CN114044986A - Low-temperature-resistant rubber, preparation method thereof and air spring end cover applying low-temperature-resistant rubber - Google Patents
Low-temperature-resistant rubber, preparation method thereof and air spring end cover applying low-temperature-resistant rubber Download PDFInfo
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- CN114044986A CN114044986A CN202111602906.7A CN202111602906A CN114044986A CN 114044986 A CN114044986 A CN 114044986A CN 202111602906 A CN202111602906 A CN 202111602906A CN 114044986 A CN114044986 A CN 114044986A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 232
- 239000005060 rubber Substances 0.000 title claims abstract description 232
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 96
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 26
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 26
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 238000004132 cross linking Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims description 17
- 238000004073 vulcanization Methods 0.000 claims description 15
- 235000021355 Stearic acid Nutrition 0.000 claims description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000008117 stearic acid Substances 0.000 claims description 14
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 11
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 51
- 239000000463 material Substances 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000013016 damping Methods 0.000 abstract description 2
- 230000006835 compression Effects 0.000 description 14
- 238000007906 compression Methods 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 238000011056 performance test Methods 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
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- 238000002425 crystallisation Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 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 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010063 rubber manufacturing process Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F9/00—Springs, vibration-dampers, shock-absorbers, or similarly-constructed movement-dampers using a fluid or the equivalent as damping medium
- F16F9/02—Springs, vibration-dampers, shock-absorbers, or similarly-constructed movement-dampers using a fluid or the equivalent as damping medium using gas only or vacuum
- F16F9/0209—Telescopic
- F16F9/0281—Details
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F9/00—Springs, vibration-dampers, shock-absorbers, or similarly-constructed movement-dampers using a fluid or the equivalent as damping medium
- F16F9/32—Details
- F16F9/3207—Constructional features
- F16F9/3235—Constructional features of cylinders
- F16F9/3242—Constructional features of cylinders of cylinder ends, e.g. caps
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the field of high polymer materials, and particularly discloses low-temperature-resistant rubber, a preparation method thereof and an air spring end cover applying the low-temperature-resistant rubber. The low-temperature-resistant rubber comprises the following substances in parts by weight: 80-100 parts of rubber, 3-8 parts of zinc oxide, 1-2 parts of catalyst, 1-2 parts of lubricant, 5-15 parts of cold resistant agent, 60-80 parts of filler, 2-3 parts of vulcanizing agent and 0.5-2 parts of crosslinking assistant, wherein the cold resistant agent is dispersed by a dispersing agent, and the dispersing agent comprises EVA and layered kaolin; the preparation method comprises the following steps: s1, mixing; and S2, vulcanizing. The low temperature resistant rubber can be used for sealing rubber rings, damping materials and life-saving articles, and has the advantage of excellent elastic effect in a low-temperature environment.
Description
Technical Field
The application relates to the field of high polymer materials, in particular to low-temperature-resistant rubber, a preparation method thereof and an air spring end cover applying the low-temperature-resistant rubber.
Background
Rubber is a high-elasticity polymer material with reversible deformation, has elasticity at room temperature, can deform and quickly recover the original shape. The rubber is widely applied in life, can be used for manufacturing tires, sealing materials, lifesaving articles, damping materials and the like, and the requirements on rubber materials are improved along with the development of science and technology and fields, so that the rubber is required to have high strength, tear resistance, medium resistance, ageing resistance, insulation and other properties, and also required to have good elasticity in a cold environment, but at a lower temperature, the rubber is easy to have a vitrification or crystallization phenomenon, so that the elasticity of the rubber is poor, and the use range of the rubber is further greatly limited. Particularly, the rubber ring applied to the end cover of the air spring is required to have higher sealing performance, and the rubber ring is crystallized and cracked under a low-temperature environment, so that the peeling phenomenon between the rubber ring and the end cover body is easy to occur.
In order to improve the use effect of the rubber ring in a low-temperature environment, a cold-resistant agent is usually added in the rubber manufacturing process to improve the low-temperature resistant effect of the rubber. The rubber added with the cold-resistant agent can effectively inhibit the crystallization of the rubber, so that the rubber can still keep better elasticity at lower temperature, and the application range of the rubber is greatly enlarged.
In view of the above-mentioned related art, the inventors thought that simply adding a cold resistance agent to rubber causes the rubber to have a defect of poor low temperature resistance uniformity, i.e., poor low temperature resistance due to poor dispersibility of the cold resistance agent in rubber.
Disclosure of Invention
In order to overcome the defect that the dispersion effect of a cold-resistant agent in a rubber material is poor, and the low-temperature resistance of rubber is poor, the application provides low-temperature-resistant rubber, a preparation method of the low-temperature-resistant rubber and an air spring end cover applying the low-temperature-resistant rubber.
In a first aspect, the present application provides a low temperature resistant rubber, which adopts the following technical scheme:
a low-temperature resistant rubber comprises the following substances in parts by weight: 80-100 parts of rubber, 3-8 parts of zinc oxide, 1-2 parts of catalyst, 1-2 parts of lubricant, 5-15 parts of cold resistant agent, 60-80 parts of filler, 2-3 parts of vulcanizing agent and 0.5-2 parts of crosslinking assistant, wherein the cold resistant agent is dispersed by a dispersing agent, and the dispersing agent comprises EVA emulsion and layered kaolin.
By adopting the technical scheme, as the crosslinking agent and the vulcanizing agent are used together, a compact and staggered crosslinking structure is formed in the low-temperature-resistant rubber, the traction effect among the components of the low-temperature-resistant rubber is improved, and the possibility of cracking of the low-temperature-resistant rubber is reduced under the low-temperature condition, namely the low-temperature-resistant effect of the low-temperature-resistant rubber is improved.
Secondly, a catalyst and a vulcanizing agent system are matched for use to form an effective sulfur vulcanization system (EV), and a compound vulcanization system is further formed by selecting a proper proportion, so that a cross-linked bond with higher bond energy is formed in the low-temperature-resistant rubber and is not easy to damage, and therefore, the use effect of the low-temperature-resistant rubber in a low-temperature environment can be stably improved, and the low-temperature-resistant effect of the low-temperature-resistant rubber is improved.
Finally, the EVA emulsion and the layered kaolin are used as dispersing agents, the layered kaolin has a layered structure, the EVA emulsion and the like are inserted and loaded on the layered kaolin, the cold-resistant agent can be loaded on the dispersing agents due to the viscosity of the EVA emulsion and the surface activity of the layered kaolin, and then the cold-resistant agent modified by the crystal dispersing agents can be uniformly dispersed in the low-temperature resistant rubber through better compatibility between the EVA emulsion and the rubber, so that the low-temperature resistant rubber can obtain a uniform low-temperature resistant effect. Meanwhile, the layered kaolin can be crosslinked with rubber and reinforces the rubber, so that the bonding effect between the cold-resistant agent and the base material in the low-temperature resistant rubber is enhanced. Therefore, the low temperature resistant rubber obtains a relatively uniform cold resistance effect.
Preferably, the dispersing agent further comprises stearic acid and pentaerythritol stearate, and the mass ratio of the EVA emulsion to the layered kaolin to the stearic acid to the pentaerythritol stearate is 3-6:2-3:4-8: 5-10.
By adopting the technical scheme, stearic acid and pentaerythritol stearate are added into the dispersing agent, and the friction between molecular chain segments of the low-temperature resistant rubber is reduced by adding the stearic acid, namely, the fluidity of the low-temperature resistant rubber is improved, and the dispersing effect of the cold-resistant agent in the low-temperature resistant rubber is further enhanced; the layered kaolin is coated by adding pentaerythritol stearate, so that the possibility of agglomeration of the layered kaolin is reduced, and the dispersion effect of the layered kaolin in the low-temperature-resistant rubber is further improved. Through the matching of stearic acid and pentaerythritol stearate, the dispersing performance of the cold-resistant agent in the low-temperature resistant rubber is synergistically improved, so that the low-temperature resistant rubber obtains a relatively uniform low-temperature resistant effect.
Meanwhile, through mutual matching between stearic acid and zinc oxide, a zinc oxide vulcanization system can be formed, stable C-C cross-linked bonds can be formed in the low-temperature-resistant rubber, the cross-linked density and the anti-cracking performance of the low-temperature-resistant rubber are enhanced, meanwhile, the stearic acid can activate the zinc oxide, the vulcanization speed of the low-temperature-resistant rubber is accelerated, the plasticizing effect is achieved, and the possibility of cracking of the low-temperature-resistant rubber in a low-temperature environment is reduced.
Preferably, the low-temperature repairing agent also comprises zinc dimethacrylate.
By adopting the technical scheme, the zinc dimethacrylate can be grafted on the rubber, and through strong electrostatic interaction between ions on the zinc dimethacrylate, the movement of a rubber chain is effectively limited to a certain extent, the strength of the low-temperature-resistant rubber is enhanced, an ion cross-linking network can be formed, the ion cross-linking network and the cross-linking network in the low-temperature-resistant rubber can be mutually permeated, a double network is formed, and the stability of the low-temperature-resistant rubber is enhanced.
The zinc dimethacrylate can be polymerized to form the zinc dimethacrylate, and the capability of forming ion clusters in an aggregation manner is obtained, so that the ion clusters on the zinc dimethacrylate can be dissociated and the ion clusters at the fracture part can be rebuilt at low temperature after the low temperature resistant rubber is fractured, and simultaneously, the rearrangement of rubber molecular chains at the fracture part is promoted, the fracture part is repaired, and the integrity of the low temperature resistant rubber is maintained, so that the low temperature resistant effect of the low temperature resistant rubber is improved.
Preferably, the low-temperature repairing agent further comprises epoxy resin and silicon rubber, and the mass ratio of the zinc dimethacrylate to the epoxy resin to the silicon rubber is 2-3:1-2: 3-5.
By adopting the technical scheme, the epoxy resin can coat the zinc dimethacrylate, enhance the combination effect of the zinc dimethacrylate and the low-temperature-resistant rubber, and can be quickly repaired after the low-temperature-resistant rubber is broken. By adding the silicon rubber into the low-temperature repairing agent, on one hand, a spiral molecular conformation molecular chain can be introduced into the low-temperature resistant rubber, so that the bond angle, the orientation freedom degree and the flexibility of the rubber molecular chain are increased, and the low-temperature resistant effect of the low-temperature resistant rubber is enhanced, and on the other hand, the dispersion effect of the low-temperature repairing agent in the low-temperature resistant rubber can be enhanced, so that the low-temperature resistant rubber obtains a uniform self-repairing effect.
Preferably, the vulcanizing agent comprises a vulcanizing agent BIBP, and the vulcanizing agent further comprises at least one of peroxide and sulfur.
By adopting the technical scheme, firstly, the vulcanizing agent BIBP and the vulcanizing agent DCP are matched with each other, the vulcanizing agent DCP is peroxide, the vulcanization effect of the low-temperature-resistant rubber is improved, the crosslinking density in the low-temperature-resistant rubber is improved, and meanwhile, the vulcanizing agent BIBP can be effectively vulcanized under the condition of adding a small amount of vulcanizing agent BIBP, so that the cold-resistant effect of the low-temperature-resistant rubber is improved. In addition, under the catalysis of peroxide, the polymerization effect of zinc dimethacrylate can be promoted, so that the electrostatic effect of the zinc dimethacrylate, namely the self-repairing effect of the low-temperature-resistant rubber, can be improved.
Secondly, a stable compound vulcanization system is formed by mutual matching of vulcanizing agents BIBP and sulfur, the crosslinking effect of the low-temperature resistant rubber is promoted, high-bond-energy crosslinking bonds of C-C and C-SX-C are formed, the crosslinking density is improved, and the using effect of the low-temperature resistant rubber in a low-temperature environment is enhanced.
In addition, the vulcanizing agent BIBP, the vulcanizing agent DCP and sulfur are adopted, so that the polymerization reaction of the low-temperature repairing agent can be promoted, the formation of high-bond-energy cross-linking bonds can be promoted, the vulcanization and cross-linking effects can be stably improved, and the use effect of the low-temperature-resistant rubber in a low-temperature environment can be improved.
Preferably, the rubber comprises ethylene propylene rubber, butadiene rubber and nitrile rubber, and the mass ratio of the ethylene propylene rubber, the butadiene rubber and the nitrile rubber is 8-12:0-3: 0-4.
By adopting the technical scheme, the ethylene propylene rubber is adopted as the matrix rubber, the ethylene propylene rubber is non-crystalline rubber, further, crystallization and breakage are not easy to occur in a low-temperature environment, the butadiene rubber and the nitrile rubber are added into the ethylene propylene rubber, the butadiene main chain and the acrylonitrile side chain are introduced into the rubber, the flexibility and the rotation potential barrier of the rubber are improved, the butadiene rubber can reduce the proportion of the acrylonitrile side chain, the flexibility of the rubber molecular chain is cooperatively enhanced, and the cold resistance of the low-temperature resistant rubber is improved.
Preferably, the lubricant comprises polyethylene glycol and maleic anhydride, and the mass ratio of the polyethylene glycol to the maleic anhydride is 2-3: 0-2.
By adopting the technical scheme, firstly, the addition of the polyethylene glycol can effectively improve the lubricity and the compatibility among all components in the low-temperature resistant rubber, namely the cold-resistant agent can be uniformly dispersed in the low-temperature resistant rubber, so that the low-temperature resistant rubber can obtain a relatively uniform low-temperature resistant effect.
And secondly, polyethylene glycol and maleic anhydride are used as lubricants, so that the lubricity among all components in the low-temperature-resistant rubber can be improved, the maleic anhydride can also be used for carrying out surface modification on the rubber, the compatibility among all components in the low-temperature-resistant rubber is enhanced, and the cold-resistant effect of the low-temperature-resistant rubber is further improved.
Preferably, the filler comprises at least one of N550, N330 and N770.
By adopting the technical scheme, the N550 has larger specific surface area and higher surface structure energy, and can stably form a large amount of carbon black gel after being added into the low-temperature-resistant rubber, and the carbon black gel has a three-dimensional network structure, so that the complexity of a staggered cross-linked structure in the low-temperature-resistant rubber is increased, the bonding strength among all components in the low-temperature-resistant rubber is enhanced, and the possibility of low-temperature-resistant rubber cracking due to low temperature is improved.
Secondly, because both N330 and N770 have lower specific surface area and lower performance structure, the filling effect of the filler in the low temperature resistant rubber is improved, and further carbon black gel which is uniformly dispersed is formed in the low temperature resistant rubber, so that the low temperature resistant rubber obtains uniform strength, the possibility of cracking of the low temperature resistant rubber caused by uneven distribution of the filler is reduced in a low temperature environment, and the use effect of the low temperature resistant rubber in the low temperature environment is improved.
In addition, N550, N330 and N770 are matched with each other, and the particle sizes of the N550, the N330 and the N770 are different, so that a stable grading effect can be formed after the matching, on one hand, the filling and reinforcing effects of the filler on the low-temperature-resistant rubber can be improved, and the strength of the low-temperature-resistant rubber can be improved; on the other hand, the dispersion effect of the whole filler in the low-temperature resistant rubber is improved, so that uniform carbon black particles are formed in the low-temperature resistant rubber, the low-temperature resistant rubber obtains uniform and stable bonding strength, the possibility of low-temperature cracking of the low-temperature resistant rubber is reduced, and the low-temperature resistant effect of the low-temperature resistant rubber is improved.
In a second aspect, the application provides a preparation method of low temperature resistant rubber, which adopts the following technical scheme:
a preparation method of low temperature resistant rubber comprises the following steps: s1, mixing: mixing rubber, a filler, a lubricant, zinc oxide and a cold-resistant agent, stirring, mixing to obtain mixed rubber, adding a crosslinking assistant, a catalyst and a vulcanizing agent into the mixed rubber, continuously mixing, and thinly passing and discharging to obtain mixed rubber; s2, vulcanization: standing the mixed rubber at room temperature, and vulcanizing to obtain the low-temperature-resistant rubber.
Through adopting above-mentioned technical scheme, mix cold-resistant agent and rubber earlier, because the component in the rubber mixture is less, and under the lubrication action of emollient for dispersion of cold-resistant agent in low temperature resistant rubber is comparatively even, adds vulcanizing agent etc. to the rubber mixture again, carries out vulcanization processing, promotes to form crisscross crosslinked structure in the rubber, consequently low temperature resistant rubber obtains homogeneous low temperature resistant effect and intensity.
In a third aspect, the present application provides an air spring end cover, which adopts the following technical scheme:
an air spring end cover applies the low-temperature-resistant rubber.
Through adopting above-mentioned technical scheme, the rubber circle that adopts low temperature resistant rubber to make has the low temperature stability of preferred for the rubber circle seals the end cover lid.
In summary, the present application has the following beneficial effects:
1. because the EVA emulsion and the layered kaolin are used as the dispersing agents, and the compatibility between the EVA emulsion and the rubber is better, the layered kaolin loaded with the EVA and the cold-resistant agent can be uniformly dispersed in the low-temperature-resistant rubber, and simultaneously, the layered kaolin can be crosslinked with the rubber for reinforcement to enhance the bonding performance between the cold-resistant agent and the rubber, so that the low-temperature-resistant rubber obtains a uniform and stable low-temperature-resistant effect.
2. Stearic acid and pentaerythritol stearate are preferably added into the dispersing agent and can be used as an internal lubricant and an external lubricant to carry out dispersion modification on the cold-resistant agent, so that on one hand, the possibility of self-aggregation of the cold-resistant agent and kaolin is reduced, on the other hand, the friction of a molecular chain segment of low-temperature resistant rubber is reduced, the flowing effect of the rubber is improved, and the dispersion effect of the cold-resistant agent in the low-temperature resistant rubber is synergistically enhanced; in addition, stearic acid can promote vulcanization and crosslinking, and the crosslinking density is enhanced, so that the low-temperature resistant rubber obtains more uniform cold resistance and strength.
3. According to the method, the cold-resistant agent is added in advance, and then the vulcanizing agent and other auxiliaries are added, so that the fluidity of the rubber before vulcanization is good, the dispersion uniformity of the cold-resistant agent in the cold-resistant rubber can be improved, and then vulcanization is carried out, a stable cross-linked reticular structure can be formed, and therefore the low-temperature resistant rubber obtains a relatively uniform low-temperature resistant effect and cross-linked strength.
Detailed Description
The present application will be described in further detail with reference to examples.
In the embodiment of the present application, the selected apparatuses are as follows, but not limited thereto:
medicine preparation: TAIC (cross-linking agent) of Hanbo trade company Limited in Shudeli of Fushan City, ethylene propylene diene monomer with the product number of 923201 of Kangyue rubber and plastic sealing element technology Limited in Qinghe county, BJ-707 type EVA emulsion of Att (Shandong) new material company Limited, ECKALITE ED type layered kaolin of Hebao plastic company Limited in Dongguan city, tin powder of alloy material company Limited in Qinghe county as a catalyst, PEG-4000 of Jinnan Yunhai chemical company Limited as polyethylene glycol, S-2100 type cold-resistant of Changhe chemical company Limited in Dongguan city, N550 and N330 type carbon blacks of Jinnan Delaware chemical company Limited, and N770 type carbon blacks of science and technology product development company Limited in Tianjin Yishi.
Preparation example
Preparation example of dispersant
Preparation examples 1 to 6
Respectively weighing EVA emulsion, layered kaolin, stearic acid and pentaerythritol stearate, wherein the specific mass is shown in Table 1, firstly stirring and mixing the layered kaolin and the EVA emulsion, carrying out impregnation treatment, filtering, retaining solids, and drying to obtain a primary product; and stirring and mixing the primary product, stearic acid and pentaerythritol stearate to prepare the dispersing agent 1-6.
TABLE 1 preparation examples 1-6 dispersant compositions
Examples of preparation of repairing agent
Preparation example 7
2kg of zinc dimethacrylate was taken as a low-temperature repairing agent 1.
Preparation examples 8 to 10
Respectively weighing zinc dimethacrylate, epoxy resin and silicon rubber, wherein the specific mass is shown in Table 2, stirring and mixing the zinc dimethacrylate and the epoxy resin to form a zinc dimethacrylate-epoxy resin microsphere structure, and mixing the microsphere structure with the silicon rubber to prepare the low-temperature repairing agent 2-4.
TABLE 2 PREPARATION EXAMPLES 8-10 LOW-TEMPERATURE REPAIR AGENT COMPOSITION
Preparation of vulcanizing agent
Preparation examples 11 to 13
Respectively taking a vulcanizing agent BIBP, a vulcanizing agent DCP and sulfur, wherein peroxide is DCP in the application, the specific mass is shown in Table 3, and stirring and mixing to prepare vulcanizing agents 1-3.
TABLE 3 preparation examples 11-13 vulcanizing agent compositions
Preparation example 14
The difference from preparation 13 is that: the vulcanizing agent 4 was prepared using hydrogen peroxide as the peroxide.
Examples of rubber preparation
Preparation examples 15 to 17
Respectively weighing ethylene propylene rubber, butadiene rubber and nitrile rubber, wherein the specific mass is shown in Table 4, and stirring and mixing to obtain the rubber 1-3.
TABLE 4 PREPARATION EXAMPLES 15-17 sulfurizing agent compositions
Examples of Filler preparation
Preparation examples 18 to 21
N550, N330 and N770 were weighed, respectively, the specific mass is shown in Table 5, and stirred and mixed to obtain fillers 1 to 4.
TABLE 5 preparation examples 18 to 21 vulcanizing agent compositions
Preparation example of Cold-resistant agent
Preparation examples 22 to 27
And (3) respectively mixing 20kg of cold-resistant agent with 1-6 kg of dispersing agent, stirring, mixing, filtering, and retaining solid matters to obtain the cold-resistant agent 1-6 subjected to dispersing treatment by the dispersing agent.
Preparation of Lubricant
Preparation examples 28 to 30
Respectively weighing polyethylene glycol and maleic anhydride, wherein the specific mass is shown in Table 6, and stirring and mixing to obtain the lubricants 1-3.
TABLE 6 preparation examples 28-30 Lubricant compositions
Examples
Examples 1 to 3
In a first aspect, the present application provides a low temperature resistant rubber comprising: the rubber 1, zinc oxide, a catalyst, a lubricant 1, a cold-resistant agent 1, a filler 1, a vulcanizing agent 1 and a crosslinking assistant, and the specific quality is shown in Table 7.
Table 7 examples 1-3 nanosilica compositions
In a second aspect, the present application provides a method for preparing a low temperature resistant rubber: placing rubber, a filler, a lubricant, zinc oxide and a cold-resistant agent into a mixing roll, mixing to prepare mixed rubber, adding a crosslinking assistant, a catalyst and a vulcanizing agent into the mixed rubber, continuing mixing, and thinly passing and discharging to prepare the mixed rubber; placing the rubber compound at room temperature for 16h, taking out the rubber compound and vulcanizing the rubber compound on a flat vulcanizing machine under the vulcanizing condition of 160 ℃ multiplied by TC90 and the vulcanization pressure is 15Mpa, and the low-temperature resistant rubber is prepared by 1-3.
In a third aspect, the application provides an air spring end cover, which comprises an end cover body and a rubber ring matched with the end cover body, wherein the rubber ring is made of low-temperature-resistant rubber.
Examples 4 to 8
The difference from example 2 is that: and respectively adopting 2-6 cold-resistant agents to prepare 4-8 low-temperature-resistant rubbers to obtain the air spring end cover.
Examples 9 to 12
The difference from example 2 is that: 1.5kg of low-temperature repairing agent 1-4 kg is added into the low-temperature resistant rubber respectively to prepare low-temperature resistant rubber 9-12, and the air spring end cover is obtained.
Examples 13 to 15
The difference from example 2 is that: and respectively adopting 2-4 vulcanizing agents to prepare 13-15 low-temperature-resistant rubbers to obtain the air spring end cover.
Examples 16 to 17
The difference from example 2 is that: and respectively adopting 2-3 parts of rubber to prepare 16-17 parts of low-temperature-resistant rubber to obtain the air spring end cover.
Examples 18 to 19
The difference from example 2 is that: and respectively adopting 2-3 parts of lubricant to prepare 18-19 parts of low temperature resistant rubber to obtain the air spring end cover.
Examples 20 to 22
The difference from example 2 is that: and respectively adopting 2-4 fillers to prepare 20-22 low-temperature-resistant rubbers to obtain the air spring end cover.
Comparative example
Comparative example 1
The difference from example 2 is that: and preparing the low-temperature-resistant rubber 23 without adding a dispersing agent to obtain the air spring end cover.
Comparative example 2
The difference from example 2 is that: the dispersing agent only adopts layered kaolin to prepare the low temperature resistant rubber 24, and the air spring end cover is obtained.
Comparative example 3
The difference from example 2 is that: and (3) preparing low-temperature-resistant rubber 24 by using sodium dodecyl benzene sulfonate as a dispersing agent to obtain the air spring end cover.
Performance test
(1) Compression cold resistance coefficient: the low temperature resistant rubber is detected and recorded according to GB/T6034-1985 determination of compression cold resistance coefficient of vulcanized rubber, and the test is carried out at-60 ℃.
(2) Brittle temperature: testing the brittleness temperature of the low-temperature resistant rubber according to a single sample method for testing the low-temperature brittleness of vulcanized rubber GB/T1682-1994, wherein a cooling medium is industrial alcohol, and the actual temperature of the test is-50 ℃;
(3) and (3) detecting the tensile property: the test is carried out according to the national standard GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber.
The rubber rings in examples 1-2 and comparative examples 1-3 were used for the test, and the specific test results are shown in Table 8.
(4) And (3) detecting the low-temperature retraction performance: the test is carried out according to the test temperature recovery method (TR test) of the low-temperature performance of the vulcanized rubber of GB/T7758 and 2002 in the national standard, the rubber rings in the examples 1-2 and the comparative examples 1-3 are taken for detection, and the detection results are shown in Table 9.
TABLE 8 Performance test of examples 1-22 and comparative examples 1-3
TABLE 9 Performance test of examples 1-22 and comparative examples 1-3
Referring to the comparison of the performance tests in tables 8 and 9, it can be found that:
(1) a comparison of examples 1 to 3 with comparative example 1 shows that: the low temperature resistant rubbers prepared in examples 1 to 3 have improved cold resistance coefficient under compression and tensile strength at break and reduced brittleness temperature and low temperature retraction temperature, which shows that the present application uses the layered kaolin and the EVA emulsion as the dispersing agent, the cold resistant agent can be loaded on the layered kaolin, and the EVA emulsion can enhance the binding performance between the cold resistant agent and the layered kaolin on one hand, and can enhance the compatibility between the cold resistant agent and the low temperature resistant rubber on the other hand, and stably improve the dispersing effect of the cold resistant agent in the low temperature resistant rubber. In addition, a system combining a crosslinking agent and a vulcanizing agent is adopted, so that the crosslinking density and the crosslinking strength in the low-temperature-resistant rubber are improved, and the low-temperature-resistant rubber materials can be stably drawn. Meanwhile, a compound vulcanization system can be formed by adjusting the proportion of the components in the low-temperature resistant rubber, a cross-linked bond with high bond energy is formed, and the use effect of the low-temperature resistant rubber in a low-temperature environment is synergistically improved. As can be seen from tables 8 and 9, the low temperature resistant rubber of example 2 is suitable in the ratio of the respective components.
(2) Comparison with examples 4-5, examples 6-8, example 2 and comparative examples 1-3 revealed that: the compression cold resistance coefficient and the tensile strength of the low temperature resistant rubber are improved, and the brittleness temperature and the low temperature retraction temperature are reduced in the examples 4 to 8, which shows that the EVA emulsion, the layered kaolin, the stearic acid and the pentaerythritol stearate are matched as the dispersing agent, so that the compatibility of the cold resistant agent and the rubber is improved, the flowability of the rubber is reduced, the possibility of agglomeration of the cold resistant agent and the layered kaolin is reduced, and the dispersing effect of the cold resistant agent in the low temperature resistant rubber is synergistically improved. As can be seen from tables 8 and 9, the low temperature resistant rubbers of examples 4 and 7 have higher cold resistance coefficient to compression and tensile strength at break and lower brittle temperature, indicating that the proportions of the components in the dispersant are more suitable.
(3) A comparison of example 9, examples 10 to 12 and example 2 shows that: in examples 9 to 12, the compression cold resistance coefficient and the tensile strength of the low temperature resistant rubber are significantly improved, and the brittleness temperature and the low temperature retraction temperature are significantly reduced, which indicates that zinc dimethacrylate, epoxy resin and silicone rubber are adopted to cooperate with each other in the present application, and ion clusters with high electrostatic effect and spiral molecular chains with high bond angles are introduced into the low temperature resistant rubber, so that the flexibility and the transfer effect of the rubber molecular chains are improved, and then after the low temperature resistant rubber is broken at a low temperature, the broken part can be repaired by dissociation and reconstruction of the ion clusters and movement of the molecular chains in the low temperature resistant rubber. As can be seen from tables 8 and 9, the low temperature resistant rubber in example 11 has a high cold resistance coefficient under compression and tensile strength at break and a low brittleness temperature and a low temperature retraction temperature, which indicates that the ratio of the components in the low temperature repairing agent is suitable.
(4) A comparison of examples 13 to 14, example 15 and example 2 shows that: the low temperature resistant rubbers prepared in examples 13 to 14 have significantly improved cold resistance coefficient and breaking strength, and significantly reduced brittleness temperature and low temperature retraction temperature, which indicates that the vulcanizing agents BIBP, peroxide and sulfur are compounded to form a compound vulcanizing system, and a better vulcanizing effect can be obtained with a small amount of the vulcanizing agents. Meanwhile, the self-polymerization reaction of the low-temperature repairing agent can be promoted, the formation of high-bond-energy cross-linking bonds can be promoted, the vulcanization and cross-linking effects can be stably improved, and the use effect of the low-temperature-resistant rubber in a low-temperature environment can be improved. As can be seen from tables 8 and 9, the low temperature resistant rubber of example 14 has a high cold resistance coefficient under compression and high tensile strength at break, and a high brittleness temperature and a low temperature retraction temperature, indicating that the ratio of the components in the vulcanizing agent is suitable.
(5) A comparison of examples 16 to 17 with example 2 shows that: the low temperature resistant rubbers prepared in examples 16 to 17 have improved cold resistance coefficient under compression and tensile strength, and reduced brittleness temperature and low temperature retraction temperature, which indicates that the ethylene propylene rubber, butadiene rubber and nitrile butadiene rubber adopted in the present application cooperate with each other, not only reducing the possibility of generating crystals in the low temperature resistant rubber, but also improving the flexibility and rotation ratio of the rubber molecular chain, and synergistically improving the cold resistance of the low temperature resistant performance. As can be seen from tables 8 and 9, the low temperature rubber in example 16 has a high cold resistance coefficient to compression and high tensile strength at break, and a high brittleness temperature and a low temperature retraction temperature, which indicate that the proportions of the components in the rubber are suitable.
(6) A comparison of examples 18 to 19 with example 2 shows that: the low temperature resistant rubbers prepared in examples 18 to 19 have improved cold resistance coefficient under compression and increased breaking strength and reduced brittleness temperature and low temperature retraction temperature, which shows that the polyethylene glycol and maleic anhydride are used as the lubricant in the application, so that not only the dispersibility and compatibility of the cold resistant agent in the low temperature resistant rubber are enhanced, but also the rubber can be modified, and the bonding performance of the cold resistant agent in the low temperature resistant rubber is enhanced. As can be seen from tables 8 and 9, the low temperature rubber in example 19 has a high cold resistance coefficient under compression and tensile strength at break and a low brittleness temperature and low retraction temperature, indicating that the proportions of the components in the lubricant are suitable.
(7) A comparison of examples 20 to 22 with example 2 shows that: the low temperature resistant rubbers prepared in examples 20-22 have improved cold resistance coefficient under compression and tensile strength, and reduced brittleness temperature and low temperature retraction temperature, which shows that the application adopts N550, N330 and N770 as fillers, on one hand, more carbon black gel can be formed to form a double cross-linked network, and on the other hand, a grading effect can be formed to stably reinforce the low temperature resistant rubber, and the cold resistance and strength of the low temperature resistant rubber can be synergistically improved. As can be seen from tables 8 and 9, the low temperature rubber in example 22 has a high cold resistance coefficient to compression and tensile strength at break and a low brittleness temperature and low retraction temperature, indicating that the ratio of the components in the filler is suitable.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The low-temperature-resistant rubber is characterized by comprising the following substances in parts by weight: 80-100 parts of rubber, 3-8 parts of zinc oxide, 1-2 parts of catalyst, 1-2 parts of lubricant, 5-15 parts of cold resistant agent, 60-80 parts of filler, 2-3 parts of vulcanizing agent and 0.5-2 parts of crosslinking assistant, wherein the cold resistant agent is dispersed by a dispersing agent, and the dispersing agent comprises EVA and layered kaolin.
2. The low temperature resistant rubber according to claim 1, wherein: the dispersing agent also comprises stearic acid and pentaerythritol stearate, and the mass ratio of the EVA to the layered kaolin to the stearic acid to the pentaerythritol stearate is 3-6:2-3:4-8: 5-10.
3. The low temperature resistant rubber according to claim 1, wherein: the low-temperature repairing agent comprises zinc dimethacrylate.
4. The low temperature resistant rubber according to claim 3, wherein: the low-temperature repairing agent also comprises epoxy resin and silicon rubber, wherein the mass ratio of the zinc dimethacrylate to the epoxy resin to the silicon rubber is 2-31-2: 3-5.
5. The low temperature resistant rubber according to claim 1, wherein: the vulcanizing agent comprises a vulcanizing agent BIBP, and the vulcanizing agent also comprises at least one of a vulcanizing agent DCP and sulfur.
6. The low temperature resistant rubber according to claim 1, wherein: the rubber comprises ethylene propylene rubber, butadiene rubber and nitrile rubber, wherein the mass ratio of the ethylene propylene rubber to the butadiene rubber to the nitrile rubber is 8-12:0-3: 0-4.
7. The low temperature resistant rubber according to claim 1, wherein: the lubricant comprises polyethylene glycol and maleic anhydride, and the mass ratio of the polyethylene glycol to the maleic anhydride is 2-3: 0-2.
8. The low temperature resistant rubber according to claim 1, wherein: the filler comprises at least one of N550, N330 and N770.
9. The method for preparing the low temperature resistant rubber according to any one of claims 1 to 8, characterized by comprising the following steps:
s1, mixing: mixing rubber, a filler, a lubricant, zinc oxide and a cold-resistant agent, stirring, mixing to obtain mixed rubber, adding a crosslinking assistant, a catalyst and a vulcanizing agent into the mixed rubber, continuously mixing, and thinly passing and discharging to obtain mixed rubber;
s2, vulcanization: standing the mixed rubber at room temperature, and vulcanizing to obtain the low-temperature-resistant rubber.
10. An air spring end cap characterized by: a low temperature resistant rubber as claimed in any one of claims 1 to 8 is used.
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Application publication date: 20220215 |