CN109517234A - A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring - Google Patents
A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring Download PDFInfo
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- CN109517234A CN109517234A CN201811287461.6A CN201811287461A CN109517234A CN 109517234 A CN109517234 A CN 109517234A CN 201811287461 A CN201811287461 A CN 201811287461A CN 109517234 A CN109517234 A CN 109517234A
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- parts
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- instrument
- sealing ring
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- 238000007789 sealing Methods 0.000 title claims abstract description 28
- 230000032683 aging Effects 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 20
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 24
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 24
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims abstract description 20
- 239000010959 steel Substances 0.000 claims abstract description 20
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004113 Sepiolite Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 19
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 19
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 19
- OXFFVYXBKPZBSW-UHFFFAOYSA-N butyl prop-2-enoate;2-methylprop-2-enoic acid;prop-2-enenitrile Chemical compound C=CC#N.CC(=C)C(O)=O.CCCCOC(=O)C=C OXFFVYXBKPZBSW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001897 terpolymer Polymers 0.000 claims abstract description 17
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000005060 rubber Substances 0.000 claims abstract description 12
- 238000004073 vulcanization Methods 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- 239000005843 Thiram Substances 0.000 claims abstract description 10
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 10
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 229960002447 thiram Drugs 0.000 claims abstract description 10
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008117 stearic acid Substances 0.000 claims abstract description 9
- IKGVILAOZDBXSV-UHFFFAOYSA-N 1-(diaminomethylidene)-3-phenylthiourea Chemical compound NC(N)=NC(=S)NC1=CC=CC=C1 IKGVILAOZDBXSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 57
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000011787 zinc oxide Substances 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000003811 acetone extraction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 238000005292 vacuum distillation Methods 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229910052684 Cerium Inorganic materials 0.000 description 7
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical group C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- OKGXJRGLYVRVNE-UHFFFAOYSA-N diaminomethylidenethiourea Chemical compound NC(N)=NC(N)=S OKGXJRGLYVRVNE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1078—Fire-resistant, heat-resistant materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring, raw material includes: 55-70 parts of nitrile rubber, 10-25 parts of butadiene-styrene rubber, 5-10 parts of chlorohydrin rubber, 1-5 parts of POE, 1-2 parts of stearic acid, 3-8 parts of modified zinc oxide, 2-3.2 parts of sulphur, 5-14 parts of compounded mix, 1-2 parts of anti-aging agent, 0.2-0.6 parts of tetra-benzyl thiram disulfide, 0.5-1.3 parts of Vulcanization accelerator TMTD, 0.1-0.7 parts, 0.2-1.3 parts of dispersing agent SDS of 1- phenyl -3- guanyl thiourea by weight；The raw material of compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, potassium titanate and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer.The ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring proposed by the present invention, elongation at break, heat resistance, resistance to ag(e)ing are good.
Description
Technical field
The present invention relates to instrument material technical field more particularly to a kind of ageing-resistant nitrile rubbers of instrument and meter sealing ring
Composite material.
Background technique
Instrument and meter is the utensil to detect, measure, observe, calculate various physical quantitys, material composition, physical parameter etc.
Or equipment, including vacuum leak detector, pressure gauge, horizontal metroscope, microscope, multiplier etc., it has been widely used in industry, agriculture at present
The various aspects such as industry, traffic, science and technology, environmental protection, national defence, culture, education and public health, people's lives.Sealing ring is that instrument and meter sealing is common close
Sealing is usually invested shell rim；Nitrile rubber is one of common material of sealing ring, the tool of sealing ring made of it
There is the good recovery under high resiliency, high intensity and compression, but there is unsaturated carbon-carbon double bond in nitrile rubber molecule, uses
Its manufactured sealing ring heat resistance and resistance to ag(e)ing be not it is too ideal, limit its application.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of ageing-resistant butyronitrile of instrument and meter sealing ring
Rubber composite material, permanent compression set is small, and elongation at break, heat resistance and ageing-resistant performance are excellent.
A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring proposed by the present invention, raw material is by weight
Include: 55-70 parts of nitrile rubber, 10-25 parts of butadiene-styrene rubber, 5-10 parts of chlorohydrin rubber, 1-5 parts of POE, 1-2 parts of stearic acid, change
Property 3-8 parts of zinc oxide, 2-3.2 parts of sulphur, 5-14 parts of compounded mix, 1-2 parts of anti-aging agent, tetra-benzyl thiram disulfide 0.2-
0.6 part, 0.5-1.3 parts of Vulcanization accelerator TMTD, 0.1-0.7 parts, 0.2-1.3 parts of dispersing agent SDS of 1- phenyl -3- guanyl thiourea；
Wherein, the raw material of the compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, oxidation
Cerium, potassium titanate and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer.
Preferably, the modified zinc oxide is prepared according to following technique: zinc oxide being added in toluene, is added after dispersion
Enter silane coupling agent KH-560,6-10h is stirred to react at 95-105 DEG C, acetone extraction is dried to obtain material A；By material A with
4,4 '-diamino-diphenylamines are added in tetrahydrofuran, 8-13h are stirred to react at 55-65 DEG C, acetone extraction is dried to obtain object
Expect B；By 5,11,17,23- tetra-terts -25,26,27,28- tetrahydroxy cup [4] aromatic hydrocarbons, potassium carbonate and anhydrous acetonitrile are mixed,
30-70min is stirred under the protection of nitrogen, 1,2- Bromofume is added, with back flow reaction 15- after anhydrous calcium chloride closed system
Then 27h, filtering, vacuum distillation are added methanol and stand, filter, be recrystallized to give material C；Under the protection of nitrogen, by material
C is added in acetonitrile, and potassium carbonate and material B, back flow reaction 8-14h is added, then dilute hydrochloric acid is added in vacuum distillation, stands, mistake
It filters, wash, being dried to obtain the modified zinc oxide.
Preferably, in the preparation process of modified zinc oxide, zinc oxide, silane coupling agent KH-560 weight ratio be 1:
0.3-0.4。
Preferably, in the preparation process of modified zinc oxide, the epoxy group on material A surface and 4,4 '-diamino-diphenylamines
In primary amine molar ratio be 1:3-5；5,11,17,23- tetra-terts -25,26,27,28- tetrahydroxy cup [4] aromatic hydrocarbons, 1,2-
The molar ratio of Bromofume is 1:8-15；The molar ratio of the primary amine in bromine and material B in material C is 1:3-5.
Preferably, in the compounded mix, nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, metatitanic acid
Potassium, methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer weight ratio are 2-10:3-8:1-5:5-12:6-9:2-
14:1-2.7.
Preferably, the average grain diameter of the nano-silicon nitride is 10-20nm；The average grain diameter of Nano carbon white is 20-
35nm。
Preferably, the anti-aging agent is anti-aging agent 1520, in antioxidant D DA-70, antioxidant MB Z, antioxidant 4010NA
One or more kinds of mixtures.
Instrument and meter sealing ring of the present invention ageing-resistant nitile-butadiene rubber composite material is with nitrile rubber in raw material
Major ingredient, while joined butadiene-styrene rubber, chlorohydrin rubber and POE three and nitrile rubber cooperation, the ratio for passing through control has
Body is 55-70:10-25:5-10:1-5, while joined dispersing agent SDS, keeps four compatibility good, plays performance collaboration and makees
With imparting composite material excellent oil resistant, solvent resistant, ozone and aging resistance and heat aging property；In the preparation of modified zinc oxide
In the process, zinc oxide is modified using silane coupling agent KH-560 as modifying agent first, is introduced on the surface of zinc oxide
Epoxy group has obtained material A, and later with material A and 4,4 '-diamino-diphenylamines are raw material, controls the condition of reaction, makes material
Amino in the epoxy group on the surface A and 4,4 '-diamino-diphenylamines is reacted, and 4,4 '-diamino-diphenylamine structures are drawn
Enter into material A, obtained amino-containing material B；By 5,11,17,23- tetra-terts -25,26,27,28- tetrahydroxy cups [4]
Bromine has been introduced into cup [4] aromatic hydrocarbons after the reaction of 2- Bromofume, material C has been obtained, later with object by the hydroxyl in aromatic hydrocarbons and 1
Material C is that raw material is reacted with material B, reacts the bromine in material C with the amino in material B, thus by 4,4 '-
Diamino-diphenylamine and calixarenes have been introduced into the surface of zinc oxide, improve the surface nature of zinc oxide, have obtained modification
Zinc oxide is added into system, the good dispersion in system, on the one hand, is easier in conjunction with promotor, being formed has high activity
Compound, reduce curing temperature, shorten vulcanization time, improve antireversion energy, improve the physical mechanical property of vulcanizate,
Extend time of scorch simultaneously, it is poor to improve zinc oxide dissolubility in system, the shortcomings that vulcanizing stability difference and easy incipient scorch, a side
Face cooperates because introducing secondary amine structure and phenolic hydroxyl group with anti-aging agent, assigns composite material excellent ageing-resistant performance；With two sulphur
Change tetra-benzyl thiram, Vulcanization accelerator TMTD, 1- phenyl -3- guanyl thiourea three cooperation addition system as promotor, makes wherein
S -- S heterolytic fission occurs under thiourea nucleation, provided with the thiourea substances of nucleation for system
One be easier quick response path, improve curingprocess rate, hence it is evident that reduce vulcanization time, while make tensile strength, hardness,
The performances such as tearing strength, compressive resistance, abrasion performance are improved, but reduce the elongation at break of system simultaneously, to overcome
This defect, cooperation joined cerium oxide and steel slag；The raw material of compounded mix be specifically chosen nano-silicon nitride, Nano carbon white,
Sepiolite powder, steel slag, cerium oxide, potassium titanate, while joined methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer,
Methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer can using in its molecule carboxyl and nano-silicon nitride, nanometer it is white
Carbon black, sepiolite powder, steel slag, cerium oxide, the hydroxyl on potassium titanate surface, imido grpup and amino react, thus to nanometer
Silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, potassium titanate realize good cladding, while butyl acrylate
On ester side group can be wound between rubber molecular chain, form strong interaction, while introducing cyano, utilize phase
Like compatibility principle, the compatibility of system is improved, makes nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, titanium
Sour potassium is evenly distributed in system, is played synergistic effect, is improved the mechanical property of composite material.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring proposed by the present invention, raw material is by weight
Include: 70 parts of nitrile rubber, 10 parts of butadiene-styrene rubber, 10 parts of chlorohydrin rubber, 1 part of POE, 2 parts of stearic acid, 3 parts of modified zinc oxide,
3.2 parts of sulphur, 5 parts of compounded mix, 2 parts of anti-aging agent, 0.2 part of tetra-benzyl thiram disulfide, 1.3 parts of Vulcanization accelerator TMTD, 1- benzene
0.1 part of base -3- guanyl thiourea, 1.3 parts of dispersing agent SDS；
Wherein, the raw material of the compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, oxidation
Cerium, potassium titanate and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer.
Embodiment 2
A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring proposed by the present invention, raw material is by weight
It include: 55 parts of nitrile rubber, 25 parts of butadiene-styrene rubber, 5 parts of chlorohydrin rubber, 5 parts of POE, 1 part of stearic acid, 8 parts of modified zinc oxide, sulphur
2 parts of sulphur, 14 parts of compounded mix, 1 part of anti-aging agent, 0.6 part of tetra-benzyl thiram disulfide, 0.5 part of Vulcanization accelerator TMTD, 1- phenyl-
0.7 part of 3- guanyl thiourea, 0.2 part of dispersing agent SDS；
Wherein, the raw material of the compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, oxidation
Cerium, potassium titanate and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer.
Embodiment 3
A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring proposed by the present invention, raw material is by weight
Include: 67 parts of nitrile rubber, 16 parts of butadiene-styrene rubber, 9 parts of chlorohydrin rubber, 2 parts of POE, 1.8 parts of stearic acid, 4 parts of modified zinc oxide,
3 parts of sulphur, 7 parts of compounded mix, 1.7 parts of anti-aging agent, 0.4 part of tetra-benzyl thiram disulfide, 1.1 parts of Vulcanization accelerator TMTD, 1- benzene
0.3 part of base -3- guanyl thiourea, 1 part of dispersing agent SDS；
Wherein, the raw material of the compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, oxidation
Cerium, potassium titanate and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer；
The modified zinc oxide is prepared according to following technique: zinc oxide being added in toluene, silane is added after dispersion
Coupling agent KH-560, is stirred to react 6h at 105 DEG C, and acetone extraction is dried to obtain material A；By material A and 4,4 '-diamino
Diphenylamines is added in tetrahydrofuran, 8h is stirred to react at 65 DEG C, acetone extraction is dried to obtain material B；By 5,11,17,23-
Tetra-tert -25,26,27,28- tetrahydroxy cup [4] aromatic hydrocarbons, potassium carbonate and anhydrous acetonitrile mixing, is stirred under the protection of nitrogen
1,2- Bromofume is added in 70min, with back flow reaction 15h after anhydrous calcium chloride closed system, filtering, vacuum distillation, then plus
Enter methanol standing, filters, is recrystallized to give material C；Under the protection of nitrogen, will material C be added acetonitrile in, be added potassium carbonate and
Material B, back flow reaction 14h, vacuum distillation, dilute hydrochloric acid is then added, stand, be filtered, washed, be dried to obtain it is described modified oxidized
Zinc；In the preparation process of modified zinc oxide, zinc oxide, silane coupling agent KH-560 weight ratio be 1:0.3；Material A surface
Epoxy group and 4,4 '-diamino-diphenylamines in primary amine molar ratio be 1:5；5,11,17,23- tetra-terts -25,26,
27,28- tetrahydroxy cup [4] aromatic hydrocarbons, 1,2- Bromofume molar ratio be 1:8；Bromine in material C and the primary amine in material B
Molar ratio is 1:5；
In the compounded mix, nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, potassium titanate, methyl
Acrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer weight ratio is 2:8:1:12:6:14:1；
The average grain diameter of the nano-silicon nitride is 10nm；The average grain diameter of Nano carbon white is 35nm；
The anti-aging agent is anti-aging agent 1520.
Embodiment 4
A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring proposed by the present invention, raw material is by weight
Include: 60 parts of nitrile rubber, 22 parts of butadiene-styrene rubber, 7 parts of chlorohydrin rubber, 4 parts of POE, 1.3 parts of stearic acid, 7 parts of modified zinc oxide,
2.3 parts of sulphur, 12 parts of compounded mix, 1.3 parts of anti-aging agent, 0.5 part of tetra-benzyl thiram disulfide, 0.7 part of Vulcanization accelerator TMTD,
0.6 part, 0.5 part of dispersing agent SDS of 1- phenyl -3- guanyl thiourea；
Wherein, the raw material of the compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, oxidation
Cerium, potassium titanate and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer；
The modified zinc oxide is prepared according to following technique: zinc oxide being added in toluene, silane is added after dispersion
Coupling agent KH-560, is stirred to react 10h at 95 DEG C, and acetone extraction is dried to obtain material A；By material A and 4,4 '-diamino
Diphenylamines is added in tetrahydrofuran, 13h is stirred to react at 55 DEG C, acetone extraction is dried to obtain material B；By 5,11,17,23-
Tetra-tert -25,26,27,28- tetrahydroxy cup [4] aromatic hydrocarbons, potassium carbonate and anhydrous acetonitrile mixing, is stirred under the protection of nitrogen
1,2- Bromofume is added in 30min, with back flow reaction 27h after anhydrous calcium chloride closed system, filtering, vacuum distillation, then plus
Enter methanol standing, filters, is recrystallized to give material C；Under the protection of nitrogen, will material C be added acetonitrile in, be added potassium carbonate and
Material B, back flow reaction 8h, vacuum distillation, dilute hydrochloric acid is then added, stand, be filtered, washed, be dried to obtain it is described modified oxidized
Zinc；In the preparation process of modified zinc oxide, zinc oxide, silane coupling agent KH-560 weight ratio be 1:0.4；Material A surface
Epoxy group and 4,4 '-diamino-diphenylamines in primary amine molar ratio be 1:3；5,11,17,23- tetra-terts -25,26,
27,28- tetrahydroxy cup [4] aromatic hydrocarbons, 1,2- Bromofume molar ratio be 1:15；Bromine in material C and the primary amine in material B
Molar ratio is 1:3；
In the compounded mix, nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, potassium titanate, methyl
Acrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer weight ratio is 10:3:5:5:9:2:2.7；
The average grain diameter of the nano-silicon nitride is 20nm；The average grain diameter of Nano carbon white is 20nm；
The anti-aging agent is the mixture of antioxidant D DA-70, antioxidant 4010NA.
Embodiment 5
A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring proposed by the present invention, raw material is by weight
Include: 62 parts of nitrile rubber, 17 parts of butadiene-styrene rubber, 8 parts of chlorohydrin rubber, 3 parts of POE, 1.6 parts of stearic acid, 7 parts of modified zinc oxide,
2.7 parts of sulphur, 9 parts of compounded mix, 1.5 parts of anti-aging agent, 0.4 part of tetra-benzyl thiram disulfide, 0.9 part of Vulcanization accelerator TMTD, 1-
0.5 part of phenyl -3- guanyl thiourea, 0.7 part of dispersing agent SDS；
Wherein, the raw material of the compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, oxidation
Cerium, potassium titanate and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer；
The modified zinc oxide is prepared according to following technique: zinc oxide being added in toluene, silane is added after dispersion
Coupling agent KH-560, is stirred to react 8h at 100 DEG C, and acetone extraction is dried to obtain material A；By material A and 4,4 '-diamino
Diphenylamines is added in tetrahydrofuran, 11h is stirred to react at 60 DEG C, acetone extraction is dried to obtain material B；By 5,11,17,23-
Tetra-tert -25,26,27,28- tetrahydroxy cup [4] aromatic hydrocarbons, potassium carbonate and anhydrous acetonitrile mixing, is stirred under the protection of nitrogen
1,2- Bromofume is added in 45min, with back flow reaction 21h after anhydrous calcium chloride closed system, filtering, vacuum distillation, then plus
Enter methanol standing, filters, is recrystallized to give material C；Under the protection of nitrogen, will material C be added acetonitrile in, be added potassium carbonate and
Material B, back flow reaction 11h, vacuum distillation, dilute hydrochloric acid is then added, stand, be filtered, washed, be dried to obtain it is described modified oxidized
Zinc；In the preparation process of modified zinc oxide, zinc oxide, silane coupling agent KH-560 weight ratio be 1:0.35；Material A surface
Epoxy group and 4,4 '-diamino-diphenylamines in primary amine molar ratio be 1:4；5,11,17,23- tetra-terts -25,26,
27,28- tetrahydroxy cup [4] aromatic hydrocarbons, 1,2- Bromofume molar ratio be 1:11；Bromine in material C and the primary amine in material B
Molar ratio is 1:4；
In the compounded mix, nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, potassium titanate, methyl
Acrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer weight ratio is 7:6:3:9:8:7:2；
The average grain diameter of the nano-silicon nitride is 15nm；The average grain diameter of Nano carbon white is 28nm；
The anti-aging agent is the mixture of anti-aging agent 1520, antioxidant D DA-70, antioxidant MB Z, antioxidant 4010NA, and
Anti-aging agent 1520, antioxidant D DA-70, antioxidant MB Z, antioxidant 4010NA weight ratio be 3:5:2:1.
Embodiment 6
A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring proposed by the present invention, raw material is by weight
Include: 62 parts of nitrile rubber, 17 parts of butadiene-styrene rubber, 8 parts of chlorohydrin rubber, 3 parts of POE, 1.6 parts of stearic acid, 7 parts of modified zinc oxide,
2.7 parts of sulphur, 9 parts of compounded mix, 1.5 parts of anti-aging agent, 0.4 part of tetra-benzyl thiram disulfide, 0.9 part of Vulcanization accelerator TMTD, 1-
0.5 part of phenyl -3- guanyl thiourea, 0.7 part of dispersing agent SDS；
Wherein, the raw material of the compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, oxidation
Cerium, potassium titanate and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer；
In the compounded mix, nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, potassium titanate, methyl
Acrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer weight ratio is 7:6:3:9:8:7:2；
The average grain diameter of the nano-silicon nitride is 15nm；The average grain diameter of Nano carbon white is 28nm；
The anti-aging agent is the mixture of anti-aging agent 1520, antioxidant D DA-70, antioxidant MB Z, antioxidant 4010NA, and
Anti-aging agent 1520, antioxidant D DA-70, antioxidant MB Z, antioxidant 4010NA weight ratio be 3:5:2:1.
Gained instrument and meter sealing ring in embodiment 1-6 is examined with the performance of ageing-resistant nitile-butadiene rubber composite material
It surveys, wherein hardness test is carried out according to GB/T 531-2008, and tensile property is carried out according to GB/T 528-2009, tear resistance
It is carried out according to GB/T 529-2008, compression set is carried out according to GB/T 7759.2-2015, and ageing properties are according to GB/
T3512-2014 is carried out, 120 DEG C × 70h of test condition；Testing result is as shown in the table:
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring, which is characterized in that its raw material wraps by weight
Include: 55-70 parts of nitrile rubber, 5-10 parts of chlorohydrin rubber, 1-5 parts of POE, 1-2 parts of stearic acid, is modified 10-25 parts of butadiene-styrene rubber
3-8 parts of zinc oxide, 2-3.2 parts of sulphur, 5-14 parts of compounded mix, 1-2 parts of anti-aging agent, tetra-benzyl thiram disulfide 0.2-0.6
Part, 0.5-1.3 parts of Vulcanization accelerator TMTD, 0.1-0.7 parts, 0.2-1.3 parts of dispersing agent SDS of 1- phenyl -3- guanyl thiourea；
Wherein, the raw material of the compounded mix includes: nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, titanium
Sour potassium and methacrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer.
2. the ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring according to claim 1, which is characterized in that described
Modified zinc oxide is prepared according to following technique: zinc oxide is added in toluene, silane coupling agent KH-560 is added after dispersion,
6-10h is stirred to react at 95-105 DEG C, acetone extraction is dried to obtain material A；By material A and 4,4 '-diamino-diphenylamines add
Enter in tetrahydrofuran, 8-13h is stirred to react at 55-65 DEG C, acetone extraction is dried to obtain material B；By 5,11,17,23- tetra-
Tert-butyl -25,26,27,28- tetrahydroxy cup [4] aromatic hydrocarbons, potassium carbonate and anhydrous acetonitrile mixing, stirs 30- under the protection of nitrogen
1,2- Bromofume is added in 70min, and with back flow reaction 15-27h after anhydrous calcium chloride closed system, filtering is evaporated under reduced pressure, so
Methanol is added afterwards to stand, filters, be recrystallized to give material C；Under the protection of nitrogen, material C is added in acetonitrile, carbonic acid is added
Then dilute hydrochloric acid is added in potassium and material B, back flow reaction 8-14h, vacuum distillation, stand, be filtered, washed, being dried to obtain described change
Property zinc oxide.
3. the ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring according to claim 2, which is characterized in that changing
Property zinc oxide preparation process in, zinc oxide, silane coupling agent KH-560 weight ratio be 1:0.3-0.4.
4. the ageing-resistant nitile-butadiene rubber composite material of the instrument and meter sealing ring according to Claims 2 or 3, which is characterized in that
In the preparation process of modified zinc oxide, the molar ratio of the primary amine in the epoxy group on material A surface and 4,4 '-diamino-diphenylamines
For 1:3-5；5,11,17,23- tetra-terts -25,26, the molar ratio of 27,28- tetrahydroxy cup [4] aromatic hydrocarbons, 1,2- Bromofume
For 1:8-15；The molar ratio of the primary amine in bromine and material B in material C is 1:3-5.
5. the ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring described in any one of -4 according to claim 1, special
Sign is, in the compounded mix, nano-silicon nitride, Nano carbon white, sepiolite powder, steel slag, cerium oxide, potassium titanate, methyl
Acrylic acid-acrylic acid butyl ester-acrylonitrile terpolymer weight ratio is 2-10:3-8:1-5:5-12:6-9:2-14:1-2.7.
6. the ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring described in any one of -5 according to claim 1, special
Sign is that the average grain diameter of the nano-silicon nitride is 10-20nm；The average grain diameter of Nano carbon white is 20-35nm.
7. the ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring described in any one of -6 according to claim 1, special
Sign is, the anti-aging agent be one of anti-aging agent 1520, antioxidant D DA-70, antioxidant MB Z, antioxidant 4010NA or
A variety of mixtures.
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