CN114806028B - Ethylene propylene diene monomer composite material and preparation method and application thereof - Google Patents
Ethylene propylene diene monomer composite material and preparation method and application thereof Download PDFInfo
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- CN114806028B CN114806028B CN202210487925.8A CN202210487925A CN114806028B CN 114806028 B CN114806028 B CN 114806028B CN 202210487925 A CN202210487925 A CN 202210487925A CN 114806028 B CN114806028 B CN 114806028B
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- ethylene propylene
- diene monomer
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- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 131
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 63
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000004073 vulcanization Methods 0.000 claims description 64
- 239000000463 material Substances 0.000 claims description 63
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 44
- 239000005662 Paraffin oil Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 239000013543 active substance Substances 0.000 claims description 30
- 239000004014 plasticizer Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 235000021355 Stearic acid Nutrition 0.000 claims description 22
- 239000006229 carbon black Substances 0.000 claims description 22
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 22
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 22
- 239000008117 stearic acid Substances 0.000 claims description 22
- 239000011787 zinc oxide Substances 0.000 claims description 22
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 21
- 230000003712 anti-aging effect Effects 0.000 claims description 20
- 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 19
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 19
- 239000007822 coupling agent Substances 0.000 claims description 13
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 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
- 239000005995 Aluminium silicate Substances 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 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 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
- 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 description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 5
- 229960002447 thiram Drugs 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 13
- 230000007774 longterm Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 description 160
- 238000004513 sizing Methods 0.000 description 33
- 239000003963 antioxidant agent Substances 0.000 description 17
- 230000003078 antioxidant effect Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 241000282320 Panthera leo Species 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 101100440919 Escherichia phage 186 CP80 gene Proteins 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 241000872198 Serjania polyphylla Species 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 230000035882 stress Effects 0.000 description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 239000013256 coordination polymer Substances 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 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
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of rubber composite materials, and particularly relates to an ethylene propylene diene monomer rubber composite material, and a preparation method and application thereof. The invention provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight: 80-120 parts of ethylene propylene diene monomer rubber; 1-30 parts of liquid ethylene propylene rubber; 20-60 parts of reinforcing filler; and the ethylene propylene diene monomer, the liquid ethylene propylene rubber and the reinforcing filler are required to satisfy the following relationship in parts by weight:wherein a represents the weight parts of ethylene propylene diene monomer, b represents the weight parts of liquid ethylene propylene rubber, and c represents the weight parts of reinforcing filler. The ethylene propylene diene monomer rubber composite material provided by the invention has excellent rebound resilience, and can be aged for 168 hours at 70 ℃, the 125% fixed tensile permanent deformation rate is less than or equal to 30%, the 150% fixed tensile permanent deformation rate is less than or equal to 35%, and the long-term use requirement of high-voltage direct current cable accessories is met.
Description
Technical Field
The invention belongs to the technical field of rubber composite materials, and particularly relates to an ethylene propylene diene monomer rubber composite material, and a preparation method and application thereof.
Background
With the increasing distance of the hvth cable, the demand for cable accessories is also increasing. Prefabricated accessories are widely used in already running land-based high voltage dc-crosslinked polyethylene cabling. The electrical and mechanical problems inside the dc cable accessory are more pronounced than with conventional ac cable accessories.
The design of the hvdc cable accessory is a complex process involving electrical, mechanical, material and thermodynamics. Because of the phenomenon of electric field stress concentration, the composite interface between the high-voltage direct-current cable and the accessory is a typical part of the weakest link and operation fault of the power transmission system. The rubber material requires a certain amount of interference or expansion to achieve contact surface pressure of the accessory to the cable fit. When the interface pressure between the cable accessory and the cable insulation reaches the range of 0.1-0.25MPa, the electric strength requirement can be met, and the installation difficulty or the cable insulation damage can not be caused. Along with the aging of the rubber material, stress relaxation occurs, so that the interface pressure between the cable accessory and the cable insulator is reduced, the service life is influenced, and accidents are caused.
At present, the method for improving the performance of the cable accessory is to regulate and control by means of a material with high J-E nonlinear conductivity, so that the cable accessory material has excellent nonlinear conductivity characteristics, has the function of homogenizing an electric field at a cable terminal, and reduces the accident probability.
Because the rubber material for the cable accessories is in a stretching and expanding state for a long time, the rubber material has the capability of recovering the original state after being released, namely the rebound resilience is used for representing the ageing resistance of the rubber material. Rebound resilience refers to the degree to which deformation stress is relieved and then the original state is quickly recovered, and the rebound resilience is characterized by adopting fixed tensile permanent deformation. However, in the prior art, the service life of the material is generally prolonged by optimizing the Mooney viscosity and the direct-current breakdown strength of the ethylene propylene diene monomer composite material, the rebound resilience performance of the material is less researched, and the influence of the rebound resilience on the service life of the material is not concerned.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that in the prior art, the service life of the material is generally improved by optimizing the Mooney viscosity and the direct current breakdown strength of the ethylene-propylene-diene monomer rubber composite material, the research on the rebound resilience performance of the material is less, the influence of the rebound resilience on the service life of the material is not concerned, the ethylene-propylene-diene monomer rubber-based cable composite material in the prior art does not have excellent rebound resilience performance and cannot meet the long-term use of high-voltage direct current cable accessories, and the like, so that the ethylene-propylene-diene monomer rubber composite material and the preparation method and the application thereof are provided.
Therefore, the invention provides the following technical proposal,
the invention provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
80-120 parts of ethylene propylene diene monomer rubber;
1-30 parts of liquid ethylene propylene rubber;
20-60 parts of reinforcing filler;
and the ethylene propylene diene monomer, the liquid ethylene propylene rubber and the reinforcing filler are required to satisfy the following relationship in parts by weight:
wherein a represents the weight parts of ethylene propylene diene monomer, b represents the weight parts of liquid ethylene propylene rubber, and c represents the weight parts of reinforcing filler.
The liquid ethylene propylene rubber is a terpolymer of ethylene, propylene and non-conjugated diene with relatively low molecular weight and number average molecular weight less than 60000, and can firstly play a role of a plasticizer in the mixing process of the ethylene propylene diene rubber, thereby being beneficial to improving the processability of the ethylene propylene diene rubber and improving the dispersibility of the reinforcing filler and reducing the problems of reduced mechanical property, volatilization and exudation of the plasticizer and the like of the ethylene propylene diene rubber caused by overhigh content of the traditional plasticizer; secondly, the liquid ethylene propylene rubber can also participate in crosslinking together with ethylene propylene diene monomer rubber in the vulcanization process, and the ethylene propylene diene monomer rubber has a triethylene group, so that the crosslinking reaction degree of the ethylene propylene diene monomer rubber compound is obviously improved; in addition, a small amount of non-conjugated diene in the liquid ethylene-propylene rubber is subjected to polymerization reaction in the rubber material and is partially grafted on a rubber molecular chain, so that the ethylene-propylene-diene monomer rubber has an excellent reinforcing effect, the crosslinking degree and the mechanical strength of the ethylene-propylene-diene monomer rubber are improved, and the rebound performance of the material is improved.
Optionally, the ethylene propylene diene monomer, the liquid ethylene propylene monomer and the reinforcing filler need to satisfy the following relationship in parts by weight:
in a preferred embodiment of the invention, the a is 100 parts by weight, b is 1-30 parts by weight, c is 20-60 parts by weight, preferably c is 40 parts, and c/a < b < c/2, preferably b=10c/a+c/5.
The content b of the liquid ethylene propylene rubber may be, for example, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight or 15 parts by weight.
The content c of the reinforcing filler may be, for example, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight or 55 parts by weight.
In a preferred embodiment of the present invention, the liquid ethylene propylene rubber is any one of TRILENE56, TRILENE65, TRILENE66, TRILENE67, TEILENECP80, TRILENE4038, liquid ethylene propylene rubber CP80 of lion chemistry, of the company TRILENE65, us You Niluo.
In a preferred embodiment of the present invention, the ethylene propylene diene monomer is selected from the group consisting of Mooney viscosity of 20-55MU at ML (1+4) 100deg.C and ethylene content of 45-75%, preferably, the ethylene propylene diene monomer is any one of 4725P of Dow, 2450 of Langshen and 2504 of Ekksen.
In a preferred embodiment of the present invention, the reinforcing filler is at least one of white carbon black, calcium carbonate, kaolin, clay, alkali silicate, and mica powder.
Optionally, the method further comprises:
3-5 parts of vulcanizing agent;
6.5-43 parts of auxiliary agent.
In a preferred embodiment of the invention, the feedstock further comprises a sulfiding agent.
In a preferred embodiment of the present invention, the vulcanizing agent comprises at least one of dicumyl peroxide or dibenzoyl peroxide.
In a preferred embodiment of the present invention, the vulcanizing agent is contained in an amount of 3 to 5 parts by weight, for example, 3.2 parts by weight, 3.4 parts by weight, 3.6 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.4 parts by weight, 4.6 parts by weight, or 4.8 parts by weight.
Optionally, the ethylene propylene diene monomer rubber composite material satisfies at least one of the following (1) - (5):
(1) The Mooney viscosity of the liquid ethylene propylene rubber is lower than 10MU under the condition of ML (1+4) 100 ℃;
(2) The Mooney viscosity of the ethylene propylene diene monomer is 20-55MU at ML (1+4) 100 ℃, and the ethylene content accounts for 45-75% of the weight of the ethylene propylene diene monomer;
typically, but not by way of limitation, the ethylene propylene diene monomer is one of the group 4025P, 2450 from langerhans, and 2504 from exxon;
(3) The reinforcing filler comprises one or more of white carbon black, calcium carbonate, kaolin, clay, alkali silicate and mica powder;
(4) The vulcanizing agent comprises one or more of sulfur, dicumyl peroxide or dibenzoyl peroxide;
(5) The auxiliary agent comprises one or more of an active agent, an anti-aging agent, a vulcanization accelerator, a coupling agent or a plasticizer.
In a preferred embodiment of the present invention, the raw material further comprises an auxiliary agent, further preferably the auxiliary agent comprises at least one of an active agent, an anti-aging agent, a vulcanization accelerator, a coupling agent or a plasticizer, most preferably the auxiliary agent comprises a combination of an active agent, an anti-aging agent, a vulcanization accelerator, a coupling agent and a plasticizer.
Optionally, the ethylene propylene diene monomer rubber composite material satisfies at least one of the following (1) - (6):
(1) The active agent comprises one or more of zinc oxide, stearic acid, zinc stearate and calcium stearate; preferably, the purity of the zinc oxide is 95.5% or more.
(2) The anti-aging agent comprises one or more of an anti-aging agent MB and an anti-aging agent RD;
(3) The vulcanization accelerator comprises one or more of tetramethylthiuram disulfide, 2-mercaptobenzothiazole, triallyl isocyanurate, N-cyclohexyl-2-benzothiazole sulfenamide and N-tertiary butyl-2-benzothiazole sulfenamide;
the triallyl isocyanurate has a density of 1.1-1.2g/m 3 The melting point is 26-28 ℃.
(4) The plasticizer comprises one or more of paraffin oil, naphthenic oil and white oil;
typically, but not limited to, the naphthenic oil may be one of Xinjiang KelamayKN 4006, 4010 of Hebei European Jia Lubricant Co.
(5) The coupling agent is a silane coupling agent;
(6) The coupling agent includes one or more of bis- (gamma-triethoxysilylpropyl) tetrasulfide and vinyltris (beta-methoxyethoxy) silane.
In a preferred embodiment of the present invention, the active agent comprises at least one of zinc oxide, stearic acid, zinc stearate and calcium stearate, preferably the zinc oxide has a purity of 95.5% or more.
In a preferred embodiment of the invention, the active agent is present in an amount of 4-7 parts by weight, for example 4.2 parts by weight, 4.4 parts by weight, 4.6 parts by weight, 4.8 parts by weight, 5 parts by weight, 5.2 parts by weight, 5.4 parts by weight, 5.6 parts by weight or 5.8 parts by weight.
In a preferred embodiment of the present invention, the anti-aging agent comprises at least one of an anti-aging agent MB, an anti-aging agent RD, preferably an anti-aging agent RD.
In a preferred embodiment of the present invention, the content of the anti-aging agent is 1 to 2 parts by weight, for example, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, or 1.9 parts by weight.
In a preferred embodiment of the present invention, the vulcanization accelerator comprises at least one of tetramethylthiuram disulfide, 2-mercaptobenzothiazole, triallyl isocyanurate, N-cyclohexyl-2-benzothiazole sulfenamide, and N-tert-butyl-2-benzothiazole sulfenamide, preferably triallyl isocyanurate.
In a preferred embodiment of the present invention, the vulcanization accelerator is contained in an amount of 0.5 to 2 parts by weight, for example, 0.7 parts by weight, 0.9 parts by weight, 1.1 parts by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7 parts by weight or 1.9 parts by weight.
In a preferred embodiment of the present invention, the plasticizer includes at least one of paraffinic oil, naphthenic oil, and white oil.
In a preferred embodiment of the invention, the plasticizer is present in an amount of 1% to 13% of the sum of the weight of the ethylene propylene diene monomer and the liquid ethylene propylene monomer, i.e. the plasticizer is present in an amount of (a+b) x 1-3%. The plasticizer content is more, the surface precipitation is easy to cause, the plasticizer content is less, and the plasticizer can not be effectively used as the plasticizer together with the liquid ethylene propylene rubber, so that the processability of the ethylene propylene diene monomer rubber is improved.
In a preferred embodiment of the present invention, the coupling agent is a silane coupling agent, preferably, the silane coupling agent includes at least one of bis- (γ -triethoxysilylpropyl) tetrasulfide and vinyltris (β -methoxyethoxy) silane.
In a preferred embodiment of the present invention, the silane coupling agent is contained in an amount of 1% to 20% by weight of the reinforcing filler.
Optionally, the ethylene propylene diene monomer rubber composite material comprises the following raw materials in parts by weight:
optionally, the ethylene propylene diene monomer composite material is aged for 168 hours at 70 ℃ and has 125% set elongation set deformation less than or equal to 30% and 150% set elongation set deformation less than or equal to 35%.
Optionally, the ethylene propylene diene monomer rubber insulating material has a hardness of 35-65A, preferably 40-60A.
In a preferred embodiment of the invention, the ethylene propylene diene monomer rubber composite material of the high-voltage direct-current cable accessory comprises the following raw materials in parts by weight:
100 parts of ethylene propylene diene monomer rubber; 6-18 parts of liquid ethylene propylene rubber; white carbon black: 20-60 parts of a lubricant; zinc oxide: 4-7 parts of a lubricant; stearic acid: 1-2 parts; anti-aging agent: 1-2 parts; and (3) a plasticizer: the content of the plasticizer is 1% -13% of the sum of the weight of the ethylene propylene diene monomer and the weight of the liquid ethylene propylene diene monomer; vulcanizing agent: 3-5 parts; vulcanization accelerators: 0.5-2 parts; coupling agent: the content of the silane coupling agent is 1-20% of the weight of the white carbon black.
The invention provides a preparation method of the ethylene propylene diene monomer composite material, which comprises the following steps,
and weighing the raw materials according to a proportion, and performing primary banburying and secondary banburying to obtain the ethylene propylene diene monomer composite material.
Specifically, the preparation method of the ethylene propylene diene monomer rubber composite material for the high-voltage direct-current cable accessory comprises the following steps:
and mixing the uniformly mixed raw materials in sequence to obtain the ethylene propylene diene monomer rubber composite material for the high-voltage direct-current cable accessory.
In a preferred embodiment of the present invention, the preparation method comprises the steps of:
(a) In order to improve the dispersibility of the filler, it is preferable to uniformly mix the reinforcing filler with the coupling agent;
(b) And (3) carrying out primary banburying: adding ethylene propylene diene monomer into an internal mixer for 2-3min, wherein the internal mixer has a rotating speed of 40-50r/min and a banburying temperature of 80-100 ℃, adding an active agent for banburying for 2-3min, and the internal mixer has a rotating speed of 40-50r/min and a banburying temperature of 80-100 ℃; adding a mixture of liquid ethylene propylene rubber, reinforcing filler and coupling agent, an anti-aging agent and 50% of plasticizer, banburying for 3-6min at a speed of 40-50r/min and a banburying temperature of 80-100 ℃, then adding the rest plasticizer, banburying for 1-3min at a speed of 40-50r/min and a banburying temperature of 80-100 ℃, and then plasticating for 15min in an open mill at a roll gap of 1-10mm, and standing for 6-12h to obtain a primary sizing material;
(c) Two-stage banburying: adding the primary sizing material into an internal mixer for 1-3min, wherein the internal mixer has the rotating speed of 40-50r/min, the internal mixing temperature of 50-70 ℃, adding a vulcanizing agent and a vulcanization accelerator, carrying out internal mixing, wherein the rotating speed of the internal mixer is 40-50r/min, the internal mixing temperature is 50-70 ℃, then carrying out plasticating for 5-15min in an open mill, the roll spacing of the open mill is 0.5-1.5mm, adding sizing material, carrying out thin-pass, carrying out triangular wrapping for 3-5 times, and carrying out blanking for 1-10mm to obtain the high-voltage direct current cable accessory ethylene propylene diene monomer rubber composite material.
The invention also provides application of the ethylene propylene diene monomer composite material or the ethylene propylene diene monomer composite material prepared by the preparation method in high-voltage direct-current cable accessory materials.
The technical proposal provided by the invention has the following advantages,
1. the invention provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight: 80-120 parts of ethylene propylene diene monomer rubber; 1-30 parts of liquid ethylene propylene rubber; 20-60 parts of reinforcing filler; and the ethylene propylene diene monomer, the liquid ethylene propylene rubber and the reinforcing filler are required to satisfy the following relationship in parts by weight:wherein a represents the weight parts of ethylene propylene diene monomer, b represents the weight parts of liquid ethylene propylene rubber, and c represents the weight parts of reinforcing filler. The ethylene propylene diene monomer rubber composite material provided by the invention has excellent rebound resilience, and can be aged for 168 hours at 70 ℃, the 125% fixed tensile permanent deformation rate is less than or equal to 30%, the 150% fixed tensile permanent deformation rate is less than or equal to 35%, and the high pressure is satisfiedThe DC cable accessory has long-term use requirement. In the composite material provided by the invention, if the content of the liquid ethylene propylene rubber is too small, the processing performance of the composite material can be reduced, and if the content of the liquid ethylene propylene rubber is too large, the crosslinking density of the composite material can be too large. The liquid ethylene propylene rubber is a terpolymer of ethylene, propylene and non-conjugated diene with the number average molecular weight less than 60000, and the liquid ethylene propylene rubber has the number average molecular weight less than 60000, can firstly play a role of a plasticizer in the mixing process of the ethylene propylene diene monomer, is beneficial to improving the processability of the ethylene propylene diene monomer and the dispersibility of the reinforcing filler, and reduces the problems of reduced mechanical property, volatilization and exudation of the plasticizer and the like of the ethylene propylene diene monomer caused by the overhigh content of the traditional plasticizer.
The invention provides an ethylene propylene diene monomer composite material, which also comprises a vulcanizing agent, wherein in the vulcanizing process, the liquid ethylene propylene rubber can also participate in crosslinking with the ethylene propylene diene monomer, and the ethylene propylene diene monomer has a triethylene group, so that the crosslinking reaction degree of the ethylene propylene diene monomer rubber compound is obviously improved; in addition, a small amount of non-conjugated diene in the liquid ethylene propylene rubber is subjected to polymerization reaction in the rubber material and is partially grafted on a rubber molecular chain, so that the ethylene propylene diene monomer rubber has an excellent reinforcing effect, the crosslinking degree and the mechanical strength of the ethylene propylene diene monomer rubber are improved, and the rebound performance of the material is improved.
2. The ethylene propylene diene monomer composite material provided by the invention contains the plasticizer, can be effectively used as the plasticizer together with the liquid ethylene propylene rubber, and improves the Mooney viscosity of the ethylene propylene diene monomer composite material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is data of 125% set after aging of an ethylene propylene diene monomer composite at 70℃for 168 hours.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
100kg of ethylene propylene diene monomer (type 4725P of Dow), 9kg of liquid ethylene propylene rubber (type liquid ethylene propylene rubber CP80 of lion chemistry), 30kg of white carbon black, 4kg of dicumyl peroxide, 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), 1kg of antioxidant RD,2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), 8kg of paraffin oil and 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The embodiment also provides a preparation method of the ethylene propylene diene monomer composite material, which comprises the following steps,
(1) Primary mixing: mixing 30kg of white carbon black with 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 100kg of ethylene propylene diene monomer (4725P with the model of Dow) into an internal mixer, mixing for 2min, wherein the mixing speed is 43r/min, mixing temperature is 90 ℃, adding 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), mixing for 2min, mixing speed is 43r/min, mixing temperature is 90 ℃, adding 9kg of liquid ethylene propylene rubber (liquid ethylene propylene rubber CP80 with the model of lion chemistry), 33kg of the mixture in the step (1), 1kg of an antioxidant RD and 4kg of paraffin oil, mixing for 5min, mixing speed is 45r/min, mixing temperature is 90 ℃, adding 4kg of paraffin oil, mixing for 2min, mixing speed is 43r/min, mixing temperature is 90 ℃, mixing for 15min, mixing roll spacing of 10mm in an open mill, and standing for 6h to obtain primary sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, adding 4kg of dicumyl peroxide and 2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), internally mixing for 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, plasticating for 5min in an open mill, the roll spacing of the open mill is 1.5mm, adding the sizing material, thinning, triangulating for 4 times, and discharging 3mm.
Example 2
The embodiment provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
100kg of ethylene propylene diene monomer (type 4725P of Dow), 9kg of liquid ethylene propylene rubber (type TRILENE 65), 30kg of white carbon black, 4kg of dicumyl peroxide, 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), 1kg of antioxidant RD,2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), 2kg of plasticizer (2 kg of paraffin oil) and 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The embodiment also provides a preparation method of the ethylene propylene diene monomer composite material, which comprises the following steps,
(1) Primary mixing: mixing 30kg of white carbon black with 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 100kg of ethylene propylene diene monomer (4725P with the model of Dow) into an internal mixer, mixing for 2min, wherein the mixing speed is 43r/min, the mixing temperature is 90 ℃, then adding 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), mixing for 2min, the mixing speed is 43r/min, the mixing temperature is 90 ℃, then adding 9kg of liquid ethylene propylene rubber (TRILENE 65), 33kg of the mixture in the step (1), 1kg of an anti-aging agent RD and 1kg of paraffin oil, mixing for 5min, the mixing speed is 45r/min, the mixing temperature is 90 ℃, then adding 1kg of paraffin oil, mixing for 2min, the mixing speed is 43r/min, the mixing temperature is 90 ℃, mixing for 15min in an open mill, the roll distance is 10mm, and standing for 6h to obtain an initial sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, adding 4kg of dicumyl peroxide and 2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), internally mixing for 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, plasticating for 5min in an open mill, the roll spacing of the open mill is 1.5mm, adding the sizing material, thinning, triangulating for 4 times, and discharging 3mm.
Embodiment 3 this embodiment provides an ethylene propylene diene monomer composite material, comprising the following raw materials by weight:
100kg of ethylene propylene diene monomer (model number TRILENE 65), 15kg of liquid ethylene propylene rubber (model number TRILENE 65), 50kg of precipitated silica, 4kg of dicumyl peroxide, 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), 1kg of antioxidant RD,2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), 5kg of paraffin oil and 6kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The embodiment also provides a preparation method of the ethylene propylene diene monomer composite material, which comprises the following steps,
(1) Primary mixing: mixing 50kg of white carbon black with 6kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 100kg of ethylene propylene diene monomer (2450 of Langsheng type) into an internal mixer, mixing for 2min at the speed of 43r/min, mixing at 90 ℃ for 2min, adding 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), mixing at 43r/min at 90 ℃ for 2min, adding 15kg of liquid ethylene propylene rubber (TRILENE 65 of TRILENE type) into the mixture of step (1), 56kg of the mixture of step (1), 1kg of antioxidant RD and 2.5kg of paraffin oil, mixing for 5min at 45r/min at 90 ℃, adding 2.5kg of paraffin oil, mixing for 2min at 43r/min at 90 ℃, mixing at 15min, mixing at 10mm of roll spacing in an open mill, and standing for 6h to obtain primary sizing;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, adding 4kg of dicumyl peroxide and 2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), internally mixing for 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, plasticating for 5min in an open mill, the roll spacing of the open mill is 1.5mm, adding the sizing material, thinning, triangulating for 4 times, and discharging 3mm.
Example 4
The embodiment provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
100kg of ethylene propylene diene monomer (type 4725P of Dow), 9kg of liquid ethylene propylene rubber (type liquid ethylene propylene rubber CP80 of lion chemistry), 30kg of calcium carbonate, 4kg of sulfur, 7kg of active agent (7 kg of stearic acid), 1kg of antioxidant MB,2kg of vulcanization accelerator (2 kg of tetramethylthiuram disulfide), 8kg of paraffin oil and 3kg of vinyltris (beta-methoxyethoxy) silane.
The embodiment also provides a preparation method of the ethylene propylene diene monomer composite material, which comprises the following steps,
(1) Primary mixing: mixing 30kg of sulphur with 3kg of vinyltris (beta-methoxyethoxy) silane;
(2) And (3) carrying out primary banburying: adding 100kg of ethylene propylene diene monomer (4725P with the model of Dow) into an internal mixer, mixing for 2min at the speed of 43r/min, mixing at 90 ℃ for 2min with 7kg of active agent (7 kg of stearic acid) at the speed of 43r/min, mixing at 90 ℃ with 9kg of liquid ethylene propylene rubber (CP 80 with the model of lion chemistry), 33kg of the mixture in the step (1), 1kg of an antioxidant MD and 4kg of paraffin oil for 5min, mixing at the speed of 45r/min at the temperature of 90 ℃, adding 4kg of paraffin oil, mixing for 2min at the speed of 43r/min, mixing at the temperature of 90 ℃ for 15min, mixing at the roll spacing of 10mm in an open mill, and standing for 6h to obtain an initial sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃,4kg of sulfur and 2kg of vulcanization accelerator (2 kg of tetramethylthiuram disulfide) are added, the internal mixing time is 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, the internal mixing is carried out for 5min, the roll gap of the internal mixer is 1.5mm, the sizing material is added, triangular bags are made for 4 times, and the blanking is 3mm.
Example 5
The embodiment provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
100kg of ethylene propylene diene monomer (type 4725P of Dow), 9kg of liquid ethylene propylene rubber (type liquid ethylene propylene rubber CP80 of lion chemistry), 30kg of kaolin, 4kg of dibenzoyl peroxide, 7kg of active agent (7 kg of calcium stearate), 1kg of antioxidant RD,2kg of vulcanization accelerator (2 kg of 2-mercaptobenzothiazole), 8kg of paraffin oil and 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The embodiment also provides a preparation method of the ethylene propylene diene monomer composite material, which comprises the following steps,
(1) Primary mixing: mixing 30kg of kaolin with 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 100kg of ethylene propylene diene monomer (4725P with the model of Dow) into an internal mixer, mixing for 2min at the speed of 43r/min, mixing at 90 ℃ for 2min with 7kg of active agent (7 kg of calcium stearate) at the speed of 43r/min, mixing at 90 ℃ with 9kg of liquid ethylene propylene rubber (CP 80 with the model of lion chemistry), 33kg of the mixture in the step (1), 1kg of an antioxidant RD and 4kg of paraffin oil, mixing for 5min at the speed of 45r/min at the mixing temperature of 90 ℃, mixing with 4kg of paraffin oil again at the mixing speed of 2min, mixing at the speed of 43r/min at the mixing temperature of 90 ℃ for 15min, mixing at the roll spacing of 10mm in an open mill, and standing for 6h to obtain an initial sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, adding 4kg of dibenzoyl peroxide and 2kg of vulcanization accelerator (2 kg of 2-mercaptobenzothiazole), banburying for 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, plasticating for 5min in an open mill, the roll spacing of the open mill is 1.5mm, adding sizing material, making triangular bags for 4 times, and blanking for 3mm.
Example 6
The embodiment provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
80kg of ethylene propylene diene monomer (type 4725P of Dow), 29kg of liquid ethylene propylene rubber (type liquid ethylene propylene rubber CP80 of lion chemistry), 60kg of white carbon black, 5kg of dicumyl peroxide, 4kg of active agent (consisting of 3kg of zinc oxide and 1kg of stearic acid), 2kg of antioxidant RD,0.5kg of vulcanization accelerator (consisting of 0.25kg of vulcanization accelerator CZ and 0.25kg of vulcanization accelerator NS), 1kg of paraffin oil and 12kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The embodiment also provides a preparation method of the ethylene propylene diene monomer composite material, which comprises the following steps,
(1) Primary mixing: mixing 60kg of white carbon black with 12kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 80kg of ethylene propylene diene monomer (4725P with the model of Dow) into an internal mixer, mixing for 2min, wherein the mixing temperature is 90 ℃ at 43r/min, adding 4kg of active agent (composed of 3kg of zinc oxide and 1kg of stearic acid), mixing for 2min, mixing at 43r/min at 90 ℃ at 29kg of liquid ethylene propylene rubber (CP 80 with the model of lion chemistry), adding 72kg of the mixture in the step (1), 2kg of an antioxidant RD and 0.5kg of paraffin oil, mixing for 5min at 45r/min at 90 ℃, adding 0.5kg of paraffin oil, mixing for 2min at 43r/min at 90 ℃, standing for 15min at an open mill, and obtaining the primary sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min at the speed of 45r/min and at the temperature of 50 ℃, adding 5kg of dicumyl peroxide and 0.5kg of vulcanization accelerator (consisting of 0.25kg of vulcanization accelerator CZ and 0.25kg of vulcanization accelerator NS), banburying for 1min at the speed of 45r/min and at the temperature of 50 ℃, plasticating for 5min in an open mill, setting the roll gap of 1.5mm, adding the sizing material into the mixture, making triangular bags for 4 times, and blanking for 3mm.
Example 7
The embodiment provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
120kg of ethylene propylene diene monomer (type 4725P of Dow), 1kg of liquid ethylene propylene rubber (type of liquid ethylene propylene rubber CP80 of lion chemistry), 60kg of white carbon black, 3kg of dicumyl peroxide, 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), 1kg of antioxidant RD,2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), 15kg of paraffin oil and 0.6kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The embodiment also provides a preparation method of the ethylene propylene diene monomer composite material, which comprises the following steps,
(1) Primary mixing: mixing 60kg of white carbon black with 0.6kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 120kg of ethylene propylene diene monomer (4725P with the model of Dow) into an internal mixer, mixing for 2min at the speed of 43r/min, mixing at 90 ℃ for 2min, adding 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), mixing at the speed of 43r/min, mixing at 90 ℃ for 2min, adding 1kg of liquid ethylene propylene rubber (liquid ethylene propylene rubber CP80 with the model of lion chemistry), 60.6kg of the mixture in the step (1), 1kg of an antioxidant RD and 7.5kg of paraffin oil, mixing for 5min at the speed of 45r/min, mixing at 90 ℃ for 2min, adding 7.5kg of paraffin oil, mixing at the speed of 43r/min, mixing at 90 ℃ for 15min, mixing at the speed of 10mm and standing for 6h to obtain an initial sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, adding 3kg of dicumyl peroxide and 2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), internally mixing for 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, plasticating for 5min in an open mill, the roll spacing of the open mill is 1.5mm, adding the sizing material, thinning, triangulating for 4 times, and discharging 3mm.
Comparative example 1
The comparative example provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
100kg of ethylene propylene diene monomer (model 4725P), 30kg of white carbon black, 4kg of dicumyl peroxide, 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), 1kg of antioxidant RD,2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), 8kg of paraffin oil and 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The comparative example also provides a preparation method of the ethylene propylene diene monomer rubber composite material, which comprises the following steps,
(1) Primary mixing: mixing 30kg of white carbon black with 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 100kg of ethylene propylene diene monomer (4725P with the type of Dow) into an internal mixer, mixing for 2min, wherein the mixing temperature is 90 ℃, adding 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), mixing for 2min, mixing at 43r/min, mixing at 90 ℃, adding 33kg of the mixture obtained in the step (1), 1kg of anti-aging agent RD and 4kg of paraffin oil, mixing for 5min, mixing at 45r/min, mixing at 90 ℃, adding 4kg of paraffin oil, mixing for 2min, mixing at 43r/min, mixing at 90 ℃, mixing at 15min, mixing at a roll gap of 10mm in an open mill, and standing for 6h to obtain primary sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, adding 4kg of dicumyl peroxide and 2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), internally mixing for 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, plasticating for 5min in an open mill, the roll spacing of the open mill is 1.5mm, adding the sizing material, thinning, triangulating for 4 times, and discharging 3mm.
Comparative example 2
The comparative example provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
100kg of ethylene propylene diene monomer (type 4725P of Dow), 30kg of liquid ethylene propylene rubber (type of liquid ethylene propylene rubber CP80 of lion chemistry), 8kg of white carbon black, 4kg of dicumyl peroxide, 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), 1kg of antioxidant RD,2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), 8kg of paraffin oil and 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The comparative example also provides a preparation method of the ethylene propylene diene monomer rubber composite material, which comprises the following steps,
(1) Primary mixing: mixing 8kg of white carbon black with 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 100kg of ethylene propylene diene monomer (4725P with the model of Dow) into an internal mixer, mixing for 2min, wherein the mixing speed is 43r/min, mixing temperature is 90 ℃, adding 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), mixing for 2min, mixing speed is 43r/min, mixing temperature is 90 ℃, adding 30kg of liquid ethylene propylene rubber (liquid ethylene propylene rubber CP80 with the model of lion chemistry), 33kg of the mixture in the step (1), 1kg of an antioxidant RD and 4kg of paraffin oil, mixing for 5min, mixing speed is 45r/min, mixing temperature is 90 ℃, adding 4kg of paraffin oil, mixing for 2min, mixing speed is 43r/min, mixing temperature is 90 ℃, mixing for 15min, mixing roll spacing of 10mm in an open mill, and standing for 6h to obtain primary sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, adding 4kg of dicumyl peroxide and 2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), internally mixing for 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, plasticating for 5min in an open mill, the roll spacing of the open mill is 1.5mm, adding the sizing material, thinning, triangulating for 4 times, and discharging 3mm.
Comparative example 3
The comparative example provides an ethylene propylene diene monomer composite material, which comprises the following raw materials in parts by weight:
100kg of ethylene propylene diene monomer (type 4725P of Dow), 15kg of liquid ethylene propylene rubber (type of liquid ethylene propylene rubber CP80 of lion chemistry), 65kg of white carbon black, 4kg of dicumyl peroxide, 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), 1kg of antioxidant RD,2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), 8kg of paraffin oil and 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide.
The comparative example also provides a preparation method of the ethylene propylene diene monomer rubber composite material, which comprises the following steps,
(1) Primary mixing: mixing 65kg of white carbon black with 3kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide;
(2) And (3) carrying out primary banburying: adding 100kg of ethylene propylene diene monomer (4725P with the model of Dow) into an internal mixer, mixing for 2min, wherein the mixing speed is 43r/min, mixing temperature is 90 ℃, adding 7kg of active agent (consisting of 5kg of zinc oxide and 2kg of stearic acid), mixing for 2min, mixing speed is 43r/min, mixing temperature is 90 ℃, adding 15kg of liquid ethylene propylene rubber (CP 80 with the model of lion chemistry), 33kg of the mixture in the step (1), 1kg of an antioxidant RD and 4kg of paraffin oil, mixing for 5min, mixing speed is 45r/min, mixing temperature is 90 ℃, adding 4kg of paraffin oil, mixing for 2min, mixing speed is 43r/min, mixing temperature is 90 ℃, mixing for 15min, mixing roll spacing is 10mm in an open mill, and standing for 6h to obtain primary sizing material;
(3) Two-stage banburying: adding the primary sizing material into an internal mixer for 2min, wherein the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, adding 4kg of dicumyl peroxide and 2kg of vulcanization accelerator (consisting of 1kg of vulcanization accelerator CZ and 1kg of vulcanization accelerator NS), internally mixing for 1min, the rotation speed of the internal mixer is 45r/min, the internal mixing temperature is 50 ℃, plasticating for 5min in an open mill, the roll spacing of the open mill is 1.5mm, adding the sizing material, thinning, triangulating for 4 times, and discharging 3mm.
Test example 1
The ethylene propylene diene monomer rubber composites prepared in examples 1 to 7 and comparative examples 1 to 3 were respectively subjected to tensile strength, elongation at break, tear strength, hardness, mooney viscosity, elastic modulus, 125% tensile set, 150% tensile set, and dc breakdown strength performance tests. The specific test method is as follows:
test method of tensile strength and elongation at break: according to GB/T528 2008 standard (dumbbell type test pieces);
hardness testing method: tested according to GB/T531.1 2008 standard;
the tearing strength test method comprises the following steps: according to GB/T529 2008 standard test (Right angle test);
the Mooney viscosity test method comprises the following steps: tested according to GB/T1232.1-2016 standard;
the method for testing the direct current breakdown strength comprises the following steps: tested according to GB/T1408.2 2006 standard;
the test methods for 125% and 150% tensile set were: referring to a method for determining the stretching permanent deformation of standard IOS 2285-2013 vulcanized rubber, preparing a standard test piece for testing the stretching performance by tabletting, presetting a standard distance of 25-50mm, fixing 125% or 150% of stretching, placing in a 70+/-2 ℃ oven for 168 hours, taking out and cooling for 30 minutes, taking down the test piece, horizontally placing in a laboratory, testing the recovery data of a product at room temperature, and determining the stretching permanent deformation rate.
The test performance index is as follows:
the specific test results are as follows:
conclusion: comparative example 1 compared with example 1, the content of the liquid ethylene propylene rubber is reduced from 9kg to 0kg, the hardness of the material is larger, the elongation at break is lower, the Mooney viscosity is larger, the tearing strength is smaller, and the 125% tensile permanent deformation rate of the material after aging for 168 hours at 70 ℃ is more than 30%.
Comparative example 2 the material breakdown strength was significantly reduced compared to example 2 by increasing the liquid ethylene propylene rubber content from 9kg to 30 kg.
Comparative example 3 compared with example 3, the white carbon black content is increased from 50kg to 65kg, the hardness of the material is improved, the filler dispersibility is poor, the elongation at break is less than 500%, the Mooney viscosity is more than 40MU, and the 125% tensile permanent deformation rate of the material after aging for 168 hours at 70 ℃ is more than 30%.
Test example 2
The ethylene propylene diene monomer rubber composites prepared in examples 1 to 7 and comparative examples 1 to 3 were respectively subjected to rebound resilience and service life performance tests. The specific test method is as follows:
the method for testing rebound performance comprises the following steps: tested according to the ISO2285-2013 standard. The sample is a small annular sample. The service life testing method comprises the following steps: experimental method an experimental scheme is formulated by referring to the tensile stress relaxation test standard for measuring the aging performance of GB/T9871-2008 vulcanized rubber or thermoplastic rubber. The stress relaxation characteristics of the ethylene propylene diene monomer rubber at the aging temperature of 70 ℃ and different stretching ratios (125% and 150%) are measured, and the aging time is 1 month.
According to the time-temperature equivalent principle, the stress relaxation characteristics of the rubber material at normal temperature are reversely deduced through researching the stress relaxation characteristics of the rubber material at high temperature and in a short time. The time-temperature equivalent method can be successfully used for predicting the reliability and the service life of the interface holding force/pressure of the accessory insulating long-term operation device. And carrying out data fitting on a time-varying relation graph of 125% and 150% of expansion rate of the material at 70 ℃ after the WLF equation is translated, and obtaining the graph through Boltzmann mathematical fitting to obtain the aged tensile permanent deformation rate, wherein the life expectancy requirement of the cable accessory is 30 years.
The specific test results are as follows:
from the above table, it can be seen that: comparative example 1 the liquid ethylene propylene rubber content was reduced from 9kg to 0kg compared with example 1, and after 125% and 150% of the material was drawn at set, the tensile set after 30 years was greater and both were greater than 40%.
Comparative example 2 the liquid ethylene propylene rubber content was increased from 9kg to 30kg compared with example 2, and after 150% stretching of the material, the tensile set after 30 years was greater than 40%.
Comparative example 3 the white carbon black content was increased from 50kg to 65kg, and after the material was stretched 125% and 150% at a constant tension, the tensile set after 30 years was large and both were greater than 40%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The ethylene propylene diene monomer rubber composite material is characterized by comprising the following raw materials in parts by weight:
80-120 parts of ethylene propylene diene monomer rubber;
1-30 parts of liquid ethylene propylene rubber;
20-60 parts of reinforcing filler;
and the ethylene propylene diene monomer, the liquid ethylene propylene rubber and the reinforcing filler are required to satisfy the following relationship in parts by weight:
，/>；
wherein a represents the weight parts of ethylene propylene diene monomer, b represents the weight parts of liquid ethylene propylene rubber, and c represents the weight parts of reinforcing filler;
the Mooney viscosity of the liquid ethylene propylene rubber is lower than 10MU under the condition of ML (1+4) 100 ℃;
the Mooney viscosity of the ethylene propylene diene monomer is 20-55MU at ML (1+4) 100 ℃, and the ethylene content accounts for 45-75% of the weight of the ethylene propylene diene monomer;
the reinforcing filler comprises one or more of white carbon black, calcium carbonate, kaolin, clay, alkali silicate and mica powder.
2. The ethylene propylene diene monomer composite material of claim 1, further comprising:
3-5 parts of vulcanizing agent;
6.5-43 parts of auxiliary agent.
3. Ethylene propylene diene monomer composite material according to claim 2, characterized in that at least one of the following (1), (2) is satisfied:
(1) The vulcanizing agent comprises one or more of sulfur, dicumyl peroxide or dibenzoyl peroxide;
(2) The auxiliary agent comprises one or more of an active agent, an anti-aging agent, a vulcanization accelerator, a coupling agent or a plasticizer.
4. The ethylene propylene diene monomer composite material according to claim 3, characterized in that at least one of the following (1) to (6) is satisfied:
(1) The active agent comprises one or more of zinc oxide, stearic acid, zinc stearate and calcium stearate;
(2) The anti-aging agent comprises one or more of an anti-aging agent MB and an anti-aging agent RD;
(3) The vulcanization accelerator comprises one or more of tetramethylthiuram disulfide, 2-mercaptobenzothiazole, triallyl isocyanurate, N-cyclohexyl-2-benzothiazole sulfenamide and N-tertiary butyl-2-benzothiazole sulfenamide;
(4) The plasticizer comprises one or more of paraffin oil, naphthenic oil and white oil;
(5) The coupling agent is a silane coupling agent;
(6) The coupling agent includes one or more of bis- (gamma-triethoxysilylpropyl) tetrasulfide and vinyltris (beta-methoxyethoxy) silane.
5. The ethylene propylene diene monomer composite material according to claim 3, wherein,
comprises the following raw materials in parts by weight:
80-120 parts of ethylene propylene diene monomer rubber;
1-30 parts of liquid ethylene propylene rubber;
20-60 parts of reinforcing filler;
3-5 parts of vulcanizing agent;
4-7 parts of an active agent;
1-2 parts of an anti-aging agent;
0.5-2 parts of vulcanization accelerator;
0.2-12 parts of coupling agent;
0.81-19.5 parts of plasticizer.
6. The ethylene propylene diene monomer composite material according to any one of claims 1 to 5, wherein the ethylene propylene diene monomer composite material has a set tension set of 125% of not more than 30% and a set tension set of 150% of not more than 35% after aging for 168 hours at 70 ℃.
7. The ethylene propylene diene monomer composite material according to any one of claims 1 to 5, characterized in that the ethylene propylene diene monomer insulating material has a hardness of 35 to 65A.
8. The ethylene propylene diene monomer composite material according to claim 7, wherein the ethylene propylene diene monomer insulating material has a hardness of 40-60A.
9. A process for preparing the composite material of EPDM rubber according to any one of claims 2-8, which comprises the following steps,
and weighing the raw materials according to a proportion, and performing primary banburying and secondary banburying to obtain the ethylene propylene diene monomer composite material.
10. Use of the ethylene propylene diene monomer composite material according to any one of claims 1 to 8 or the ethylene propylene diene monomer composite material prepared by the preparation method according to claim 9 in high-voltage direct current cable accessory materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102585379A (en) * | 2011-01-13 | 2012-07-18 | 北京橡胶工业研究设计院 | Ethylene propylene diene rubber composition and preparation method |
| CN103254518A (en) * | 2013-06-08 | 2013-08-21 | 武汉科能电气有限公司 | Electric insulating rubber and fabrication method thereof |
| CN109957179A (en) * | 2017-12-22 | 2019-07-02 | 特变电工股份有限公司 | Ultra-clean EP rubbers cable insulating material of 35kV and preparation method thereof |
| CN113024958A (en) * | 2021-03-16 | 2021-06-25 | 无锡百年通工业输送有限公司 | High-elongation rubber for joints and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585379A (en) * | 2011-01-13 | 2012-07-18 | 北京橡胶工业研究设计院 | Ethylene propylene diene rubber composition and preparation method |
| CN103254518A (en) * | 2013-06-08 | 2013-08-21 | 武汉科能电气有限公司 | Electric insulating rubber and fabrication method thereof |
| CN109957179A (en) * | 2017-12-22 | 2019-07-02 | 特变电工股份有限公司 | Ultra-clean EP rubbers cable insulating material of 35kV and preparation method thereof |
| CN113024958A (en) * | 2021-03-16 | 2021-06-25 | 无锡百年通工业输送有限公司 | High-elongation rubber for joints and preparation method thereof |
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