CN116285195A - High-wear-resistance sheath material for locomotive cable and preparation method thereof - Google Patents
High-wear-resistance sheath material for locomotive cable and preparation method thereof Download PDFInfo
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- CN116285195A CN116285195A CN202310354088.6A CN202310354088A CN116285195A CN 116285195 A CN116285195 A CN 116285195A CN 202310354088 A CN202310354088 A CN 202310354088A CN 116285195 A CN116285195 A CN 116285195A
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- evm
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- banburying
- sheath material
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 230000003137 locomotive effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 33
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004073 vulcanization Methods 0.000 claims abstract description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003292 glue Substances 0.000 claims abstract description 3
- 239000006229 carbon black Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000012752 auxiliary agent Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 27
- 229920001971 elastomer Polymers 0.000 claims description 26
- 239000005060 rubber Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 238000005299 abrasion Methods 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 4
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- VQBBXLZPRXHYBO-UHFFFAOYSA-N 2-methoxyterephthalic acid Chemical compound COC1=CC(C(O)=O)=CC=C1C(O)=O VQBBXLZPRXHYBO-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 claims description 2
- VQIKAPKIEUECEL-UHFFFAOYSA-N 2-phenoxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(OC=2C=CC=CC=2)=C1 VQIKAPKIEUECEL-UHFFFAOYSA-N 0.000 claims description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 2
- WUKNPIYSKBLCQI-UHFFFAOYSA-N CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O Chemical compound CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O WUKNPIYSKBLCQI-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 19
- 230000032683 aging Effects 0.000 abstract description 13
- 125000003700 epoxy group Chemical group 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 93
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 44
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 36
- 239000005038 ethylene vinyl acetate Substances 0.000 description 26
- 239000011787 zinc oxide Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 235000021355 Stearic acid Nutrition 0.000 description 16
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 16
- 239000008117 stearic acid Substances 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 15
- 230000003078 antioxidant effect Effects 0.000 description 15
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229920000459 Nitrile rubber Polymers 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- DEKVAWHRMRNKMI-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1OOC(C)(C)C DEKVAWHRMRNKMI-UHFFFAOYSA-N 0.000 description 9
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DDKIXUQHRSUCMN-UHFFFAOYSA-N n-butylbutan-1-amine;propan-2-one Chemical compound CC(C)=O.CCCCNCCCC DDKIXUQHRSUCMN-UHFFFAOYSA-N 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 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 description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003051 synthetic 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
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 relates to the technical field of cable sheath materials, in particular to a high-wear-resistance sheath material for locomotive cables and a preparation method thereof, and the high-wear-resistance sheath material comprises the following preparation processes: mixing EVM with acrylonitrile, butadiene and unsaturated monomer, heating to react to obtain modified EVM; respectively banburying the modified EVM and EVM-GMA to obtain a banburying glue; mixing and vulcanizing to obtain the sheath material. The modified EVM is obtained by in-situ copolymerization of acrylonitrile, butadiene and unsaturated monomers in an EVM solution, the polarity is improved, the intermolecular acting force is stronger, and the wear resistance, oil resistance, ageing resistance and strength of the modified EVM are improved; in the mixing vulcanization, epoxy groups in EVM-GMA are ring-opened and react with carboxyl/isocyanate groups in modified EVM, so that the crosslinking density of EVM-GMA and modified EVM is improved, the crosslinking network structure is more perfect, the tensile strength and tearing strength of the prepared sheath material are improved, and the performances of wear resistance, ageing resistance, hardness and the like are effectively improved.
Description
Technical Field
The invention relates to the technical field of cable sheath materials, in particular to a high-wear-resistance sheath material for locomotive cables and a preparation method thereof.
Background
Along with the rapid development of the China rail transit industry, the control of rail locomotives, motor train units and high-speed units is more and more complex, and the number of matched electrical control equipment is more and more. The demand for cables used by rail transit vehicles has also increased. The cross-linked polyolefin material with higher hardness used for the traditional locomotive cable is inconvenient to install and lay. The EVM has excellent performances, and can be widely applied to cable products as special rubber. But the wear resistance is poor, and the abrasion-resistant rubber is extremely easy to damage after being rubbed with the outside in the installation and use processes. Therefore, we propose a high wear-resistant sheath material for locomotive cables and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a high-wear-resistance sheath material for locomotive cables and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the high-wear-resistance sheath material for the locomotive cable comprises the following preparation processes:
step 1: mixing the EVM solution with acrylonitrile, butadiene, unsaturated monomer and catalyst under the protection of nitrogen atmosphere, and heating to react to obtain modified EVM;
taking modified EVM, adding carbon black, a vulcanizing agent and an auxiliary agent, plasticizing and banburying to obtain modified EVM banburying;
step 2: taking EVM-GMA, adding carbon black, a vulcanizing agent and an auxiliary agent, plasticizing and banburying to obtain EVM-GMA banburying glue;
step 3: and (3) placing the modified EVM rubber compound and the EVM-GMA rubber compound into an open mill for mixing, and performing plate vulcanization to obtain the sheath material.
Further, the modified EVM is prepared from the following components in parts by weight: 100-150 parts of EVM, 30-40 parts of acrylonitrile, 57-68 parts of butadiene, 2-3 parts of unsaturated monomer and 0.4-0.8 part of catalyst;
the catalyst is triisobutylaluminum and octanol substituted MoCl 5 The molar ratio is 2.5:1; octanol substituted MoCl 5 In MoCl 5 The molar ratio of octanol is 1:2;
the EVM solution contains 10-15 g/100mL of toluene as solvent.
Further, the modified EVM masterbatch was prepared from the following components by weight: 100 parts of modified EVM, 20-40 parts of carbon black, 2.0-3.0 parts of vulcanizing agent and 7.2-10.0 parts of auxiliary agent.
Further, the EVM-GMA masterbatch was prepared from the following components by weight: 100 parts of EVM-GMA, 20-40 parts of carbon black, 2.0-3.0 parts of vulcanizing agent and 7.2-10.0 parts of auxiliary agent.
Further, the sheath material is prepared from 100 parts by mass of modified EVM (ethylene-vinyl acetate) rubber compound and 100-150 parts by mass of EVM-GMA rubber compound.
Further, carbon black: n550, from Jiangxi black cat carbon black Co., ltd;
the vulcanizing agent is one of dicumyl peroxide DCP and di-tert-butyl peroxyisopropyl benzene BIPB;
the auxiliary agent comprises the following components in parts by weight: 2.4 to 5.0 parts of zinc oxide, 0.8 to 2.0 parts of stearic acid, 1.0 to 2.0 parts of accelerator DM and 1.0 to 2.0 parts of anti-aging agent RD;
zinc oxide: from Jiangsu Pu Le Si Biotech Co., ltd;
EVM (ethylene-vinyl acetate rubber): EVM500 and EVM700 in a mass ratio of 1:1, derived from Lang Cheng Gongsi, germany;
EVM-GMA: the epoxy group content was 2.9% and was from lang, germany.
Further, the step 1 comprises the following preparation processes:
placing the EVM solution in a sealed reaction kettle, protecting the EVM solution in a nitrogen atmosphere, sequentially adding acrylonitrile, butadiene, unsaturated monomers and catalysts, and reacting for 9-10 h at 60-65 ℃; placing the mixture in ethanol for aggregation, and drying the mixture at 60-80 ℃ to constant weight to obtain modified EVM;
drying the modified EVM for 8 hours at 80 ℃, placing the dried EVM in a rheometer for banburying for 2-3 min, adding an auxiliary agent for banburying for 2-3 min, adding carbon black for banburying for 3-4 min, adding a vulcanizing agent for banburying for 5-6 min, wherein the rotation speed of the rheometer is 50-60 r/min, and the banburying temperature is 80-120 ℃ to obtain the modified EVM banburying.
Further, the step 2 comprises the following preparation process:
placing EVM-GMA in a rheometer for banburying for 2-3 min, adding an auxiliary agent for banburying for 2-3 min, adding carbon black for banburying for 3-4 min, adding a vulcanizing agent for banburying for 5-6 min, wherein the rotation speed of the rheometer is 25-30 r/min, and the banburying temperature is 60-65 ℃ to obtain the EVM-GMA banburying.
Further, the step 3 comprises the following preparation process:
placing the modified EVM rubber compound and the EVM-GMA rubber compound into an open mill, mixing for 6-8 min at 25-40 ℃, and standing for 16-24 h at room temperature; and (3) performing plate vulcanization under the vulcanization condition of 170-175 ℃ and 10-15 MPa multiplied by T90 to obtain the sheath material.
Further, the unsaturated monomer is an unsaturated carboxylic acid or an unsaturated isocyanate.
The unsaturated carboxylic acid is acrylic acid or methacrylic acid;
the unsaturated isocyanate is one or more of 3-propylene isocyanate, vinyl isocyanate, propylene isocyanate, isocyanate ethyl acrylate, methacryloyl isocyanate, isocyano ethyl methacrylate and modified monomer.
Further, the modified monomer is prepared by the following process:
mixing deionized water, diamine, sodium hydroxide and sodium dodecyl sulfate, and stirring for dissolution; stirring in ice water bath at 0-4 ℃, slowly adding acryloyl chloride, recovering the room temperature after the addition is completed for 30min, and reacting for 3-8 h; filtering, washing with water until the pH value of the filtrate is neutral, and drying at 60-80 ℃ for 8-12 h to obtain unsaturated amine;
mixing ethanol and diacid, slowly adding diamine, and finishing the addition within 30min; heating to 70-80 ℃, and condensing and refluxing for 3-5 h; unsaturated amine is added to continue the reaction for 20 to 40 minutes; distilling under reduced pressure, and drying to obtain amino-terminated polyamide;
mixing acetone and diisocyanate, heating to 50-55 ℃ in nitrogen atmosphere, vigorously stirring, slowly adding amino-terminated amide, and finishing the addition for 2 hours; and (3) restoring the room temperature, adding a catalyst dibutyltin dilaurate, and reacting for 1-5 min to obtain the unsaturated monomer.
Further, the unsaturated isocyanate is blocked by methyl ethyl ketoxime, and the specific process is as follows:
mixing acetone and unsaturated isocyanate, adding methyl ethyl ketoxime, and carrying out end capping reaction for 30min; the content of residual isocyanate groups was determined by titration with acetone-di-n-butylamine until the advantageous isocyanate group content was no longer changed.
Further, the molar ratio of diamine to acrylic chloride is 1:1.01;
diamine, sodium hydroxide and sodium dodecyl sulfonate in the molar ratio of 1:2:0.01;
the proportion of diamine and deionized water is (10-15) g to 100mL.
Further, the mol ratio of diacid, diamine and unsaturated amine is 10:10 (1.1-1.3);
the ratio of diacid to ethanol is 5g/100mL.
Further, the molar ratio of amino groups to diisocyanate in the amino-terminated polyamide is 1:1;
the ratio of diisocyanate to acetone is 5g/100mL;
further, the ratio of unsaturated isocyanate to acetone was 12g/100mL.
Further, the diamine is one or more of p-phenylenediamine, 3 '-dimethyl-4, 4' -biphenyl diamine, 4 '-diaminodiphenylmethane, 4' -biphenyl diamine, 3 '-dimethoxy-4, 4' -diaminophenylmethane.
Further, the diacid is one or more of terephthalic acid, 2-methoxy terephthalic acid, 2-phenoxy terephthalic acid and 4,4' -biphenyl dicarboxylic acid.
Further, the diisocyanate is one or more of naphthalene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, isophorone diisocyanate and dimethylbiphenyl diisocyanate.
In the technical scheme, the sheath material is prepared by mixing and vulcanizing EVM-GMA containing epoxy groups and modified EVM. The modified EVM is obtained by in-situ copolymerization of acrylonitrile, butadiene and unsaturated monomers in an EVM solution, and is nitrile rubber modified EVM, so that the polarity of the EVM is improved, and the intermolecular acting force is stronger; compared with mechanical blending, the nitrile rubber and the EVM are more uniformly dispersed, the compatibility is better, and the wear resistance and oil resistance of the modified EVM can be effectively improved. Carboxyl/isocyanate groups are introduced through unsaturated monomers, so that the polarity of the modified EVM is further enhanced, and the wear resistance, oil resistance, ageing resistance and strength of the modified EVM are improved; after mixing EVM-GMA and modified EVM, at the temperature in the plate vulcanization process, the epoxy groups in EVM-GMA open loop and can react with carboxyl/isocyanate groups in modified EVM to crosslink EVM-GMA and modified EVM, the crosslinking density of EVM-GMA and modified EVM is improved, the crosslinking network structure is more perfect, the capability of resisting external stress is improved, so that the wear resistance is good, the tensile and tearing strength of the prepared sheath material is improved, and the performances of wear resistance, aging resistance, hardness and the like are effectively improved.
And respectively plasticizing and banburying the EVM-GMA and the modified EVM before mixing. In the modified EVM banburying process, when unsaturated monomers in the modified EVM are unsaturated carboxylic acid (containing carboxyl), ionic bonds are formed between zinc oxide and carboxyl, so that the prepared sheath material can be reinforced. When unsaturated monomer in the modified EVM is unsaturated isocyanate (containing isocyanate group), the blocking agent methyl ethyl ketoxime deblocks the isocyanate group at the banburying process temperature, and the isocyanate group reacts with the surface hydroxyl of zinc oxide, so that the prepared sheath material can be reinforced.
When the unsaturated monomer in the modified EVM is a modified monomer (containing amide group), partial charge is changed from C=O double bond to Zn-O bond, electron density of the C=O double bond is reduced, hydrogen bond action between the C=O double bond and N-H is destroyed, complex coordination is carried out between the amide group and zinc ion to form a more stable hydrogen bond, interface strength between the modified EVM and zinc oxide can be improved, and dispersion of zinc oxide in the modified EVM is promoted; the mechanical property and the oil resistance of the modified EVM rubber compound and the prepared sheath material are improved, the thermal oxidative aging of the modified EVM can be prevented, and the fatigue resistance and the aging resistance of the modified EVM rubber compound are improved, so that the wear resistance of the modified EVM rubber compound and the prepared sheath material in the thermal oxidative aging process is improved; and the friction heat generation and the degradation of molecular chains and the fatigue abrasion generated by the strong shearing action are prevented in the abrasion resistance test process. And secondly, the modified monomer is prepared from diamine, diacid and diisocyanate containing benzene ring/naphthalene ring/cyclohexene/biphenyl structures, isocyanate groups in the modified EVM can react with epoxy groups in EVM-GMA to obtain an oxazole elastomer (heterocycle), and the benzene ring, heterocycle and aramid molecular chain structures are introduced into a modified EVM molecular system, so that the strength, mechanical property and wear resistance of the modified EVM can be further improved.
Compared with mechanical blending, the in-situ generation of the nitrile rubber in the EVM ensures that the EVM and the nitrile rubber in the prepared modified EVM are more uniformly dispersed, the dispersibility and the compatibility are better, and the wear resistance of the modified EVM and the prepared sheath material can be effectively improved.
Carbon black is added into the sheath material system as a reinforcing material, so that the particle size is small, the specific surface area is large, the structural degree is high, the crosslinking degree with EVM-GMA and modified EVM is increased, the abrasion volume of the prepared sheath material is reduced, and the abrasion resistance is improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The catalyst in the step 1 is triisobutylaluminum and octanol substituted MoCl 5 The molar ratio is 2.5:1; octanol substituted MoCl 5 In MoCl 5 The molar ratio of octanol is 1:2, and the octanol is prepared by reacting for 24 hours at room temperature under the protection of nitrogen;
carbon black: n550, from Jiangxi black cat carbon black Co., ltd;
zinc oxide: particle size of 0.3-0.7 μm, which is from Jiangsu Pu Le Si biological technology Co., ltd;
EVM (ethylene-vinyl acetate rubber): EVM500 and EVM700 in a mass ratio of 1:1, derived from Lang Cheng Gongsi, germany;
EVM-GMA (ethylene-vinyl acetate-glycidyl methacrylate rubber): the epoxy group content was 2.9% and was derived from german lang Cheng Gongsi;
NBR (nitrile butadiene rubber): n230, acrylonitrile content 35%, was obtained from Japanese synthetic rubber Co., ltd.
Example 1: step 1:
placing EVM solution (1250gEVM+10L toluene) in a sealed reaction kettle, protecting the atmosphere of nitrogen, sequentially adding 350g acrylonitrile, 625g butadiene, 25g unsaturated monomer acrylic acid and 6g catalyst, and reacting at 62 ℃ for 9h; placing in ethanol for aggregation, and drying at 80deg.C to constant weight to obtain modified EVM;
taking 1000g of modified EVM, drying at 80 ℃ for 8 hours, placing in a rheometer, banburying for 2 minutes, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2 minutes, adding 300g of carbon black, banburying for 3 minutes, adding 25g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB, banburying for 5 minutes, wherein the rotation speed of the rheometer is 60r/min, and the banburying temperature is 80 ℃ to obtain modified EVM banburying;
step 2: placing 1000g of EVM-GMA in a rheometer, banburying for 2min, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2min, adding 300g of carbon black, banburying for 3min, adding 25g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB, banburying for 5min, wherein the rotation speed of the rheometer is 30r/min, and the banburying temperature is 60 ℃ to obtain EVM-GMA banburying;
step 3: placing 1kg of modified EVM (ethylene-vinyl acetate) rubber masterbatch and 1.2kg of EVM-GMA rubber masterbatch into an open mill, mixing for 7min at 35 ℃, and standing for 20h at room temperature; and (3) performing plate vulcanization under the vulcanization condition of 170 ℃ and 12MPa multiplied by T90 to obtain the sheath material.
Example 2: step 1:
100mL of acetone and 12g of isocyanoethyl methacrylate are taken and mixed, 6.8g of methyl ethyl ketoxime is added for end-capping reaction for 30min; detecting the content of the residual isocyanate groups by titration of acetone-di-n-butylamine until the content of the favorable isocyanate groups is not changed any more;
placing EVM solution (1250gEVM+10L toluene) in a sealed reaction kettle, protecting the nitrogen atmosphere, sequentially adding 350g acrylonitrile, 625g butadiene, 25g unsaturated monomer isocyanoethyl methacrylate and 6g catalyst, and reacting at 62 ℃ for 9h; placing in ethanol for aggregation, and drying at 80deg.C to constant weight to obtain modified EVM;
taking 1000g of modified EVM, drying at 80 ℃ for 8 hours, placing in a rheometer, banburying for 2 minutes, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2 minutes, adding 300g of carbon black, banburying for 3 minutes, adding 25g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB, banburying for 5 minutes, wherein the rotation speed of the rheometer is 60r/min, and the banburying temperature is 80 ℃ to obtain modified EVM banburying;
step 2: placing 1000g of EVM-GMA in a rheometer, banburying for 2min, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2min, adding 300g of carbon black, banburying for 3min, adding 25g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB, banburying for 5min, wherein the rotation speed of the rheometer is 30r/min, and the banburying temperature is 60 ℃ to obtain EVM-GMA banburying;
step 3: placing 1kg of modified EVM (ethylene-vinyl acetate) rubber masterbatch and 1.2kg of EVM-GMA rubber masterbatch into an open mill, mixing for 7min at 35 ℃, and standing for 20h at room temperature; and (3) performing plate vulcanization under the vulcanization condition of 170 ℃ and 12MPa multiplied by T90 to obtain the sheath material.
Example 3: step 1:
100mL of deionized water, 10.8g of p-phenylenediamine, 8.0g of sodium hydroxide and 0.27g of sodium dodecyl sulfate are taken, mixed and stirred for dissolution; in 2 ℃ ice water bath, stirring, slowly adding 9.1g of acryloyl chloride, recovering to room temperature after 30min, and reacting for 5h; filtering, washing with water until the pH of the filtrate is neutral, and drying at 70 ℃ for 10 hours to obtain unsaturated amine;
mixing 332mL of ethanol and 16.6g of terephthalic acid, slowly adding 10.8g of p-phenylenediamine, and finishing the addition within 30min; heating to 75 ℃, and condensing and refluxing for 4 hours; 1.9g of unsaturated amine is added, and the reaction is continued for 30min; distilling under reduced pressure, and drying to obtain amino-terminated polyamide;
444mL of acetone and 22.2g of isophorone diisocyanate are taken and mixed, the temperature is raised to 52 ℃ in a nitrogen atmosphere, the mixture is stirred vigorously, 26.3g of amino-terminated amide is slowly added, and the addition is completed in 2 hours; returning to room temperature, adding 0.3g of catalyst dibutyltin dilaurate, and reacting for 3min; 8.7g of methyl ethyl ketoxime is added for end capping reaction for 30min; detecting the content of the residual isocyanate groups by titration of acetone-di-n-butylamine until the content of the favorable isocyanate groups is not changed any more, so as to obtain a modified monomer;
placing EVM solution (1250gEVM+10L toluene) in a sealed reaction kettle, protecting the atmosphere of nitrogen, sequentially adding 350g acrylonitrile, 625g butadiene, 25g modified monomer and 6g catalyst, and reacting at 62 ℃ for 9h; placing in ethanol for aggregation, and drying at 80deg.C to constant weight to obtain modified EVM;
taking 1000g of modified EVM, drying at 80 ℃ for 8 hours, placing in a rheometer, banburying for 2 minutes, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2 minutes, adding 300g of carbon black, banburying for 3 minutes, adding 25g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB, banburying for 5 minutes, wherein the rotation speed of the rheometer is 60r/min, and the banburying temperature is 80 ℃ to obtain modified EVM banburying;
step 2: placing 1000g of EVM-GMA in a rheometer, banburying for 2min, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2min, adding 300g of carbon black, banburying for 3min, adding 25g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB, banburying for 5min, wherein the rotation speed of the rheometer is 30r/min, and the banburying temperature is 60 ℃ to obtain EVM-GMA banburying;
step 3: placing 1kg of modified EVM (ethylene-vinyl acetate) rubber masterbatch and 1.2kg of EVM-GMA rubber masterbatch into an open mill, mixing for 7min at 35 ℃, and standing for 20h at room temperature; and (3) performing plate vulcanization under the vulcanization condition of 170 ℃ and 12MPa multiplied by T90 to obtain the sheath material.
Example 4: step 1:
125mL deionized water, 18.4g of 4,4' -biphenyl diamine, 8.0g of sodium hydroxide and 0.27g of sodium dodecyl sulfate are taken, mixed and stirred for dissolution; in an ice-water bath at 4 ℃, stirring, slowly adding 9.14g of acryloyl chloride, recovering the room temperature after the addition is completed for 30min, and reacting for 3h; filtering, washing with water until the pH of the filtrate is neutral, and drying at 60 ℃ for 8 hours to obtain unsaturated amine;
mixing 484mL of ethanol and 24.2g of 4,4 '-biphenyl diamine, slowly adding 18.4g of 4,4' -biphenyl diamine, and finishing the addition within 30min; heating to 70 ℃, and condensing and refluxing for 3 hours; 2.6g of unsaturated amine is added, and the reaction is continued for 20min; distilling under reduced pressure, and drying to obtain amino-terminated polyamide;
348mL of acetone and 17.4g of toluene diisocyanate are taken and mixed, the temperature is raised to 50 ℃ in a nitrogen atmosphere, the mixture is stirred vigorously, 40.4g of amino-terminated amide is slowly added, and the addition is completed in 2 hours; returning to room temperature, adding 0.3g of catalyst dibutyltin dilaurate, and reacting for 1min; 8.7g of methyl ethyl ketoxime is added for end capping reaction for 30min; detecting the content of the residual isocyanate groups by titration of acetone-di-n-butylamine until the content of the favorable isocyanate groups is not changed any more, so as to obtain a modified monomer;
placing EVM solution (1500 g EVM+10L toluene) in a sealed reaction kettle, protecting the sealed reaction kettle in a nitrogen atmosphere, sequentially adding 300g acrylonitrile, 680g butadiene, 20g modified monomer and 4g catalyst, and reacting for 9h at 60 ℃; placing in ethanol for aggregation, and drying at 60deg.C to constant weight to obtain modified EVM;
taking 1000g of modified EVM, drying at 80 ℃ for 8 hours, placing in a rheometer, banburying for 2 minutes, adding 72g of auxiliary agent (40 g of zinc oxide, 12g of stearic acid, 10g of accelerator DM and 10g of antioxidant RD), banburying for 2 minutes, adding 200g of carbon black, banburying for 3 minutes, adding 20g of vulcanizing agent dicumyl peroxide DCP, banburying for 5 minutes, wherein the rotation speed of the rheometer is 50r/min, and the banburying temperature is 80 ℃ to obtain modified EVM banburying;
step 2: placing 1000g of EVM-GMA in a rheometer for banburying for 2min, adding 72g of auxiliary agent (40 g of zinc oxide, 12g of stearic acid, 10g of accelerator DM and 10g of antioxidant RD) for banburying for 2min, adding 200g of carbon black for banburying for 3min, adding 20g of vulcanizing agent dicumyl peroxide DCP for banburying for 5min, wherein the rotation speed of the rheometer is 25r/min, and the banburying temperature is 60 ℃ to obtain EVM-GMA banburying;
step 3: 1kg of modified EVM (ethylene-vinyl acetate) rubber masterbatch and 1.5kg of EVM-GMA rubber masterbatch are placed in an open mill to be mixed for 6min at 25 ℃, and the mixture is kept stand for 16h at room temperature; and (3) performing plate vulcanization under the vulcanization condition of 170 ℃ and 10MPa multiplied by T90 to obtain the sheath material.
Example 5: step 1:
100mL of deionized water, 33.4g of 3,3 '-dimethoxy-4, 4' -diaminophenylmethane, 8.0g of sodium hydroxide and 0.27g of sodium dodecyl sulfate are taken, mixed and stirred for dissolution; in an ice-water bath at 0 ℃, stirring, slowly adding 9.1g of acryloyl chloride, recovering the room temperature after the addition is completed for 30min, and reacting for 8h; filtering, washing with water until the pH of the filtrate is neutral, and drying at 80 ℃ for 12 hours to obtain unsaturated amine;
392mL of ethanol and 19.6g of 2-methoxy terephthalic acid are taken and mixed, 33.4g of 3,3 '-dimethoxy-4, 4' -diaminophenylmethane is slowly added, and the addition is completed within 30 minutes; heating to 80 ℃, and condensing and refluxing for 5 hours; 5.0g of unsaturated amine is added, and the reaction is continued for 40min; distilling under reduced pressure, and drying to obtain amino-terminated polyamide;
444mL of acetone and 21.0g of naphthalene diisocyanate are taken and mixed, the temperature is raised to 55 ℃ in a nitrogen atmosphere, the mixture is stirred vigorously, 51.2g of amino-terminated amide is slowly added, and the addition is completed in 2 hours; returning to room temperature, adding 0.3g of catalyst dibutyltin dilaurate, and reacting for 5min; 8.7g of methyl ethyl ketoxime is added for end capping reaction for 30min; detecting the content of the residual isocyanate groups by titration of acetone-di-n-butylamine until the content of the favorable isocyanate groups is not changed any more, so as to obtain a modified monomer;
placing EVM solution (1000 g EVM+10L toluene) in a sealed reaction kettle, protecting the sealed reaction kettle in a nitrogen atmosphere, sequentially adding 400g acrylonitrile, 570g butadiene, 30g modified monomer and 8g catalyst, and reacting for 10 hours at 65 ℃; placing in ethanol for aggregation, and drying at 80deg.C to constant weight to obtain modified EVM;
taking 1000g of modified EVM, drying at 80 ℃ for 8 hours, placing in a rheometer, banburying for 3 minutes, adding 100g of auxiliary agent (50 g of zinc oxide, 20g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 3 minutes, adding 400g of carbon black, banburying for 4 minutes, adding 30g of vulcanizing agent dicumyl peroxide DCP and bis-tert-butyl peroxyisopropyl benzene BIPB, banburying for 6 minutes, wherein the rotation speed of the rheometer is 60r/min, and the banburying temperature is 120 ℃ to obtain modified EVM banburying;
step 2: placing 1000g of EVM-GMA in a rheometer for banburying for 3min, adding 100g of auxiliary agent (50 g of zinc oxide, 20g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD) for banburying for 3min, adding 400g of carbon black for banburying for 4min, adding 30g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB for banburying for 6min, wherein the rotation speed of the rheometer is 30r/min, and the banburying temperature is 65 ℃ to obtain EVM-GMA banburying;
step 3: placing 1kg of modified EVM (ethylene-vinyl acetate) rubber masterbatch and 1.0kg of EVM-GMA rubber masterbatch into an open mill, mixing for 8min at 40 ℃, and standing for 24h at room temperature; and (3) performing plate vulcanization under the conditions of 175 ℃ and 15MPa multiplied by T90 to obtain the sheath material.
Comparative example 1: step 1:
100mL of deionized water, 10.8g of p-phenylenediamine, 8.0g of sodium hydroxide and 0.27g of sodium dodecyl sulfate are taken, mixed and stirred for dissolution; in 2 ℃ ice water bath, stirring, slowly adding 9.1g of acryloyl chloride, recovering to room temperature after 30min, and reacting for 5h; filtering, washing with water until the pH of the filtrate is neutral, and drying at 70 ℃ for 10 hours to obtain unsaturated amine;
mixing 332mL of ethanol and 16.6g of terephthalic acid, slowly adding 10.8g of p-phenylenediamine, and finishing the addition within 30min; heating to 75 ℃, and condensing and refluxing for 4 hours; 1.9g of unsaturated amine is added, and the reaction is continued for 30min; distilling under reduced pressure, and drying to obtain amino-terminated polyamide;
444mL of acetone and 22.2g of isophorone diisocyanate are taken and mixed, the temperature is raised to 52 ℃ in a nitrogen atmosphere, the mixture is stirred vigorously, 26.3g of amino-terminated amide is slowly added, and the addition is completed in 2 hours; returning to room temperature, adding 0.3g of catalyst dibutyltin dilaurate, and reacting for 3min; 8.7g of methyl ethyl ketoxime is added for end capping reaction for 30min; detecting the content of the residual isocyanate groups by titration of acetone-di-n-butylamine until the content of the favorable isocyanate groups is not changed any more, so as to obtain a modified monomer;
10L of toluene is placed in a sealed reaction kettle, and is protected by nitrogen atmosphere, 350g of acrylonitrile, 620g of butadiene, 25g of modified monomer and 6g of catalyst are sequentially added, and the mixture is reacted for 9 hours at 62 ℃; placing the mixture in ethanol for aggregation, and drying the mixture at 80 ℃ to constant weight to obtain modified NBR;
taking 556g of EVM and 444g of modified NBR, drying at 80 ℃ for 8 hours, placing in a rheometer, banburying for 2 minutes, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2 minutes, adding 300g of carbon black, banburying for 3 minutes, adding 25g of vulcanizing agent bis-tert-butyl peroxy isopropyl benzene BIPB, banburying for 5 minutes, and obtaining modified EVM banburying at 80 ℃ at the rotation speed of 60 r/min;
step 2: placing 1000g of EVM-GMA in a rheometer, banburying for 2min, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2min, adding 300g of carbon black, banburying for 3min, adding 25g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB, banburying for 5min, wherein the rotation speed of the rheometer is 30r/min, and the banburying temperature is 60 ℃ to obtain EVM-GMA banburying;
step 3: placing 1kg of modified EVM (ethylene-vinyl acetate) rubber masterbatch and 1.2kg of EVM-GMA rubber masterbatch into an open mill, mixing for 7min at 35 ℃, and standing for 20h at room temperature; and (3) performing plate vulcanization under the vulcanization condition of 170 ℃ and 12MPa multiplied by T90 to obtain the sheath material.
Comparative example 2: step 1:
taking 556g of EVM and 444g of NBR, drying at 80 ℃ for 8 hours, placing in a rheometer, banburying for 2 minutes, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2 minutes, adding 300g of carbon black, banburying for 3 minutes, adding 25g of vulcanizing agent bis-tert-butyl peroxy isopropyl benzene BIPB, banburying for 5 minutes, wherein the rotation speed of the rheometer is 60r/min, and banburying at 80 ℃ to obtain modified EVM banburying;
step 2: placing 1000g of EVM-GMA in a rheometer, banburying for 2min, adding 80g of auxiliary agent (35 g of zinc oxide, 15g of stearic acid, 15g of accelerator DM and 15g of antioxidant RD), banburying for 2min, adding 300g of carbon black, banburying for 3min, adding 25g of vulcanizing agent bis-tert-butylperoxy isopropyl benzene BIPB, banburying for 5min, wherein the rotation speed of the rheometer is 30r/min, and the banburying temperature is 60 ℃ to obtain EVM-GMA banburying;
step 3: placing 1kg of modified EVM (ethylene-vinyl acetate) rubber masterbatch and 1.2kg of EVM-GMA rubber masterbatch into an open mill, mixing for 7min at 35 ℃, and standing for 20h at room temperature; and (3) performing plate vulcanization under the vulcanization condition of 170 ℃ and 12MPa multiplied by T90 to obtain the sheath material.
Comparative example 3: step 1:
taking 1556g EVM and 444g NBR, drying at 80 ℃ for 8 hours, placing in a rheometer, banburying for 2 minutes, adding 160g auxiliary agent (70 g zinc oxide, 30g stearic acid, 30g accelerator DM and 30g antioxidant RD), banburying for 2 minutes, adding 600g carbon black, banburying for 3 minutes, adding 50g vulcanizing agent bis-tert-butyl peroxy isopropyl benzene BIPB, banburying for 5 minutes, and obtaining modified EVM banburying at 80 ℃ at the rotational speed of 60 r/min;
step 2: placing the modified EVM rubber concentrate into an open mill, mixing for 7min at 35 ℃, and standing for 20h at room temperature; and (3) performing plate vulcanization under the vulcanization condition of 170 ℃ and 12MPa multiplied by T90 to obtain the sheath material.
Experiment
Taking the sheath materials obtained in examples 1-5 and comparative examples 1-3, preparing samples, respectively detecting the performances of the samples and recording the detection results:
mechanical properties: using GB/T528-2009 as a reference standard, adopting an electronic tensile machine to test the tensile strength of a sample, adopting a dumbbell-shaped sample, and stretching at a rate of 500mm/min;
DIN abrasion: using GB/T2526-2010 as a reference standard, and adopting a DIN abrasion tester to test the abrasion resistance of the sample;
compression set: compression set test is carried out at 100 ℃, the compression amount is 25%, the test is carried out for 24 hours, the test is taken out, the test is kept stand for 30 minutes, and the height of the test sample is measured again; calculating the compression set of the sample ((initial height of sample-post-experiment height)/(initial height of sample-stopper height) ×100%);
aging performance: and (3) taking GB/T3512 as a reference standard, and adopting an aging box to test the hot air aging performance of the sample, wherein the experimental condition is 150 ℃ multiplied by 24 hours.
| Tensile Strength (MPa) | Tensile Strength after aging (MPa) | Compression set (%) | DIN abrasion (mm) 3 ) | |
| Example 1 | 14.4 | 11.2 | 31 | 128 |
| Example 2 | 13.6 | 10.9 | 28 | 120 |
| Example 3 | 16.3 | 14.0 | 25 | 96 |
| Example 4 | 14.7 | 13.2 | 30 | 117 |
| Example 5 | 18.1 | 14.5 | 22 | 78 |
| Comparative example 1 | 13.1 | 10.9 | 27 | 109 |
| Comparative example 2 | 13.0 | 9.9 | 35 | 142 |
| Comparative example 3 | 12.7 | 9.7 | 37 | 154 |
From the data in the above table, the following conclusions can be clearly drawn:
the jacket materials obtained in examples 1 to 5 were compared with the jacket materials obtained in comparative examples 1 to 3, and it was found that the detection results,
compared with examples 1-2 and comparative examples 1-3, the jacket materials obtained in examples 3-5 have higher tensile strength data before and after hot air aging test and lower compression set and DIN abrasion data, which fully demonstrates that the invention realizes improvement of mechanical property, wear resistance and heat resistance of the prepared jacket materials.
Compared to example 3, the modified EVM in comparative example 1 is obtained by mechanical blending of modified NBR and EVM; comparative example 2 on the basis of comparative example 1, no modification of the NBR was made; the sheath material in comparative example 3 is obtained by mixing and vulcanizing EVM and NBR; the tensile strength data before and after the hot air aging test in comparative examples 1-3 are reduced, the compression set and DIN abrasion data are increased, and the invention can improve the mechanical property, the wear resistance and the heat resistance of the prepared sheath material by setting the modified EVM component and the process thereof.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-wear-resistance sheath material for locomotive cables is characterized by comprising the following steps of: the preparation method comprises the following preparation processes:
step 1: mixing the EVM solution with acrylonitrile, butadiene, unsaturated monomer and catalyst under the protection of nitrogen atmosphere, and reacting for 9-10 h at 60-65 ℃ to obtain modified EVM;
taking modified EVM, adding carbon black, a vulcanizing agent and an auxiliary agent, plasticizing and banburying to obtain modified EVM banburying;
step 2: taking EVM-GMA, adding carbon black, a vulcanizing agent and an auxiliary agent, plasticizing and banburying to obtain EVM-GMA banburying glue;
step 3: placing the modified EVM rubber compound and the EVM-GMA rubber compound into an open mill for mixing and performing plate vulcanization to obtain a sheath material;
the mass ratio of the modified EVM rubber compound to the EVM-GMA rubber compound is 1 (1.0-1.5).
2. The method for preparing the high wear-resistant sheath material for locomotive cables according to claim 1, which is characterized in that: the modified EVM is prepared from the following components in parts by weight: 100 to 150 parts of EVM, 30 to 40 parts of acrylonitrile, 57 to 68 parts of butadiene, 2 to 3 parts of unsaturated monomer and 0.4 to 0.8 part of catalyst.
3. The method for preparing the high wear-resistant sheath material for locomotive cables according to claim 1, which is characterized in that: the modified EVM masterbatch is prepared from the following components in parts by weight: 100 parts of modified EVM, 20-40 parts of carbon black, 2.0-3.0 parts of vulcanizing agent and 7.2-10.0 parts of auxiliary agent;
the EVM-GMA masterbatch is prepared from the following components in parts by weight: 100 parts of EVM-GMA, 20-40 parts of carbon black, 2.0-3.0 parts of vulcanizing agent and 7.2-10.0 parts of auxiliary agent.
4. The method for preparing the high wear-resistant sheath material for locomotive cables according to claim 1, which is characterized in that: the step 1 comprises the following preparation processes:
placing the EVM solution in a sealed reaction kettle, protecting the EVM solution in a nitrogen atmosphere, sequentially adding acrylonitrile, butadiene, unsaturated monomers and catalysts, and reacting for 9-10 h at 60-65 ℃ to obtain a modified EVM;
drying the modified EVM for 8 hours at 80 ℃, placing the dried EVM in a rheometer for banburying for 2-3 min, adding an auxiliary agent for banburying for 2-3 min, adding carbon black for banburying for 3-4 min, adding a vulcanizing agent for banburying for 5-6 min, wherein the rotation speed of the rheometer is 50-60 r/min, and the banburying temperature is 80-120 ℃ to obtain the modified EVM banburying.
5. The method for preparing the high wear-resistant sheath material for locomotive cables according to claim 1, which is characterized in that: the step 3 comprises the following preparation process:
placing the modified EVM rubber compound and the EVM-GMA rubber compound into an open mill, mixing for 6-8 min at 25-40 ℃, standing for 16-24 h at room temperature, and performing plate vulcanization under the vulcanization condition of 170-175 ℃ and 10-15 MPa multiplied by T90 to obtain the sheath material.
6. The method for preparing the high wear-resistant sheath material for locomotive cables according to claim 1, which is characterized in that: the unsaturated monomer is unsaturated carboxylic acid or unsaturated isocyanate; the unsaturated carboxylic acid is acrylic acid or methacrylic acid.
7. The method for preparing the high-wear-resistance sheath material for locomotive cables according to claim 6, which is characterized in that: the unsaturated isocyanate is one of 3-propylene isocyanate, vinyl isocyanate, propylene isocyanate, ethyl isocyanate acrylate, methacryloyl isocyanate, isocyano ethyl methacrylate and modified monomer;
the modified monomer is prepared by the following process:
mixing deionized water, diamine, sodium hydroxide and sodium dodecyl sulfate, and stirring for dissolution; stirring in ice water bath at 0-4 ℃, slowly adding acryloyl chloride, recovering the room temperature after the addition is completed for 30min, and reacting for 3-8 h to obtain unsaturated amine;
mixing ethanol and diacid, slowly adding diamine, and finishing the addition within 30min; heating to 70-80 ℃, and condensing and refluxing for 3-5 h; adding unsaturated amine, and continuing to react for 20-40 min to obtain amino-terminated polyamide;
mixing acetone and diisocyanate, heating to 50-55 ℃ in nitrogen atmosphere, vigorously stirring, slowly adding amino-terminated amide, and finishing the addition for 2 hours; and (3) restoring the room temperature, adding a catalyst dibutyl tin dilaurate, and reacting for 1-5 min to obtain the modified monomer.
8. The method for preparing the high-wear-resistance sheath material for locomotive cables according to claim 7, which is characterized in that: the mol ratio of the diacid to the diamine to the unsaturated amine is 10:10 (1.1-1.3).
9. The method for preparing the high-wear-resistance sheath material for locomotive cables according to claim 7, which is characterized in that: the diamine is one of p-phenylenediamine, 3 '-dimethyl-4, 4' -biphenyl diamine, 4 '-diaminodiphenyl methane, 4' -biphenyl diamine and 3,3 '-dimethoxy-4, 4' -diaminophenyl methane;
the diacid is one of terephthalic acid, 2-methoxy terephthalic acid, 2-phenoxy terephthalic acid and 4,4' -biphenyl dicarboxylic acid;
the diisocyanate is one of naphthalene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, isophorone diisocyanate and dimethylbiphenyl diisocyanate.
10. A highly abrasion resistant sheath material for locomotive cables prepared by the preparation method according to any one of claims 1 to 9.
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