethylene propylene diene monomer is doubly reinforced by organic metallocene polyethylene and inorganic filler white carbon black subjected to surface treatment by a coupling agent, the tensile strength of the ethylene propylene rubber is improved, meanwhile, the metallocene polyethylene is used as an organic reinforcing agent to retain the flexibility of the material to a greater degree, and the white carbon black is used as an inorganic reinforcing agent to retain the electrical insulating property of the material to a greater degree, so that the insulating material disclosed by the invention has the characteristics of high strength, high elongation and high resistivity, is easy to process and prepare, has a smooth surface, is low in equipment requirement, is green and environment-friendly, and can be widely applied to the insulation of marine shore power cables, wind power anti-torsion cables and other cables which bear high mechanical stress for a long time.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, but are all commercially available.
The invention provides an ethylene propylene diene monomer insulating material with high mechanical property, which comprises 60-95 parts of ethylene propylene diene monomer, 5-40 parts of metallocene polyethylene, 0.5-2 parts of peroxide vulcanizing agent, 0.5-2 parts of vulcanizing assistant, 30-50 parts of reinforcing filler, 0.8-1.2 parts of stearic acid, 4-6 parts of zinc oxide, 1-3 parts of plasticizer, 1-3 parts of anti-aging agent and 1-3 parts of coupling agent.
Further, the ethylene propylene diene monomer is 75-90 parts, in the embodiment of the invention, the ethylene propylene diene monomer is a polymer formed by copolymerizing ethylene, propylene and a third monomer ENB, the preferred ethylene propylene diene monomer of the invention has a content of ethylene groups of 45-70%, a content of ethylidene norbornene groups (third monomer ENB) of 4.0-8.0% and the balance of propylene groups. In the examples of the present invention, the ethylene-propylene-diene rubber is type number Dow 4570H (ethylene content 50%, ethylidene norbornene 5%, propylene 45%).
Furthermore, 10-40 parts of metallocene polyethylene, wherein the metallocene polyethylene is prepared by copolymerizing ethylene and 1-hexene or 1-octene under the action of a metallocene catalyst, in the embodiment of the invention, the metallocene polyethylene is prepared by copolymerizing ethylene and 1-octene, the relative molecular weight distribution of the metallocene polyethylene is 2.0-2.5, the density is 0.864-0.936 g/cm3, and the melt flow rate is 0.5-10.0 g/10 min. In the examples of the invention, the metallocene polyethylene was type number Homitomo GH030 (density 0.912g/cm3, melt flow rate 0.5g/10 min).
Further, the peroxide vulcanizing agent is one of dicumyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and bis-tert-butylperoxy-diisopropylbenzene.
Further, the vulcanizing assistant is one or more of triallyl isocyanurate, trimethylallyl isocyanate, N '- (1, 4-phenylene) bismaleimide, N' -m-phenylene bismaleimide, 1, 2-phenylene-bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, triallyl (phenyl) silane, tetraallyl silane, methyl triallyl silane and triallyl amine.
Furthermore, the reinforcing filler is non-conductive reinforcing filler and is one or more of fumed silica, alumina fiber, titanium dioxide and mica powder.
Further, the plasticizer is one or more of paraffin oil, pine tar, triethylene glycol and diisodecyl phthalate.
The antioxidant is one or more of antioxidant 1010, antioxidant 6PPD, antioxidant UOP88, antioxidant SP, antioxidant 2246S, and antioxidant 264. The coupling agent is any one of gamma-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, triisostearyl isopropyl titanate, sodium stearate and hexadecyl trimethyl ammonium bromide.
The invention also provides a method for preparing the ethylene propylene diene monomer insulating material with high mechanical property, which comprises the following steps:
(1) sequentially adding 60-95 parts of ethylene propylene diene monomer, 5-40 parts of metallocene polyethylene, 30-50 parts of reinforcing filler, 1-3 parts of coupling agent, 1 part of stearic acid, 5 parts of zinc oxide, 1-3 parts of plasticizer and 1-3 parts of anti-aging agent into an internal mixer, melting and blending for 10-30 min at 50-150 ℃, then adding 0.5-2 parts of peroxide vulcanizing agent and 0.5-2 parts of vulcanizing assistant, uniformly mixing, and taking out a primary mixture;
(2) placing the primary mixture in a mold, preheating for 3-7 min on a flat vulcanizing machine at the temperature of 115 +/-5 ℃ without pressurizing, then hot-pressing for 25-35 min under the conditions that the temperature is 170 +/-5 ℃ and the pressurizing pressure is 15-20 Mpa, and finally pressurizing and cooling to room temperature and taking out to obtain the ethylene propylene diene monomer insulating material with high mechanical property.
For better comparison, the preparation conditions in the examples of the invention and the comparative examples are the same, namely: (1) sequentially adding ethylene propylene diene monomer, metallocene polyethylene, reinforcing filler, coupling agent, stearic acid, zinc oxide, anti-aging agent and plasticizer into an internal mixer, melting and blending for 20min at 100 ℃, then adding peroxide vulcanizing agent and vulcanizing assistant, uniformly mixing, and taking out the primary mixture;
(2) And weighing 30g of the primary mixture, placing the primary mixture in the middle of a mold, preheating the primary mixture on a flat vulcanizing machine for 5min without pressurization, then hot-pressing the primary mixture for 30min at the temperature of 170 ℃ under the pressure of 15MPa, and then taking out the primary mixture after pressurization and cooling to room temperature to obtain the ethylene propylene diene monomer insulating material with high mechanical property.
Meanwhile, in order to illustrate the implementation effect of the embodiment, the ethylene propylene diene monomer insulating material with high mechanical property prepared in the embodiment is subjected to test analysis on a rubber sample after vulcanization molding. The mechanical properties (tensile strength, elongation at break) before and after rubber aging were determined according to GB/T528-2009 test for tensile stress strain Properties of vulcanized rubber or thermoplastic rubber and GB/T2951.12-2008 general test methods for Cable and Cable insulation and sheath materials, part 12, respectively: the general test method-thermal aging test method "was used to determine the sample size for a standard dumbbell sample. The volume resistivity of the EPDM rubber insulating material is determined according to GB/T31838.2-2019 part 2 dielectric and resistance characteristics of solid insulating materials: resistance characteristics (DC method) volume resistance and volume resistivity. The dielectric strength of the ethylene propylene diene monomer insulating material is determined according to GB/T1408.1-2016 insulating material electrical strength test method part 1: and testing according to the test standard under the power frequency.
The samples prepared in each order were numbered, and the ingredients used in each example and comparative example are shown in tables 1 and 2, and the specific properties are shown in table 3.
TABLE 1 examples
TABLE 2 comparative examples
TABLE 3 physical properties of EPT rubber insulating material
As shown in tables 1 to 3, the test method was consistent with the test procedure in all tests. The ethylene propylene diene monomer insulation materials prepared in examples 1 to 9 were excellent in mechanical properties, aging properties and electrical properties. Comparative example 1 compares with example 4, metallocene polyethylene is changed into low density polyethylene, the elongation at break is lower, the flexibility of the insulating material is poor, the processing is more difficult, and the application of the insulating material to the occasion needing to bear mechanical stress for a long time can not be realized. Compared with the example 2, the comparative example 2 does not use metallocene polyethylene and a coupling agent, the mechanical property of the insulating material is greatly reduced before and after aging, and the cable has potential safety hazards of mechanical stress and breakage and cracking after aging; therefore, the addition of the metallocene polyethylene and the coupling agent can improve the mechanical properties of the insulating material before and after aging, so that the insulating material can be widely applied to marine shore power cables and wind power torsion-resistant cables which need to bear high mechanical stress for a long time. Compared with the example 2, the filler is changed into carbon black, so that the electrical property is greatly reduced, the electrical insulating property is poor, and the filler is not suitable for cables; therefore, the electrical insulation performance of the insulation material can be improved by adopting the reinforcing fillers such as fumed silica, alumina fiber, titanium dioxide, mica powder and the like.
In conclusion, according to the preparation method of the ethylene propylene diene monomer insulating material with high mechanical property provided by the patent, the ethylene propylene diene monomer and the metallocene polyethylene are used as the matrix, the reinforcing filler and the auxiliary agent are added, so that the ethylene propylene diene monomer insulating material with excellent mechanical property, thermal stability and electrical insulating property is obtained, the processing and preparation process is easy, the surface is smooth, the requirement on equipment is low, the environment is protected, and the ethylene propylene diene monomer insulating material can be widely applied to the insulation of marine shore power cables, wind power torsion resistant cables and other cables which need to bear high mechanical stress for a long time.
The upper and lower limits and interval values of the raw materials and the upper and lower limits and interval values of the process parameters can all realize the invention, and examples are not listed in the description.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations can be devised by those skilled in the art in light of the above teachings. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. An ethylene propylene diene monomer insulating material with high mechanical property is characterized in that: the rubber composition comprises 60-95 parts of ethylene propylene diene monomer, 5-40 parts of metallocene polyethylene, 0.5-2 parts of peroxide vulcanizing agent, 0.5-2 parts of vulcanizing assistant, 30-50 parts of reinforcing filler, 0.8-1.2 parts of stearic acid, 4-6 parts of zinc oxide, 1-3 parts of plasticizer, 1-3 parts of anti-aging agent and 1-3 parts of coupling agent.
2. The high-mechanical-property ethylene propylene diene monomer insulating material according to claim 1, wherein: and 75-90 parts of ethylene propylene diene monomer.
3. The high mechanical property ethylene propylene diene monomer insulating material according to claim 1, wherein: 10-40 parts of metallocene polyethylene.
4. The high mechanical property ethylene propylene diene monomer insulating material according to claim 1, wherein: the peroxide vulcanizing agent is one of dicumyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and di-tert-butylperoxy diisopropylbenzene.
5. The high mechanical property ethylene propylene diene monomer insulating material according to claim 1, wherein: the vulcanizing assistant is one or more of triallyl isocyanurate, tri-allylisocyanate, N '- (1, 4-phenylene) bismaleimide, N' -m-phenylene bismaleimide, 1, 2-phenylene-bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, triallyl (phenyl) silane, tetraallylsilane, methyl triallylsilane and triallylamine.
6. The high-mechanical-property ethylene propylene diene monomer insulating material according to claim 1, wherein: the reinforcing filler is non-conductive reinforcing filler and is one or more of fumed silica, alumina fiber, titanium dioxide and mica powder.
7. The high mechanical property ethylene propylene diene monomer insulating material according to claim 1, wherein: the plasticizer is one or more of paraffin oil, pine tar, triethylene glycol and diisodecyl phthalate.
8. The high mechanical property ethylene propylene diene monomer insulating material according to claim 1, wherein: the antioxidant is one or more of antioxidant 1010, antioxidant 6PPD, antioxidant UOP88, antioxidant SP, antioxidant 2246S and antioxidant 264.
9. The high mechanical property ethylene propylene diene monomer insulating material according to claim 1, wherein: the coupling agent is any one of gamma-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, triisostearoyl isopropyl titanate, sodium stearate and hexadecyl trimethyl ammonium bromide.
10. The preparation method of the ethylene propylene diene monomer insulating material with high mechanical property is characterized by comprising the following steps:
(1) Sequentially adding 60-95 parts of ethylene propylene diene monomer, 5-40 parts of metallocene polyethylene, 30-50 parts of reinforcing filler, 1-3 parts of coupling agent, 1 part of stearic acid, 5 parts of zinc oxide, 1-3 parts of plasticizer and 1-3 parts of anti-aging agent into an internal mixer, melting and blending for 10-30 min at 50-150 ℃, then adding 0.5-2 parts of peroxide vulcanizing agent and 0.5-2 parts of vulcanizing assistant, uniformly mixing, and taking out a primary mixture;
(2) placing the primary mixture in a mold, preheating the primary mixture for 3-7 min on a flat vulcanizing machine at the temperature of 115 +/-5 ℃ without pressurizing, then hot-pressing the primary mixture for 25-35 min under the conditions that the temperature is 170 +/-5 ℃ and the pressurizing pressure is 15-20 Mpa, and finally pressurizing and cooling the primary mixture to room temperature and taking the primary mixture out to obtain the ethylene propylene diene monomer insulating material with high mechanical property.
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