CN112521667A - Composite rubber, high-wear-resistance sealing element composite material and preparation method thereof - Google Patents
Composite rubber, high-wear-resistance sealing element composite material and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 108
- 239000005060 rubber Substances 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 238000007789 sealing Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 31
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 29
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 12
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008117 stearic acid Substances 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 8
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 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
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical group C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 4
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 claims description 4
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000233855 Orchidaceae Species 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a composite rubber, a high-wear-resistance sealing element composite material and a preparation method thereof. The high-wear-resistance sealing element composite material comprises the following components in parts by weight: compounding rubber: 133-150 parts of carbon black: 50-70 parts of a vulcanizing agent: 4-8 parts of a coupling agent: 4-7 parts of a plasticizer: 2-8 parts of an anti-aging agent: 3.5-7 parts of active zinc oxide: 3-5 parts of stearic acid: 0.5-1.5 parts; the composite rubber comprises the following components in parts by weight: nitrile rubber: 80-90 parts of polyurethane rubber: 20-10 parts of polytetrafluoroethylene micro powder: 20-30 parts of a nano reinforcing agent: 12-18 parts of organic tin heat stabilizer: 1-2 parts. According to the invention, when the composite material is prepared, the composite rubber is independently refined, other materials are added step by step for mixing, and through reasonable formula design and process optimization, the prepared composite material has excellent wear resistance, can meet the high wear resistance requirement of a high-speed reciprocating motion sealing element product, and greatly prolongs the service life of the product.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a composite rubber, a high-wear-resistance sealing element composite material and a preparation method thereof.
Background
Along with the acceleration of national industry transformation and upgrading pace, the well-jet type growth of automation equipment and intelligent equipment occurs, and the demand on pneumatic components and hydraulic components with high precision and long service life is increased very rapidly. The reciprocating sealing element mounted on hydraulic and pneumatic components or relevant mechanical equipment can play a sealing role in a static or moving state in certain temperature, pressure and different liquids and gases to prevent the liquid or gas from leaking. Therefore, as a core part of hydraulic and starting components, the reciprocating seal member is required to have good elasticity and sealing property, and has high requirements on wear resistance, high temperature resistance, corrosion resistance, oil resistance, aging resistance, fatigue resistance and the like. However, the existing reciprocating motion sealing element has the defects of poor wear resistance, high dynamic heat generation, easy aging and hardening, and the like, so that the sealing failure of components and parts and leakage sometimes occur, the service life of the product is short, the reciprocating motion of about 10-100 ten thousand times can be borne, the equipment maintenance frequency is high, and the use requirement of high reciprocating motion of hydraulic and pneumatic components or other sealing mechanical equipment cannot be met.
At present, the reciprocating motion sealing element is mainly made of fluororubber, hydrogenated nitrile rubber, ethylene propylene diene monomer rubber, chloroprene rubber and other materials, and the common materials have certain elasticity and sealing property but poor wear resistance. Because hydraulic and pneumatic components cause inevitable wear to equipment during reciprocating motion, it is important to improve the wear resistance of reciprocating seals.
Disclosure of Invention
The invention aims to solve the technical problems, provides the composite rubber with a reasonable formula, and prepares the sealing element composite material with excellent wear resistance through an optimized process, so that the service life of the product is greatly prolonged.
The above object of the present invention is achieved by the following technical solutions:
the composite rubber comprises the following components in parts by weight: nitrile rubber: 80-90 parts of polyurethane rubber: 20-10 parts of polytetrafluoroethylene micro powder: 20-30 parts of a nano reinforcing agent: 12-18 parts of organic tin heat stabilizer: 1-2 parts.
The most important performances of the reciprocating motion sealing element are wear resistance, oil resistance and high temperature aging resistance, and the key for prolonging the service life of the product is to improve the performances of wear resistance, oil resistance, high temperature resistance and the like. Based on the above, the composite rubber of the invention uses nitrile rubber with good oil resistance and sealing elasticity as a main material, but the wear resistance of the nitrile rubber is difficult to meet the requirement of a high-speed reciprocating motion sealing element, polyurethane with excellent wear resistance and elasticity is required to be matched, and polytetrafluoroethylene micro powder with low friction coefficient is added to reduce the friction coefficient of the composite material and improve the wear resistance. The polytetrafluoroethylene micro powder also has better heat resistance and weather resistance, the polyurethane has poorer heat resistance, a small amount of organic tin heat stabilizer is added to improve the heat resistance of the composite rubber, the composite rubber can still maintain enough sealing performance of the composite rubber under the high-temperature and long-time motion state, and the nano reinforcing agent further increases the strength of the composite rubber, so that the composite rubber has longer service life.
The composite rubber is matched with polyurethane rubber and polytetrafluoroethylene micro powder on the basis of nitrile rubber to realize performance complementation, and simultaneously, the wear resistance, oil resistance and high-temperature aging resistance of the composite rubber are improved under the cooperation of the nano reinforcing agent and the organic tin heat stabilizer. If the proportion of the polyurethane rubber or the polytetrafluoroethylene micro powder is too large, the service life of the product is shortened, and the strength of the rubber sealing element is influenced by increasing the polytetrafluoroethylene part.
Further, the composite rubber comprises the following components in parts by weight: nitrile rubber: 85 parts of polyurethane rubber: 15 parts of polytetrafluoroethylene micro powder: 25 parts of nano reinforcing agent: 15 parts of organic tin heat stabilizer: and 2 parts.
Furthermore, the particle size of the polytetrafluoroethylene micro powder is 0.5-5 μm.
Furthermore, the particle size of the nano reinforcing agent is 5-20 nm.
Further, the nano reinforcing agent of the present invention may be at least one selected from nano calcium carbonate or nano silica.
Further, the composite rubber is prepared by the following method:
(1) weighing nitrile rubber, polyurethane rubber, polytetrafluoroethylene micro powder, a nano reinforcing agent and an organic tin heat stabilizer according to a proportion;
(2) starting an internal mixer to preheat to 160-175 ℃, adding nitrile rubber, polyurethane rubber, polytetrafluoroethylene micro powder and an organic tin heat stabilizer to mix;
(3) adding the nano reinforcing agent for pressure mixing, discharging the mixed rubber material to an open mill for sheet discharge, cooling, and standing at room temperature for 24-72 hours;
(4) and (3) placing the mixed rubber material on an open mill, carrying out hot refining at the temperature of 60-70 ℃, adjusting the roller distance to 0.3-0.6 mm, carrying out thin passing for 4-6 times, adjusting the roller distance to 3-5 mm, and discharging to obtain the composite rubber.
In the composite rubber, because the composition proportion of different components is greatly different, the nano reinforcing agent has small particle size and small addition amount, and is difficult to uniformly mix with rubber particles with large particle size. Therefore, before the composite material is prepared, the composite rubber is separately refined, and the composite rubber is mixed at a higher temperature so that different materials can be fully integrated. The nano reinforcing agent has small grain size and larger proportion of atoms with incomplete coordination on the surface, so that the surface of the nano reinforcing agent has active centers such as physically adsorbed and chemically adsorbed groups and molecules, inherent vacancies, dangling bonds, non-chemical ratios and the like, has large surface activity and can generate strong physical action with rubber molecules. However, if the nano reinforcing agent is directly mixed with the rubber particles, local combination is easy to occur, so that the dispersion is uneven, and the overall performance of the material is affected, so that the mixing uniformity of the composite rubber is better ensured by adding the nano reinforcing agent after other materials are uniformly mixed. The polytetrafluoroethylene micro powder has good compatibility and dispersibility, no self-agglomeration and no electrostatic effect, and high self-lubrication, and is easier to be uniformly mixed with the rubber component compared with the conventional polytetrafluoroethylene.
Further, the mixing in the steps (2) and (3) is specifically mixing for 3 to 5 minutes, lifting the upper plug to stay for 20 to 40 seconds, and then pressurizing and mixing for 3 to 5 minutes. The upper top bolt is lifted up in the middle and stays for the purpose of changing the position and redistributing the materials of each component in the internal mixer, and the problems of uneven mixing, partial slipping and the like of the materials are avoided.
The invention also aims to provide a high-wear-resistance sealing element composite material which comprises the following components in parts by weight: compounding rubber: 133-150 parts of carbon black: 50-70 parts of a vulcanizing agent: 4-8 parts of a coupling agent: 4-7 parts of a plasticizer: 2-8 parts of an anti-aging agent: 3.5-7 parts of active zinc oxide: 3-5 parts of stearic acid: 0.5 to 1.5 portions.
Further, the composite material comprises the following components in parts by weight: compounding rubber: 142 parts of carbon black: 60 parts of vulcanizing agent: 5 parts of coupling agent: 6 parts of plasticizer: 5 parts of an anti-aging agent: 5.5 parts of active zinc oxide: 4 parts and stearic acid: 1 part.
Further, the antioxidant is a composite antioxidant comprising at least two of N-isopropyl-N' -phenyl-p-phenylenediamine (4010NA), 2-Mercaptobenzimidazole (MB), and nickel dibutyldithiocarbamate (NBC).
More preferably, the anti-aging agent is a composite anti-aging agent prepared by mixing 4010NA, MB and NBC according to the mass ratio of (2-4) to (1-2) to 0.5.
Still more preferably, the anti-aging agent is a composite anti-aging agent prepared by mixing 4010NA, MB and NBC according to the mass ratio of 3:2: 0.5.
The coupling agent is one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (SI-69s) and vinyl triethoxysilane (A151) and vinyl tri (beta-methoxyethoxy) silane (A172). Wherein, the silane coupling agent SI-69s not only can be used as a coupling agent, but also has the function of accelerating vulcanization.
Further preferably, the weight part of the silane coupling agent SI-69s is not less than 2.5 parts.
Further, the vulcanizing agent may be a single vulcanizing agent or a composite vulcanizing agent added with an accelerator.
Further, the sulfurizing agent contains at least dicumyl peroxide (DCP).
Further preferably, the accelerator is a combination accelerator of at least two of zinc dithiophosphate, benzothiazole and sulfenamide accelerators.
Further preferably, the vulcanizing agent is a composite vulcanizing agent consisting of DCP, sulfur, zinc dithiophosphate, benzothiazole and sulfenamide accelerators.
The invention also aims to provide a preparation method of the high-wear-resistance sealing element composite material, which comprises the following steps:
(1) weighing the composite rubber, and putting the composite rubber into an internal mixer for preheating at the temperature of 70-80 ℃;
(2) weighing carbon black, a coupling agent, a plasticizer, an anti-aging agent, active zinc oxide and stearic acid according to a proportion, putting the mixture into an internal mixer, stirring the mixture with composite rubber, and pressurizing and mixing the mixture until the temperature is 130-140 ℃ for rubber discharge;
(3) smashing the rubber, discharging the slices, cooling to room temperature, and standing for more than 24 hours to obtain rubber compound;
(4) and (3) placing the rubber compound on an open mill for roll wrapping, setting the temperature of the open mill to be 55-60 ℃, adding a vulcanizing agent for open milling, uniformly smashing the rubber, thinly passing for 2-4 times, and adjusting the roll distance to be 3-5 mm to obtain the sheet.
Further, in the preparation method of the high-wear-resistance sealing element composite material, the preheating time in the step (1) is 1-3 min, and the mixing time in the step (2) is 5-8 min.
Further, in the preparation method of the high-wear-resistance sealing element composite material, the roller wrapping time in the step (4) is 1-2 min, the glue smashing time is 2-3 min, and the thin passing time is 2-3 min.
The invention first fully and uniformly mixes the composite rubber with the coupling agent, the anti-aging agent, the plasticizer and other matching materials, and finally adds the vulcanizing agent for low-temperature mixing during open mixing, thereby being beneficial to preparing the composite rubber material with uniform dispersion and good stability. The composite material prepared according to the formula and the process can be used for producing high-wear-resistance and oil-resistance reciprocating sealing elements, the use frequency of high-speed reciprocating motion of more than 2000 ten thousand times can be achieved through a bench test, and the service life of the product is greatly prolonged.
Compared with the prior art, the invention has the following beneficial effects:
1. the composite rubber disclosed by the invention takes nitrile rubber as a main raw material, is matched with polyurethane rubber with good wear resistance and polytetrafluoroethylene micro powder with low friction coefficient, and is added with a nano reinforcing agent and organic tin with proper proportion to improve the strength and heat resistance of the composite rubber, so that the comprehensive performance of the composite rubber is improved together.
2. Through reasonable formula design and process optimization, the prepared composite material has excellent wear resistance, can meet the high wear resistance requirement of high-speed reciprocating sealing element products, and can effectively prolong the service life of the products.
3. The polytetrafluoroethylene micro powder added in the invention has good compatibility, dispersibility and self-lubricity, not only can improve the wear resistance of the composite material, but also is beneficial to forming composite rubber with uniform dispersion.
4. According to the invention, when the composite material is prepared, the composite rubber is independently refined, the nitrile rubber, the polyurethane rubber, the polytetrafluoroethylene micro powder and the nano reinforcing agent are fully mixed and integrated through high-temperature mixing, and other materials are added step by step for mixing, so that the dispersion uniformity of different materials is better ensured, and the comprehensive performance of the product is improved.
Detailed Description
The technical solution of the present invention is further described and illustrated by the following specific examples. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified. It should be understood that the specific embodiments described herein are merely to aid in the understanding of the invention and are not intended to limit the invention specifically.
A high-wear-resistance sealing element composite material comprises the following components in parts by weight: compounding rubber: 133-150 parts of carbon black: 50-70 parts of a vulcanizing agent: 4-8 parts of a coupling agent: 4-7 parts of a plasticizer: 2-8 parts of an anti-aging agent: 3.5-7 parts of active zinc oxide: 3-5 parts of stearic acid: 0.5 to 1.5 portions.
The high-wear-resistance sealing element composite material in the embodiment of the invention is prepared by the following method:
(1) weighing the composite rubber according to a proportion, putting the composite rubber into an internal mixer for preheating for 1-3 min, wherein the preheating temperature is 70-80 ℃;
(2) weighing carbon black, a coupling agent, a plasticizer, an anti-aging agent, active zinc oxide and stearic acid according to a proportion, putting the mixture into an internal mixer, stirring the mixture with composite rubber, and carrying out pressurized mixing for 5-8 min to discharge rubber at 130-140 ℃;
(3) smashing rubber, discharging pieces, cooling to room temperature, and standing for 24-72 hours to obtain rubber compound;
(4) and (3) placing the rubber compound on an open mill for roll wrapping, setting the roll distance to be 3-5 mm, setting the roll wrapping time to be 1-2 min, setting the temperature to be 55-60 ℃, adding a vulcanizing agent, then carrying out open milling for 2-3 min, uniformly smashing the rubber, carrying out thin passing for 2-4 times when the roll distance is the minimum, setting the roll distance to be 3-5 mm, discharging the sheet, and cooling to obtain the rubber.
The composite rubber is prepared by the following method:
(1) according to the weight ratio (80-90): (20-10): (20-30): (12-18): (1-2) respectively weighing nitrile rubber, polyurethane rubber, polytetrafluoroethylene micro powder, a nano reinforcing agent and an organic tin heat stabilizer;
(2) starting an internal mixer to preheat to 160-175 ℃, adding nitrile rubber, polyurethane rubber, polytetrafluoroethylene micro powder and an organic tin heat stabilizer to mix for 3-5 minutes, lifting an upper plug to stay for 20-40 seconds, and then pressurizing and mixing for 3-5 minutes;
(3) adding a nano reinforcing agent, performing pressure mixing for 3-5 minutes, lifting the upper top plug again, staying for 20-40 seconds, performing pressure mixing for 3-5 minutes, discharging materials to an open mill, discharging to obtain a mixed rubber material with the thickness of 3-5 mm, cooling to room temperature, and standing for 24-72 hours;
(4) and (3) placing the mixed rubber material on an open mill, carrying out hot refining at the temperature of 60-70 ℃, adjusting the roller distance to 0.3-0.6 mm, carrying out thin passing for 4-6 times, adjusting the roller distance to 3-5 mm, and discharging to obtain the composite rubber.
Example 1
Example 1 provides a compounded rubber, which is specifically prepared by the following method:
(1) weighing nitrile rubber (N41, synthetic rubber factory of orchidaceae), polyurethane rubber (E1035, synthetic rubber factory of orchidaceae), polytetrafluoroethylene micro powder (F5, particle size is less than or equal to 5 mu m, Suwei company in America), a nano reinforcing agent (nano silicon dioxide H10, Shanghai Yangjiang chemical industry Co., Ltd.) and an organic tin heat stabilizer (181, Jinan Fengxiang Wei chemical industry Co., Ltd.) according to a mass ratio of 85:15:25:15: 2;
(2) starting an internal mixer (SM type) to preheat to 170 ℃, adding nitrile rubber, polyurethane rubber, polytetrafluoroethylene micro powder and an organic tin heat stabilizer to mix for 4 minutes, lifting a top plug to stay for 30 seconds, and then pressurizing and mixing for 5 minutes;
(3) adding a nano reinforcing agent, pressurizing and mixing for 4 minutes, lifting the upper top plug again, staying for 30 seconds, pressurizing and mixing for 3 minutes, discharging materials to an open mill, discharging to obtain a mixed rubber material with the thickness of 4mm, cooling to room temperature, and standing for 24 hours;
(4) and (3) placing the mixed rubber material on an open mill, carrying out hot refining at 70 ℃, adjusting the roller spacing to 0.5mm, carrying out thin passing for 5 times, adjusting the roller spacing to 4mm, and discharging to obtain the composite rubber.
Example 2
Embodiment 2 provides a high wear-resistant sealing element composite material, which comprises the following components in parts by weight: compounding rubber: 142 parts of carbon black: 60 parts of vulcanizing agent: 5 parts of coupling agent: 6 parts of plasticizer: 5 parts of an anti-aging agent: 5.5 parts of active zinc oxide: 4 parts and stearic acid: 1 part; wherein the compounded rubber is the compounded rubber prepared in the example 1; the vulcanizing agent is dicumyl peroxide (DCP-40, Shanghai Gaoqiao petrochemical Co., Ltd.); the coupling agent is a composite coupling agent consisting of silane coupling agent SI-69s (Hubei Wanyi medicine Co., Ltd.) and A151 (Shanghai Merlin Biotechnology Co., Ltd.) according to the mass ratio of 5: 1; the plasticizer is trioctyl trimellitate (TOTM plasticizer, Shanghai Michelin Biochemical technology, Ltd.); the anti-aging agent is a composite anti-aging agent prepared by mixing anti-aging agents 4010NA, MB and NBC (purchased from Shanghai Michelin Biochemical technology Co., Ltd.) according to the mass ratio of 3:2: 0.5; carbon black was purchased from Shanghai Cabot, activated Zinc oxide from Xinjingmu, and stearic acid from Changshanming Rui chemical Co.
The high-wear-resistance sealing element composite material of the embodiment is prepared by the following method:
(1) putting the composite rubber prepared in the embodiment 1 into an internal mixer for preheating for 2min, wherein the preheating temperature is 80 ℃;
(2) weighing carbon black, a vulcanizing agent, a coupling agent, a plasticizer, an anti-aging agent, active zinc oxide and stearic acid according to a proportion, putting the mixture into an internal mixer, stirring the mixture with composite rubber for 40s, and carrying out pressurized mixing for 6min to discharge rubber at 130 ℃;
(3) smashing the rubber, discharging the slices, cooling to room temperature, and standing for more than 24 hours to obtain rubber compound;
(4) and (3) placing the rubber compound on an open mill for roll coating, setting the roll distance to be 4mm, coating the roll for 1min, setting the temperature of the open mill to be 60 ℃, adding a vulcanizing agent, then open milling for 3min, uniformly smashing the rubber, thinly passing for 2 times when the roll distance is minimum, setting the roll distance to be 4mm, discharging the sheet, and cooling to obtain the rubber compound.
Examples 3 to 10
Examples 3-10 provided high abrasion seal composite materials differing from example 2 only in the parts by weight of the raw material components, the types and sources of the raw materials and the preparation method of the compounded rubber were the same as example 2, and the raw material formulations of examples 3-10 are shown in table 1.
Table 1 raw material composition and parts by weight of composite material for high wear-resistant sealing member in examples 3 to 10
The high wear seal composites of examples 3-10 were prepared using the method of example 2.
Example 11
Example 11 provides a highly abrasion resistant seal composite which differs from example 1 only in that the vulcanizing agent is DCP-40, sulfur and an accelerator LHG-80 (Ningbo Ex K.K. New Material Co., Ltd.) are mixed in a weight ratio of 4:0.5:2.5 to obtain a composite vulcanizing agent, and the remaining raw material types and sources and the preparation method of the compounded rubber are the same as those of example 2.
The high wear-resistant sealing element composite material of the embodiment is prepared by the preparation method of the embodiment 2.
Example 12
The high abrasion-resistant sealing member composite material provided in example 12 is different from that of example 2 only in that the preheating temperature of an internal mixer is 155 ℃ in the preparation process of the compounded rubber, and the types, sources and other process parameters of various raw materials are the same as those of example 2.
The high wear-resistant sealing element composite material of the embodiment is prepared by the preparation method of the embodiment 2.
Example 13
Example 13 provides a high abrasion seal composite material which differs from example 2 only in that the preheating temperature of the internal mixer is 180 ℃ during the preparation of the compounded rubber, and the types, sources and other process parameters of the raw materials are the same as those of example 2.
The high wear-resistant sealing element composite material of the embodiment is prepared by the preparation method of the embodiment 2.
Comparative example 1
The sealing element composite material provided in comparative example 1 is different from that of example 2 only in that polytetrafluoroethylene XPP-514 (average particle size 13 μm, Suwei, USA) is used instead of polytetrafluoroethylene micropowder F5, and the types and sources of the rest of raw materials and the preparation method of the composite rubber are the same as those of example 2.
The high-wear-resistance sealing element composite material of the comparative example is prepared by the preparation method of the example 2.
Comparative example 2
Comparative example 2 a seal composite was prepared as follows:
(1) directly putting the nitrile rubber, the polyurethane rubber, the polytetrafluoroethylene micro powder, the nano reinforcing agent and the organic tin heat stabilizer in the embodiment 1 into an internal mixer for preheating for 2min, wherein the preheating temperature is 80 ℃;
(2) weighing carbon black, a vulcanizing agent, a coupling agent, a plasticizer, an anti-aging agent, active zinc oxide and stearic acid according to a proportion, putting the mixture into an internal mixer, stirring the mixture with composite rubber for 40s, and mixing for 6min to 130 ℃ for rubber discharge;
(3) smashing the rubber, discharging the slices, cooling to room temperature, and standing for more than 24 hours to obtain rubber compound;
(4) and (3) placing the rubber compound on an open mill for roll coating, setting the roll distance to be 4mm, coating the roll for 1min, setting the temperature of the open mill to be 60 ℃, adding a vulcanizing agent, then open milling for 3min, uniformly smashing the rubber, thinly passing for 2 times when the roll distance is minimum, setting the roll distance to be 4mm, discharging the sheet, and cooling to obtain the rubber compound.
The sealer composites prepared in examples 2-13 and comparative examples 1-2 were subjected to performance tests, respectively. The hardness test method refers to GB/T531, the strength and elongation test method refers to GB/T528, the wear resistance test method refers to GB/T1689-. The results of the various performance tests are shown in table 2.
TABLE 2 results of Performance test of examples 2 to 13 and comparative examples 1 to 2
Comparing the performance test results of the above examples and comparative examples, it can be seen that the reciprocating motion sealing element prepared by the method of the invention using raw materials with reasonable proportioning and reasonably controlling the process conditions has excellent wear resistance and oil resistance, and the bench test of the product can be used for more than 2000 ten thousand times. On the basis of nitrile rubber, polyurethane rubber and polytetrafluoroethylene micropowder with good wear resistance are compounded, so that the wear resistance of composite materials and sealing element products can be effectively enhanced, the elasticity and the ageing resistance of the products can be influenced by excessive addition of polyurethane, the strength of the products can be reduced by excessive addition of the polytetrafluoroethylene micropowder, and the service life of the sealing element products can be shortened. The compounded rubber is composed of a plurality of materials with different properties, and is prepared into a rubber material which is fully fused and uniformly dispersed by separately high-temperature mixing, but the mixing uniformity can be influenced by too high or too low mixing temperature, so that the Akron abrasion of the sealing element material can be increased, as shown in the test results of examples 12 and 13. The polytetrafluoroethylene micropowder selected by the invention has excellent dispersibility and compatibility and is also beneficial to the uniform fusion of composite rubber, while the common polytetrafluoroethylene adopted in the comparative example 1 has relatively larger particle size, the effect of improving the wear resistance of the sealing element material is inferior to that of the example 2, and the use frequency of bench tests can only reach 1709 ten thousand times. In example 11, not only two vulcanizing agents, namely DCP-40 and sulfur, are used, but also an LHG-80 comprehensive accelerator is used, wherein the LHG-80 contains zinc dithiophosphate, benzothiazole and sulfenamide accelerators, the vulcanization efficiency of a subsequent sealing element product is improved through the combined synergistic effect of multiple components, and the composite vulcanizing agent can be quickly mixed with rubber, has good dispersibility and is also beneficial to the high-efficiency production of a composite material.
According to the invention, the composite rubber is independently refined, other materials are added step by step for mixing, and through reasonable formula design and process optimization, the prepared composite material has excellent wear resistance, can meet the high wear resistance requirement of a high-speed reciprocating motion sealing element product, and greatly prolongs the service life of the product.
The above embodiments are not exhaustive of the range of parameters of the claimed technical solutions of the present invention and the new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the claimed technical solutions of the present invention, and if no specific description is given for all the parameters involved in the technical solutions of the present invention, there is no unique combination of the parameters with each other that is not replaceable.
The specific embodiments described herein are merely illustrative of the spirit of the invention and do not limit the scope of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (7)
1. The composite rubber is characterized by comprising the following components in parts by weight: nitrile rubber: 80-90 parts of polyurethane rubber: 20-10 parts of polytetrafluoroethylene micro powder: 20-30 parts of a nano reinforcing agent: 12-18 parts of organic tin heat stabilizer: 1-2 parts.
2. The compounded rubber according to claim 1, which is produced by the following method:
(1) weighing nitrile rubber, polyurethane rubber, polytetrafluoroethylene micro powder, a nano reinforcing agent and an organic tin heat stabilizer according to a proportion;
(2) starting an internal mixer to preheat to 160-175 ℃, adding nitrile rubber, polyurethane rubber, polytetrafluoroethylene micro powder and an organic tin heat stabilizer to mix;
(3) adding the nano reinforcing agent for pressure mixing, discharging the mixed rubber material to an open mill for sheet discharge, cooling and standing at room temperature;
(4) and (3) placing the mixed rubber material on an open mill, carrying out hot refining at the temperature of 60-70 ℃, adjusting the roller distance to 0.3-0.6 mm, carrying out thin passing for 4-6 times, adjusting the roller distance to 3-5 mm, and discharging to obtain the composite rubber.
3. The high-wear-resistance sealing element composite material is characterized by comprising the following components in parts by weight: the compounded rubber of claim 1: 133-150 parts of carbon black: 50-70 parts of a vulcanizing agent: 4-8 parts of a coupling agent: 4-7 parts of a plasticizer: 2-8 parts of an anti-aging agent: 3.5-7 parts of active zinc oxide: 3-5 parts of stearic acid: 0.5 to 1.5 portions.
4. The high wear seal composite of claim 3 wherein the vulcanizing agent is a single vulcanizing agent or a composite vulcanizing agent in combination with an accelerator that is a combination of at least two of zinc dithiophosphate, benzothiazole and sulfenamide accelerators.
5. The high-abrasion-resistance sealing element composite material is characterized in that the anti-aging agent is N-isopropyl-N' -phenyl-p-phenylenediamine, 2-mercaptobenzimidazole and nickel dibutyl dithiocarbamate, and the mass ratio of the anti-aging agent to the nickel dibutyl dithiocarbamate is (2-4): (1-2): 0.5 of a mixed composite anti-aging agent.
6. The high-abrasion-resistance sealing element composite material as claimed in claim 3, wherein the coupling agent is a composite coupling agent consisting of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide and at least one silane coupling agent, and the weight part of the bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide is not less than 2.5 parts.
7. A method for preparing the high abrasion-resistant seal composite material according to any one of claims 3 to 6, comprising the steps of:
(1) weighing the composite rubber, and putting the composite rubber into an internal mixer for preheating at the temperature of 70-80 ℃;
(2) weighing carbon black, a coupling agent, a plasticizer, an anti-aging agent, active zinc oxide and stearic acid according to a proportion, putting the mixture into an internal mixer, stirring the mixture with composite rubber, and pressurizing and mixing the mixture until the temperature is 130-140 ℃ for rubber discharge;
(3) smashing the rubber, discharging the sheet, cooling, and standing at room temperature to obtain rubber compound;
(4) and (3) placing the rubber compound on an open mill for roll wrapping, wherein the temperature of the open mill is 55-60 ℃, adding a vulcanizing agent for open milling, uniformly stirring the rubber, thinly passing for 2-4 times, and adjusting the roll distance to be 3-5 mm to obtain the sheet.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113930021A (en) * | 2021-10-25 | 2022-01-14 | 南京利德东方橡塑科技有限公司 | Light-color flame-retardant low-odor environment-friendly ethylene propylene diene monomer composition and preparation method thereof |
| CN115558175A (en) * | 2022-09-23 | 2023-01-03 | 浙江国泰萧星密封材料股份有限公司 | Oil-resistant rubber gasket, preparation method and high-strength oil-resistant rubber expansion joint |
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