CN114561049A - High-low temperature-resistant oil-resistant sealing rubber material and preparation method thereof - Google Patents
High-low temperature-resistant oil-resistant sealing rubber material and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 152
- 239000005060 rubber Substances 0.000 title claims abstract description 152
- 238000007789 sealing Methods 0.000 title claims abstract description 107
- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 70
- 239000011256 inorganic filler Substances 0.000 claims abstract description 46
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 46
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 44
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 41
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 239000003921 oil Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 239000004945 silicone rubber Substances 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 239000003086 colorant Substances 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 46
- 239000003822 epoxy resin Substances 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 40
- 239000007822 coupling agent Substances 0.000 claims description 24
- 238000007599 discharging Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- -1 amino diatomite Chemical compound 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 10
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 9
- 239000004200 microcrystalline wax Substances 0.000 claims description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005909 Kieselgur Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- 229960001124 trientine Drugs 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 claims description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 3
- HYTJADYUOGDVRL-UHFFFAOYSA-N n-phenyl-n-(2-phenylpropan-2-yl)aniline Chemical compound C=1C=CC=CC=1C(C)(C)N(C=1C=CC=CC=1)C1=CC=CC=C1 HYTJADYUOGDVRL-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 239000010410 layer Substances 0.000 description 18
- 239000006229 carbon black Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000032683 aging Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001073507 Callicarpa Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 235000013757 Juglans Nutrition 0.000 description 1
- 241000758789 Juglans Species 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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)
- Sealing Material Composition (AREA)
Abstract
The invention relates to the technical field of sealing rubber materials, and discloses a high-low temperature resistant and oil resistant sealing rubber material and a preparation method thereof. The sealing rubber material comprises the following raw materials in parts by weight: 100 parts of nitrile rubber, 18-30 parts of silicone rubber, 5-8 parts of a vulcanizing agent, 4-8 parts of an anti-aging agent, 4-8 parts of a plasticizer, 50-100 parts of an inorganic filler, 8-16 parts of an auxiliary agent and 0-10 parts of a coloring agent. By adopting the formula disclosed by the invention, the sealing rubber material has better high-temperature resistance and better oil-resistant medium performance, can meet the sealing requirements in extremely cold and high-temperature environments, and can be used for a long time in an environment of-42-140 ℃.
Description
Technical Field
The invention relates to the technical field of sealing rubber materials, in particular to a high-low temperature resistant oil-resistant sealing rubber material and a preparation method thereof.
Background
Nitrile-butadiene rubber (NBR) is a random copolymer prepared by polymerizing butylene and acrylonitrile through free radical initiated emulsion, and the nitrile-butadiene rubber as a general rubber has good physical and mechanical properties, and the side group of a molecular chain has strong polarity, so that the nitrile-butadiene rubber has excellent tolerance to fuel oil, mineral oil and aromatic solvents, therefore, the nitrile-butadiene rubber is widely used as a main material of an oil-resistant sealing formula in pipelines of mediums such as petroleum hydraulic oil, glycol hydraulic oil, diester lubricating oil, gasoline, water, silicon lubricating grease, silicon oil and the like and industrial mechanical seals, and the nitrile-butadiene rubber oil-resistant seal is developed into a rubber sealing product with the widest application and the lowest cost.
As technology advances and customer activity areas expand, sealed articles are required to have a wider range of applications. If the working condition temperature is increased, the temperature difference in different regions of south and north, and the influence of contacted media, the requirements of the products such as a sealing gasket, a sealing ring, a sealing layer sheet and the like higher than the previous requirements on high temperature resistance and low temperature resistance are provided besides engine oil resistance. The nitrile rubber has the phenomena of hardness increase and elasticity reduction at low temperature, and thermal oxidation aging occurs at high temperature, so that the use temperature range of the nitrile rubber sealing material is limited. The traditional NBR rubber material has the use temperature range of-40-100 ℃ or-30-120 ℃, and is difficult to meet the sealing requirements in extremely cold and high-temperature environments, so that the use temperature range of the NBR sealing material is widened, the NBR sealing material has good oil-resistant medium performance and high and low temperature resistance, and the NBR rubber material has important significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-low temperature resistant oil-resistant sealing rubber material and a preparation method thereof. The sealing rubber material has good oil-resistant medium performance and high and low temperature resistance, and can meet the sealing requirements in extremely cold and high temperature environments.
The specific technical scheme of the invention is as follows:
the high-low temperature resistant oil-resistant sealing rubber material comprises the following raw materials in parts by weight:
100 parts of nitrile rubber;
15-30 parts of silicon rubber;
5-8 parts of a vulcanizing agent;
3-8 parts of an anti-aging agent;
4-8 parts of a plasticizer;
50-105 parts of an inorganic filler;
8-16 parts of an auxiliary agent;
0-10 parts of a coloring agent.
By adopting the formula disclosed by the invention, the sealing rubber material has better high-temperature resistance and better oil-resistant medium performance, can meet the sealing requirements in extremely cold and high-temperature environments, and can be used for a long time in an environment of-42-140 ℃.
Preferably, the silicone rubber is a mixed rubber of methyl vinyl silicone rubber and precipitated silica.
Preferably, the sulfurizing agent comprises dicumyl peroxide and/or 1, 3-bis (tert-butylperoxyisopropyl) benzene; the sealing rubber material also comprises the following raw materials in parts by weight: 1-3 parts of triallyl isocyanurate.
When peroxide is used as a vulcanizing agent, the formed-C-C-crosslinking bond has a large energy, and thus the sealing rubber material can be endowed with better heat resistance.
Preferably, the auxiliary agent comprises the following components in parts by weight: 2-5 parts of a first auxiliary agent, 1-3 parts of a second auxiliary agent and 5-8 parts of a third auxiliary agent; the first auxiliary agent comprises ferric oxide or cerium oxide; the second aid comprises microcrystalline wax 40/60; the third additive comprises QST-100 silicon-based coupling agent.
Preferably, the anti-aging agent comprises one or more of 2, 6-di-tert-butyl-p-cresol, 4 '-methylenebis (phenyl isocyanate), 2-mercaptobenzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline polymer and 4,4' -bis (phenylisopropyl) diphenylamine.
Preferably, the plasticizer comprises plasticizer TP759 and/or plasticizer RS 735.
Preferably, the colorant comprises carbon black. The carbon black may be furnace carbon black such as carbon black N550, carbon black N774, carbon black N330, etc.
Preferably, the inorganic filler comprises the following components in parts by weight: 0-45 parts of non-modified inorganic filler and 60-70 parts of temperature-controlled slow-release modified inorganic filler; the temperature-controlled slow-release modified inorganic filler is diatomite of which the surface is coated with an epoxy resin layer and is loaded with an anti-aging agent; the curing agent adopted in the epoxy resin layer comprises a curing agent containing DA bonds.
The anti-aging agent can reduce the damage of hot oxygen to rubber molecular chains, thereby improving the high temperature resistance of rubber products. However, the addition amount of the anti-aging agent is limited, and when the addition amount is too large, the anti-aging agent can move among rubber macromolecular crosslinked networks and is enriched on the rubber surface to generate a 'frost spray' phenomenon due to small molecular weight of the anti-aging agent, so that the anti-aging agent migrating to the rubber surface is difficult to effectively exert an anti-aging effect, and can pollute substances contacting the anti-aging agent.
Therefore, the invention adopts the temperature-controlled slow-release modified inorganic filler, the anti-aging agent is loaded in the diatomite, and the diatomite is coated by the epoxy resin layer. Under the effect of epoxy resin layer and diatomaceous earth, can slow down the release of antioxidant to, utilize the characteristic of epoxy resin layer high temperature expansion, low temperature shrink, and DA bond high temperature fracture, the characteristic of low temperature reformation, can realize the control by temperature change release of antioxidant, specifically: when the rubber is used at a lower temperature, the rubber is not aged, and the anti-aging agent is not needed to play a role, at the moment, the thermal expansion rate of the epoxy resin layer is lower, the DA bond is not broken, the cross-linked network of the epoxy resin is compact, the porosity is low, so that the anti-aging agent is very slow in release speed, and the frost spray phenomenon can be prevented; when the rubber sealing material is used at high temperature, the anti-aging agent is required to play a role in slowing down rubber aging, at the moment, the epoxy resin layer is subjected to large-degree thermal expansion, the porosity is greatly improved, and meanwhile, the DA bond is broken under the action of high temperature (122 ℃ and above), so that the porosity of the epoxy resin layer can be further improved, the release speed of the anti-aging agent is increased, the anti-aging effect can be well played, and the high-temperature resistance of the sealing rubber material is improved. Through the mode, the release amount of the anti-aging agent at high temperature can be improved while the effect of the anti-aging agent is prevented from being influenced by the 'frost spraying' phenomenon, and further the high-temperature resistance of the sealing rubber material is improved.
In addition, under the action of high temperature during vulcanization, although the release of the anti-aging agent is accelerated, only part of the anti-aging agent is released during vulcanization due to the slow release effect of the epoxy resin coating layer and the diatomite porous material; and, the temperature is lowered after completion of vulcanization, the epoxy resin layer shrinks, and the DA bond is reformed.
Preferably, the preparation method of the temperature-controlled slow-release modified inorganic filler comprises the following steps:
(1.1) under the protection of inert gas, taking N, N '- (4,4' -methylene diphenyl) bismaleimide and furfuryl amine in a mass ratio of 1.2-1.6: 1 as raw materials, carrying out Diels-Alder reaction, and separating out a product to obtain a curing agent containing DA bonds;
(1.2) adding diatomite into an aminosilane coupling agent solution, performing a dehydration condensation reaction, and separating out a product to obtain amino diatomite;
(1.3) dissolving epoxy resin, a curing agent containing DA bonds and triethylene tetramine in an acetone according to the mass ratio of 1: 0.65-0.85: 0.09-0.12, adding amino diatomite into the acetone, carrying out coating reaction, and separating out a product to obtain the amino diatomite @ epoxy resin;
(1.4) heating and melting 2, 6-di-tert-butyl-p-cresol, adding amino diatomite @ epoxy resin, uniformly dispersing, vacuumizing, heating to 122-130 ℃, stirring for 25-35 min, then filling nitrogen to the air pressure of 0.13-0.20 MPa, stirring for 1.5-2.5 h, separating out a product, and cooling to obtain the temperature-controlled slow-release modified inorganic filler.
In the preparation process, firstly coating epoxy resin on the surface of diatomite and then loading the anti-aging agent 2, 6-di-tert-butyl-p-cresol, because: when epoxy resin is coated, acetone is used as a reaction medium to dissolve a curing agent containing DA bonds, 2, 6-di-tert-butyl-p-cresol is soluble in acetone, and if 2, 6-di-tert-butyl-p-cresol is loaded firstly and then epoxy resin is coated, the loaded part of 2, 6-di-tert-butyl-p-cresol in diatomite is dissolved out in the epoxy resin coating process, so that the ageing resistance of the temperature-controlled slow-release modified inorganic filler is weakened, and the high temperature resistance of the rubber sealing material is further influenced.
Further, the specific process of step (1.1) is as follows: under the protection of inert gas, dissolving N, N '- (4,4' -methylene diphenyl) bismaleimide and furfuryl amine in a mass ratio of 1.2-1.6: 1 in tetrahydrofuran, performing reflux reaction at 65-75 ℃ for 15-20 h, and separating out a product to obtain the curing agent containing DA bonds.
Further, in the step (1.1), the mass-to-volume ratio of the furfuryl amine to the tetrahydrofuran is 1g: 8-15 mL.
Further, in the step (1.2), the concentration of the aminosilane coupling agent in the aminosilane coupling agent solution is 10-15 wt%; the mass volume ratio of the diatomite to the aminosilane coupling agent solution is 1g: 6-10 mL.
Further, in the step (1.2), the temperature of the dehydration condensation reaction is 40-50 ℃ and the time is 1-1.5 h.
Preferably, the non-modified inorganic filler includes one or more of neutral white carbon, basic white carbon, neutral diatomaceous earth and basic diatomaceous earth.
A preparation method of the sealing rubber material comprises the following steps:
(1) adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber to obtain NBR rubber compound;
(2) adding the mixed rubber into an open mill for mixing, and discharging to obtain NBR rubber material;
(3) and adding the silicon rubber into an open mill for primary mixing, then adding the NBR rubber material, performing secondary mixing, and discharging to obtain the sealing rubber material.
Preferably, in the step (1), the rubber is discharged after the temperature reaches 115-125 ℃.
Preferably, in the steps (2) and (3), the roll spacing of the open mill is 0.5-1 mm.
Preferably, in the step (3), the temperature of the primary mixing is 40-60 ℃, and the time is 3-5 min; the temperature of the secondary mixing is 40-60 ℃, and the time is 10-15 min.
Compared with the prior art, the invention has the following advantages:
(1) the sealing rubber material disclosed by the invention has good oil-resistant medium performance and high and low temperature resistance, can meet the sealing requirements in extremely cold and high temperature environments, and can be used for a long time in an environment at-42-140 ℃;
(2) By adding the thermal controlled slow release type modified inorganic filler into the sealing rubber material, the thermal controlled release of the antioxidant can be realized by utilizing the characteristics of high-temperature expansion and low-temperature contraction of the epoxy resin layer and the characteristics of high-temperature breakage and low-temperature reformation of DA bonds, so that the release amount of the antioxidant at high temperature is improved while the effect of the antioxidant is prevented from being influenced by the frost spray phenomenon, and the high-temperature resistance of the sealing rubber material is further improved.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
The high-low temperature resistant oil-resistant sealing rubber material comprises the following raw materials in parts by weight: 100 parts of nitrile rubber, 15-30 parts of silicone rubber, 5-8 parts of a vulcanizing agent, 1-3 parts of a crosslinking agent, 3-8 parts of an anti-aging agent, 4-8 parts of a plasticizer, 50-105 parts of an inorganic filler, 8-16 parts of an auxiliary agent and 0-10 parts of a coloring agent.
The silicone rubber is a mixed rubber of methyl vinyl silicone rubber and precipitated white carbon black.
The sulfurizing agent comprises dicumyl peroxide (DCP) and/or 1, 3-bis (tert-butylperoxyisopropyl) benzene (BIPB).
The crosslinker comprises triallyl isocyanurate (TAIC).
The anti-aging agent comprises one or more of 2, 6-di-tert-butyl-p-cresol (BHT), 4 '-methylenebis (phenyl isocyanate) (MBI), 2-mercaptobenzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD) and 4,4' -bis (phenylisopropyl) diphenylamine (KY-405).
The plasticizer comprises plasticizer TP759 and/or plasticizer RS 735.
The auxiliary agent comprises the following components in parts by weight: 2-5 parts of a first auxiliary agent, 1-3 parts of a second auxiliary agent and 5-8 parts of a third auxiliary agent; the first auxiliary agent comprises ferric oxide or cerium oxide; the second aid comprises microcrystalline wax 40/60; the third additive comprises QST-100 silicon-based coupling agent.
The colorant comprises carbon black.
As an embodiment, the inorganic filler includes one or more of neutral white carbon, basic white carbon, neutral diatomaceous earth, and basic diatomaceous earth.
As an embodiment, the inorganic filler includes the following components in parts by weight: 0-45 parts of non-modified inorganic filler and 60-70 parts of temperature-controlled slow-release modified inorganic filler; the non-modified inorganic filler comprises one or more of neutral white carbon black, basic white carbon black, neutral diatomite and basic diatomite; the preparation method of the temperature-controlled slow-release modified inorganic filler comprises the following steps:
(1.1) under the protection of inert gas, dissolving N, N '- (4,4' -methylenediphenyl) bismaleimide and furfuryl amine in a mass ratio of 1.2-1.6: 1 in tetrahydrofuran, wherein the mass-volume ratio of the furfuryl amine to the tetrahydrofuran is 1g: 8-15 mL, carrying out reflux reaction at 65-75 ℃ for 15-20 h, and separating out a product to obtain a DA bond-containing curing agent;
(1.2) adding kieselguhr into 10-15 wt% of aminosilane coupling agent solution, wherein the mass volume ratio of the kieselguhr to the aminosilane coupling agent solution is 1g: 6-10 mL, performing dehydration condensation reaction at 40-50 ℃ for 1-1.5 h, and separating out a product to obtain amino kieselguhr;
(1.3) dissolving epoxy resin, a curing agent containing DA bonds and triethylene tetramine in an acetone according to a mass ratio of 1: 0.65-0.85: 0.09-0.12, adding amino diatomite into the acetone, wherein the mass volume ratio of the epoxy resin to the amino diatomite to the acetone is 1g: 6-8 g: 25-35 mL, carrying out coating reaction at 45-55 ℃ for 1.5-2 h, and separating out a product to obtain the amino diatomite @ epoxy resin;
(1.4) heating and melting 2, 6-di-tert-butyl-p-cresol, adding amino diatomite @ epoxy resin, uniformly dispersing, vacuumizing, heating to 122-130 ℃, stirring for 25-35 min, then filling nitrogen to the air pressure of 0.13-0.20 MPa, stirring for 1.5-2.5 h, separating out a product, and cooling to obtain the temperature-controlled slow-release modified inorganic filler.
The preparation method of the sealing rubber material comprises the following steps:
(1) adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber after the temperature reaches 115-125 ℃ to obtain NBR rubber compound;
(2) Adding the rubber compound into an open mill with the roll spacing of 0.5-1 mm for mixing, performing thin passing for 3-4 times, adjusting the roll spacing, and discharging to obtain an NBR rubber material;
(3) adding silicon rubber into an open mill with the roller spacing of 0.5-1 mm, carrying out primary mixing for 3-5 min at 40-60 ℃, then adding NBR rubber material, carrying out secondary mixing for 10-15 min at 40-60 ℃, carrying out thin passing for 5-8 times, and discharging to obtain the sealing rubber material.
Example 1
The raw materials in the table 1 are adopted to prepare the high-low temperature resistant oil-resistant sealing rubber material through the following steps:
(1) adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber after the temperature reaches 120 ℃ to obtain NBR rubber compound;
(2) adding the rubber compound into an open mill with the roll spacing of 0.5mm for mixing, performing thin passing for 3 times, adjusting the roll spacing to perform sheet feeding to obtain NBR rubber material;
(3) adding silicon rubber into an open mill with the roll spacing of 0.5mm, carrying out primary mixing for 5min at 50 ℃, then adding NBR rubber material, carrying out secondary mixing for 10min at 50 ℃, thinly passing for 5 times, and discharging to obtain the sealing rubber material.
TABLE 1
1Silicon rubber: the mixed rubber of the methyl vinyl silicone rubber and the precipitated white carbon black is purchased from Lanxingsi organosilicon;
2microcrystalline wax: std from Kassel International co;
3QST-100 silicon-based coupling agent: orCalled ST-100, purchased from Juglans chemical.
Example 2
The raw materials in the table 2 are adopted to prepare the high-low temperature resistant oil-resistant sealing rubber material through the following steps:
(1) adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber after the temperature reaches 120 ℃ to obtain NBR rubber compound;
(2) adding the rubber compound into an open mill with the roller spacing of 1mm for mixing, performing thin passing for 3 times, adjusting the roller spacing to discharge sheets to obtain NBR rubber material;
(3) adding silicon rubber into an open mill with the roller spacing of 1mm, carrying out primary mixing for 3min at 40 ℃, then adding NBR rubber material, carrying out secondary mixing for 15min at 40 ℃, thinly passing for 8 times, and discharging to obtain the sealing rubber material.
TABLE 2
1Silicon rubber: the mixed rubber of the methyl vinyl silicone rubber and the precipitated white carbon black is purchased from Lanxingsi organosilicon;
2microcrystalline wax: std, Kassel International co;
3QST-100 silicon-based coupling agent: or ST-100, from jalpita chemical.
Example 3
The raw materials in the table 3 are adopted to prepare the high-low temperature resistant oil-resistant sealing rubber material through the following steps:
(1) adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber after the temperature reaches 120 ℃ to obtain NBR rubber compound;
(2) Adding the rubber compound into an open mill with the roll spacing of 0.5mm for mixing, performing thin passing for 4 times, adjusting the width of the roll spacing, and discharging to obtain NBR rubber material;
(3) adding silicon rubber into an open mill with the roll spacing of 0.5mm, carrying out primary mixing for 5min at 40 ℃, then adding NBR rubber material, carrying out secondary mixing for 15min at 40 ℃, thinly passing for 8 times, and discharging to obtain the sealing rubber material.
TABLE 3
1Silicon rubber: the mixed rubber of the methyl vinyl silicone rubber and the precipitated white carbon black is purchased from Lanxingsi organosilicon;
2microcrystalline wax: std from Kassel International co;
3QST-100 silicon-based coupling agent: or ST-100, from jalpita chemical.
Example 4
The raw materials in the table 4 are adopted to prepare the high-low temperature resistant oil-resistant sealing rubber material through the following steps:
(1) preparing the temperature-controlled slow-release type modified inorganic filler:
(1.1) dissolving N, N '- (4,4' -methylene diphenyl) bismaleimide and furfuryl amine in tetrahydrofuran according to the mass-volume ratio of 1.4g:1g:10mL in a nitrogen atmosphere, performing reflux reaction at 70 ℃ for 18 hours, performing rotary evaporation to remove tetrahydrofuran, washing with ethanol and diethyl ether in sequence, and drying to obtain a curing agent containing DA bonds;
(1.2) dissolving a silane coupling agent KH-550 in water to prepare a 10 wt% coupling agent solution; adding neutral kieselguhr into a coupling agent solution according to the mass volume ratio of 1g to 10mL, reacting for 1.5h at 45 ℃, performing centrifugal separation, washing the precipitate with water, and drying to obtain amino kieselguhr;
(1.3) dissolving epoxy resin, a curing agent containing DA bonds and triethylene tetramine in a mass-volume ratio of 1g:0.75g:0.1g:30mL in acetone, adding amino diatomite with the mass 7 times that of the epoxy resin into the acetone, carrying out reflux reaction for 1.5 hours at 50 ℃, carrying out centrifugal separation, washing precipitates by using acetone and water in sequence, and drying to obtain the amino diatomite @ epoxy resin;
(1.4) heating 2, 6-di-tert-butyl-p-cresol to 80 +/-3 ℃ to melt, adding amino diatomite @ epoxy resin, uniformly dispersing, vacuumizing to 0.02MPa, heating to 125 ℃, stirring for 30min, then filling nitrogen to the air pressure of 0.15MPa, stirring for 2h, cooling to 80 +/-5 ℃, filtering and draining, and cooling to room temperature to obtain the temperature-controlled slow-release modified inorganic filler;
(2) adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber after the temperature reaches 120 ℃ to obtain NBR rubber compound;
(3) adding the rubber compound into an open mill with the roll spacing of 0.5mm for mixing, performing thin passing for 4 times, adjusting the roll spacing to perform sheet feeding to obtain NBR rubber material;
(4) adding silicon rubber into an open mill with the roll spacing of 0.5mm, carrying out primary mixing for 5min at 40 ℃, then adding NBR rubber material, carrying out secondary mixing for 15min at 40 ℃, thinly passing for 8 times, and discharging to obtain the sealing rubber material.
TABLE 4
1Silicon rubber: the mixed rubber of the methyl vinyl silicone rubber and the precipitated white carbon black is purchased from Lanxingsi organosilicon;
2microcrystalline wax: std from Kassel International co;
3QST-100 silicon-based coupling agent: or ST-100, from jalpita chemical.
Example 5
The raw materials in the table 5 are adopted to prepare the high-low temperature resistant oil-resistant sealing rubber material through the following steps:
(1) preparing the temperature-controlled slow-release type modified inorganic filler:
(1.1) dissolving N, N '- (4,4' -methylene diphenyl) bismaleimide and furfuryl amine in tetrahydrofuran according to the mass-volume ratio of 1.2g:1g:8mL in a nitrogen atmosphere, performing reflux reaction at 65 ℃ for 20 hours, performing rotary evaporation to remove tetrahydrofuran, washing with ethanol and diethyl ether in sequence, and drying to obtain a curing agent containing DA bonds;
(1.2) dissolving a silane coupling agent KH-550 in water to prepare a 15 wt% coupling agent solution; adding diatomite into a coupling agent solution according to the mass-volume ratio of 1g to 8mL, reacting for 1h at 50 ℃, after centrifugal separation, washing and drying the precipitate to obtain amino diatomite;
(1.3) dissolving epoxy resin, a curing agent containing DA bonds and triethylene tetramine in a mass-volume ratio of 1g:0.85g:0.09g:25mL in acetone, adding amino diatomite with the mass 8 times that of the epoxy resin into the acetone, carrying out reflux reaction at 55 ℃ for 2 hours, carrying out centrifugal separation, washing precipitates by using acetone and water in sequence, and drying to obtain the amino diatomite @ epoxy resin;
(1.4) heating 2, 6-di-tert-butyl-p-cresol to 80 +/-3 ℃ to melt, adding amino diatomite @ epoxy resin, uniformly dispersing, vacuumizing to 0.03MPa, heating to 130 ℃, stirring for 35min, then filling nitrogen to the air pressure of 0.20MPa, stirring for 1.5h, cooling to 80 +/-5 ℃, filtering and draining, and cooling to room temperature to obtain the temperature-controlled slow-release modified inorganic filler;
(2) adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber after the temperature reaches 120 ℃ to obtain NBR rubber compound;
(3) adding the rubber compound into an open mill with the roll spacing of 0.5mm for mixing, performing thin passing for 4 times, adjusting the width of the roll spacing, and discharging to obtain NBR rubber material;
(4) adding silicon rubber into an open mill with the roll spacing of 0.5mm, carrying out primary mixing for 5min at 40 ℃, then adding NBR rubber material, carrying out secondary mixing for 15min at 40 ℃, thinly passing for 8 times, and discharging to obtain the sealing rubber material.
TABLE 5
1Silicon rubber: the mixed rubber of the methyl vinyl silicone rubber and the precipitated white carbon black is purchased from Lanxingsi organosilicon;
2microcrystalline wax: std from Kassel International co;
3QST-100 silicon-based coupling agent: or ST-100, from Callicarpa chemical;
example 6
The raw materials in the table 6 are adopted to prepare the high-low temperature resistant oil-resistant sealing rubber material through the following steps:
(1) Preparing the temperature-controlled slow-release type modified inorganic filler:
(1.1) dissolving N, N '- (4,4' -methylene diphenyl) bismaleimide and furfuryl amine in tetrahydrofuran according to the mass-to-volume ratio of 1.6g:1g:15mL in a nitrogen atmosphere, performing reflux reaction at 75 ℃ for 15 hours, removing tetrahydrofuran by rotary evaporation, washing with ethanol and diethyl ether in sequence, and drying to obtain a curing agent containing DA bonds;
(1.2) dissolving a silane coupling agent KH-550 into water to prepare a 13 wt% coupling agent solution; adding diatomite into the coupling agent solution according to the mass volume ratio of 1g:6mL, reacting for 1.5h at 40 ℃, after centrifugal separation, washing and drying the precipitate to obtain amino diatomite;
(1.3) dissolving epoxy resin, a curing agent containing DA bonds and triethylene tetramine in a mass-volume ratio of 1g:0.65g:0.12g:35mL in acetone, adding amino diatomite with the mass 6 times that of the epoxy resin into the acetone, carrying out reflux reaction for 1.5 hours at 45 ℃, carrying out centrifugal separation, washing precipitates by using acetone and water in sequence, and drying to obtain the amino diatomite @ epoxy resin;
(1.4) heating 2, 6-di-tert-butyl-p-cresol to 80 +/-3 ℃ to melt, adding amino diatomite @ epoxy resin, uniformly dispersing, vacuumizing to 0.01MPa, heating to 122 ℃, stirring for 25min, then filling nitrogen to the air pressure of 0.13MPa, stirring for 2.5h, cooling to 80 +/-5 ℃, filtering and draining, and cooling to room temperature to obtain the temperature-controlled slow-release modified inorganic filler;
(2) Adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber after the temperature reaches 120 ℃ to obtain NBR rubber compound;
(3) adding the rubber compound into an open mill with the roll spacing of 0.5mm for mixing, performing thin passing for 4 times, adjusting the roll spacing to perform sheet feeding to obtain NBR rubber material;
(4) adding silicon rubber into an open mill with the roll spacing of 0.5mm, carrying out primary mixing for 5min at 40 ℃, then adding NBR rubber material, carrying out secondary mixing for 15min at 40 ℃, thinly passing for 8 times, and discharging to obtain the sealing rubber material.
TABLE 6
1Silicon rubber: the mixed rubber of the methyl vinyl silicone rubber and the precipitated white carbon black is purchased from Lanxingsi organosilicon;
2microcrystalline wax: std from Kassel International co;
3QST-100 silicon-based coupling agent: or ST-100, from jalpita chemical.
Comparative example 1
The comparative example selects the formula of the conventional sealing rubber material, the raw materials are shown in table 7, and the sealing rubber material is prepared by the following steps:
(1) adding all the raw materials into an internal mixer for mixing, and discharging rubber after the temperature reaches 120 ℃ to obtain NBR rubber compound;
(2) and adding the rubber compound into an open mill with the roll spacing of 0.5mm for mixing, performing thin passing for 3 times, and adjusting the width of the roll spacing for blanking to obtain the sealing rubber material.
TABLE 7
Comparative example 2
The comparative example differs from example 4 in that: the temperature-controlled slow-release modified inorganic filler in example 4 was replaced with 55 parts of amino diatomaceous earth @ epoxy resin and 10 parts of 2, 6-di-t-butyl-p-cresol; the amino diatomaceous earth @ epoxy resin was prepared according to the procedures (1.1) - (1.3) of example 4. The remaining raw materials and preparation process were the same as in example 4.
Comparative example 3
This comparative example differs from example 4 in that: the temperature-controlled slow-release modified inorganic filler in the example 4 is replaced by the slow-release modified inorganic filler with the same mass; the slow-release modified inorganic filler was prepared according to the procedure (1.4) in example 4, and the amino diatomaceous earth @ epoxy resin in the procedure (1.4) was changed to neutral diatomaceous earth of equal mass. The remaining raw materials and preparation process were the same as in example 4.
Comparative example 4
This comparative example differs from example 4 in that: the DA bond-containing curing agent in step (1.3) of example 4 was replaced with ethylenediamine in an equivalent amount. The remaining raw materials and preparation process were the same as in example 4.
Comparative example 5
This comparative example differs from example 4 in that: the temperature-controlled slow-release modified inorganic filler used in the comparative example was prepared according to the following procedure:
(1.1) dissolving N, N '- (4,4' -methylene diphenyl) bismaleimide and furfuryl amine in tetrahydrofuran according to the mass-to-volume ratio of 1.4g:1g:10mL in a nitrogen atmosphere, performing reflux reaction at 70 ℃ for 18 hours, removing tetrahydrofuran by rotary evaporation, washing with ethanol and diethyl ether in sequence, and drying to obtain a curing agent containing DA bonds;
(1.2) heating 2, 6-di-tert-butyl-p-cresol to 80 +/-3 ℃ for melting, adding neutral diatomite into the heated 2, 6-di-tert-butyl-p-cresol, uniformly dispersing, vacuumizing to 0.02MPa, heating to 125 ℃, stirring for 30min, then filling nitrogen into the mixture until the air pressure is 0.15MPa, stirring for 2h, cooling to 80 +/-5 ℃, filtering and draining, and cooling to room temperature to obtain supported diatomite;
(1.3) dissolving a silane coupling agent KH-550 into water to prepare a 10 wt% coupling agent solution; adding the load type diatomite into a coupling agent solution according to the mass volume ratio of 1g:10mL, reacting for 1.5h at 45 ℃, after centrifugal separation, washing and drying the precipitate to obtain load type amino diatomite;
(1.4) dissolving epoxy resin, a curing agent containing DA bonds and triethylene tetramine in a mass-volume ratio of 1g:0.75g:0.1g:30mL in acetone, adding load type amino diatomite with the mass 7 times that of the epoxy resin into the acetone, carrying out reflux reaction for 1.5 hours at the temperature of 50 ℃, carrying out centrifugal separation, washing precipitates by using acetone and water in sequence, and drying to obtain the temperature-controlled slow-release modified inorganic filler.
The remaining raw materials and preparation process were the same as in example 4.
Test example 1: performance test
The sealing rubber materials prepared in examples 1 to 6 and comparative examples 1 to 5 were heated and vulcanized (175 ℃, 15min), standard test pieces were prepared, and after standing at room temperature for 3 months, performance tests were carried out, the test items and methods are shown in table 8, and the results are shown in tables 9 to 10.
TABLE 8
TABLE 9
Watch 10
Data analysis and conclusions:
(1) compared with the comparative example 1, the high-temperature resistance and the low-temperature resistance of the sealing rubber materials in the examples 1 to 4 are both obviously improved, and particularly the compression permanent deformation is obviously reduced, which shows that the formula provided by the invention can improve the high-temperature resistance and the low-temperature resistance of the sealing rubber materials and meet the sealing requirements in extremely cold and high-temperature environments.
(2) Compared with the example 3 and the comparative example 2, the high temperature resistance of the sealing rubber material of the example 4 is obviously improved, which shows that compared with the method that the thermal controlled slow release type modified inorganic filler is not added or the anti-aging agent and the amino diatomite @ epoxy resin are dispersedly added, the anti-aging agent is loaded in the amino diatomite @ epoxy resin to prepare the thermal controlled slow release type modified inorganic filler, which is beneficial to improving the high temperature resistance of the sealing rubber material. The reason is presumed to be: when the anti-aging agent and the amino diatomite @ epoxy resin are dispersedly added, the anti-aging agent is easy to migrate to the surface of the material during the storage of the sealing rubber material, so that the high-temperature resistance of the material is reduced. When the modified inorganic filler is added in a temperature-controlled slow-release type manner, the temperature is lower during the storage of the sealing rubber material, the thermal expansion rate of the epoxy resin layer is lower, and the DA bond is not broken, so that the release speed of the anti-aging agent is very low, and the anti-aging agent can be prevented from migrating to the surface of the material to lose efficacy; when the sealing rubber material is in a high-temperature environment, the epoxy resin layer is subjected to large-degree thermal expansion, and DA bonds are broken, so that the release speed of the anti-aging agent is accelerated, and the high-temperature resistance of the sealing rubber material is improved.
(3) Compared with the comparative example 3, the sealing rubber material of example 4 has better high temperature resistance, which shows that the high temperature resistance of the sealing rubber material can be improved by coating the epoxy resin layer outside the diatomite loaded with the anti-aging agent. The reason is presumed to be: when the epoxy resin layer is not coated, the release speed difference of the anti-aging agent at high temperature and low temperature is small, the release amount is large during the storage of the sealing rubber material, and the released anti-aging agent fails after migrating to the surface of the material, so that the high temperature resistance of the material is reduced. After the epoxy resin layer is coated, the temperature-controlled release of the anti-aging agent can be realized, so that the loss of the anti-aging agent during storage is less, more anti-aging agent can be released in a high-temperature environment, and the high-temperature resistance of the sealing rubber material is improved.
(4) The sealing rubber material of example 4 has better high temperature resistance than that of comparative example 4, which shows that the high temperature resistance of the sealing rubber material can be improved by using the curing agent containing the DA bond in the epoxy resin layer. The reason is presumed to be: the DA bond has the characteristics of high-temperature fracture and low-temperature reformation, and the porosity of the epoxy resin layer can be adjusted on the basis of the DA bond, so that the difference of the release speed of the anti-aging agent at low temperature and high temperature can be improved, and the high-temperature resistance of the sealing rubber material is improved.
(5) Compared with the comparative example 5, the sealing rubber material of the example 4 has better high temperature resistance, which shows that in the process of preparing the temperature-controlled slow-release modified inorganic filler, compared with the process of loading the anti-aging agent first and then coating the epoxy resin, the high temperature resistance of the sealing rubber material can be improved by adopting a mode of coating first and then loading. The reason is presumed to be: when epoxy resin is coated, acetone is used as a reaction medium to dissolve a curing agent containing DA bonds, 2, 6-di-tert-butyl-p-cresol is soluble in acetone, and if 2, 6-di-tert-butyl-p-cresol is loaded firstly and then epoxy resin is coated, the loaded part of 2, 6-di-tert-butyl-p-cresol in diatomite is dissolved out in the epoxy resin coating process, so that the ageing resistance of the temperature-controlled slow-release modified inorganic filler is weakened, and the high temperature resistance of the rubber sealing material is further influenced.
Test example 2: tightness test
The sealing rubber materials prepared in examples 1 to 6 and comparative examples 1 to 5 were used respectively, and 5 sealing rings were prepared and installed in a sealing pump.
The sealing pump is placed in a low-temperature box at minus 42 ℃ for low-temperature treatment for 24 hours, and after being taken out, the sealing pump is rapidly subjected to a sealing performance test under the condition of room temperature, and the performance test result and the appearance are described as follows: 5 of the sealing rings of the examples 1 to 6 and the comparative examples 4 to 5 did not leak, and 4 of the sealing rings of the comparative example 3 leaked; the appearance of all the seal rings of each example and comparative example was not deteriorated.
The sealing pump is placed in a high-temperature aging box at 140 ℃ for hot air aging for 200 hours, the sealing pump is cooled for 1 hour at room temperature after being taken out, then the sealing performance test is carried out at room temperature, and the performance test result and the appearance are described as follows: 5 sealing rings of examples 1-6 and comparative examples 2-5 did not leak, and 5 sealing rings of comparative example 1 all leaked; 5 of the seal rings of examples 1 to 6 and comparative examples 2 to 5 had no damage in appearance, and 5 of the seal ring of comparative example 1 had cracks.
The sealing pump is placed in a high-temperature aging box at 140 ℃ for hot air aging for 200 hours, the sealing pump is cooled for 1 hour at room temperature after being taken out, then the sealing performance test is carried out at room temperature, and the performance test result and the appearance are described as follows: 5 sealing rings of examples 1-6 and comparative examples 2-5 did not leak, and 5 sealing rings of comparative example 1 all leaked; 5 of the seal rings of examples 1 to 6 and comparative examples 2 to 5 had no damage in appearance, and 5 of the seal ring of comparative example 1 had cracks.
The sealing pump is placed in a high-temperature aging box at 150 ℃ for hot air aging for 300 hours, the sealing pump is cooled for 1 hour at room temperature after being taken out, then the sealing performance test is carried out at room temperature, and the performance test result and the appearance are described as follows: 5 sealing rings of examples 4 to 6 did not leak, 5 sealing rings of comparative example 1 leaked, 4, and 5 sealing rings of examples 1 to 3 leaked, and 4, 3, 2, and 3 sealing rings of comparative examples 2 to 5 leaked, respectively; the seal rings of examples 4 to 6 were not damaged in appearance in 5, the seal ring of comparative example 1 was broken in 5, the seal rings of examples 1 to 3 were broken in 2, 2 and 3, respectively, and the seal rings of comparative examples 2 to 5 were broken in 2, 0 and 1, respectively.
And (4) conclusion: the sealing rubber material prepared by the formula can be used for a long time at-42-140 ℃; and when the temperature-controlled slow-release type modified inorganic filler is adopted, the high-temperature resistance of the sealing rubber material can be further improved, so that the sealing rubber material can be used for a long time at 150 ℃.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The high-low temperature resistant oil-resistant sealing rubber material is characterized by comprising the following raw materials in parts by weight:
100 parts of nitrile rubber;
15-30 parts of silicon rubber;
5-8 parts of a vulcanizing agent;
3-8 parts of an anti-aging agent;
4-8 parts of a plasticizer;
50-105 parts of an inorganic filler;
8-16 parts of an auxiliary agent;
0-10 parts of a coloring agent.
2. The sealing rubber material according to claim 1, wherein the silicone rubber is a mixed rubber of methyl vinyl silicone rubber and precipitated silica.
3. The sealing rubber material of claim 1, wherein the vulcanizing agent comprises dicumyl peroxide and/or 1, 3-bis (t-butylperoxyisopropyl) benzene; the sealing rubber material also comprises the following raw materials in parts by weight: 1-3 parts of triallyl isocyanurate.
4. The sealing rubber material as claimed in claim 1, wherein the auxiliary comprises the following components in parts by weight: 2-5 parts of a first auxiliary agent, 1-3 parts of a second auxiliary agent and 5-8 parts of a third auxiliary agent; the first auxiliary agent comprises ferric oxide or cerium oxide; the second aid comprises microcrystalline wax 40/60; the third additive comprises QST-100 silicon-based coupling agent.
5. The sealing rubber material of claim 1, wherein the antioxidant comprises one or more of 2, 6-di-tert-butyl-p-cresol, 4 '-methylenebis (phenyl isocyanate), 2-mercaptobenzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, and 4,4' -bis (phenylisopropyl) diphenylamine.
6. The sealing rubber material according to claim 1, wherein the inorganic filler comprises the following components in parts by weight: 0-45 parts of non-modified inorganic filler and 60-70 parts of temperature-controlled slow-release modified inorganic filler; the temperature-controlled slow-release modified inorganic filler is diatomite of which the surface is coated with an epoxy resin layer and is loaded with an anti-aging agent; the curing agent adopted in the epoxy resin layer comprises a curing agent containing DA bonds.
7. The sealing rubber material according to claim 6, wherein the temperature-controlled slow-release modified inorganic filler is prepared by a method comprising:
(1.1) under the protection of inert gas, taking N, N '- (4,4' -methylene diphenyl) bismaleimide and furfuryl amine in a mass ratio of 1.2-1.6: 1 as raw materials, carrying out Diels-Alder reaction, and separating out a product to obtain a curing agent containing DA bonds;
(1.2) adding diatomite into an aminosilane coupling agent solution, performing a dehydration condensation reaction, and separating out a product to obtain amino diatomite;
(1.3) dissolving epoxy resin, a curing agent containing DA bonds and triethylene tetramine in an acetone according to the mass ratio of 1: 0.65-0.85: 0.09-0.12, adding amino diatomite into the acetone, carrying out coating reaction, and separating out a product to obtain the amino diatomite @ epoxy resin;
(1.4) heating and melting 2, 6-di-tert-butyl-p-cresol, adding amino diatomite @ epoxy resin, uniformly dispersing, vacuumizing, heating to 122-130 ℃, stirring for 25-35 min, then filling nitrogen to the air pressure of 0.13-0.20 MPa, stirring for 1.5-2.5 h, separating out a product, and cooling to obtain the temperature-controlled slow-release modified inorganic filler.
8. The sealing rubber material according to claim 7, wherein in the step (1.3), the temperature of the coating reaction is 45 to 55 ℃ and the time is 1.5 to 2 hours.
9. The seal rubber material of claim 6, wherein the non-modified inorganic filler comprises one or more of neutral white carbon, basic white carbon, neutral diatomaceous earth, and basic diatomaceous earth.
10. A method for producing a sealing rubber material according to any one of claims 1 to 9, comprising the steps of:
(1) adding all the raw materials except the silicon rubber into an internal mixer for mixing, and discharging rubber to obtain NBR rubber compound;
(2) adding the mixed rubber into an open mill for mixing, and discharging to obtain NBR rubber material;
(3) and adding the silicon rubber into an open mill for primary mixing, then adding the NBR rubber material, performing secondary mixing, and discharging to obtain the sealing rubber material.
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