CN116874894A - Automobile rubber shock pad and preparation method thereof - Google Patents
Automobile rubber shock pad and preparation method thereof Download PDFInfo
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- CN116874894A CN116874894A CN202310839773.8A CN202310839773A CN116874894A CN 116874894 A CN116874894 A CN 116874894A CN 202310839773 A CN202310839773 A CN 202310839773A CN 116874894 A CN116874894 A CN 116874894A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 116
- 239000005060 rubber Substances 0.000 title claims abstract description 116
- 230000035939 shock Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 67
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 67
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 238000013016 damping Methods 0.000 claims abstract description 32
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229920000728 polyester Polymers 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002671 adjuvant Substances 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000004073 vulcanization Methods 0.000 claims description 40
- 244000043261 Hevea brasiliensis Species 0.000 claims description 33
- 229920003052 natural elastomer Polymers 0.000 claims description 33
- 229920001194 natural rubber Polymers 0.000 claims description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000006229 carbon black Substances 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002978 peroxides Chemical class 0.000 claims description 11
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000009832 plasma treatment Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 3
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical class NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 230000032683 aging Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 7
- 239000004636 vulcanized rubber Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
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- 239000012530 fluid Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical class [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 2
- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical class NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000030279 gene silencing Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 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
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of rubber products, and particularly discloses an automobile rubber shock pad and a preparation method thereof. The automobile rubber shock pad is prepared from the following raw materials in parts by weight: 60-70 parts of rubber, 10-20 parts of modified polytetrafluoroethylene, 10-20 parts of damping agent and 5-10 parts of auxiliary agent; the modified polytetrafluoroethylene is prepared by coating and modifying zinc methacrylate and polybutadiene grafted maleic anhydride; the damping agent is a mixture of polyester long fibers and graphene powder; the preparation method of the automobile rubber shock pad comprises the following steps: mixing rubber at 70-100deg.C for 1-2min, adding modified polytetrafluoroethylene and damping agent, mixing for 6-10min, adding adjuvants, mixing for 1-3min, and vulcanizing at 160-180deg.C for 20-30 min. According to the application, the wear resistance and creep resistance of the rubber pad are improved by adding the modified polytetrafluoroethylene and the damping agent into the rubber system.
Description
Technical Field
The application relates to the technical field of rubber products, in particular to an automobile rubber shock pad and a preparation method thereof.
Background
At this time, the generation of vibration may have some adverse effects, for example, machine vibration may generate noise, and increase power consumption. To reduce these adverse effects, damping elements are often used to isolate the transmission of vibrations and to absorb the shock caused by the vibrations. The shock pad is the most common shock absorbing element, is usually used as a supporting piece or a connecting piece, has the advantages of simple structure, easy manufacture, low cost and the like, and can meet most of shock absorbing requirements. The method is widely applied to various mechanical equipment, vehicles, bridges and buildings. Rubber has a good damping effect due to its high elasticity, and is therefore used as a main damping material.
The rubber vibration damping pad product is used for eliminating or reducing the transmission of mechanical vibration, so as to achieve the purposes of damping, silencing and reducing the damage caused by impact. The rubber shock pad is widely applied to the aspects of elevators, high-speed rails, mechanical equipment, vehicles, ships and the like. The rubber shock pad is characterized by high elasticity and high viscosity. However, the conventional rubber vibration-damping pad has certain disadvantages when in use, such as: the existing rubber vibration-damping pad has poor wear resistance and creep resistance in the using process of the automobile, and the service life of the vibration-damping pad is shortened.
Therefore, the wear resistance and creep resistance of the automobile rubber pad are improved, and the automobile rubber pad has important significance for prolonging the service life of the automobile shock pad.
Disclosure of Invention
The application provides an automobile rubber shock pad and a preparation method thereof in order to improve the wear resistance and creep resistance of the automobile rubber shock pad.
In a first aspect, the application provides an automobile rubber shock pad, which adopts the following technical scheme:
the automobile rubber shock pad is prepared from the following raw materials in parts by weight: 60-70 parts of rubber, 10-20 parts of modified polytetrafluoroethylene, 10-20 parts of damping agent and 5-10 parts of auxiliary agent;
the modified polytetrafluoroethylene is formed by coating and modifying zinc methacrylate and polybutadiene grafted maleic anhydride;
the damping agent is a mixture of polyester long fibers and graphene powder.
By adopting the technical scheme, the polytetrafluoroethylene has excellent medium resistance and atmospheric aging resistance, good self-lubricating performance and small friction factor, but because the polytetrafluoroethylene has low surface energy, the polytetrafluoroethylene is difficult to be compatible with other materials, the polytetrafluoroethylene surface is provided with a plurality of active groups through the acting force of grafting maleic anhydride with the polytetrafluoroethylene by zinc methacrylate and polybutadiene, the modified polytetrafluoroethylene has good compatibility with rubber, and is easy to be dispersed into a rubber substrate, so that uniform mixing and dispersion are realized in the rubber substrate, and the wear resistance of rubber products is improved;
the damping agent disclosed by the application uses the mixture of the polyester long fiber and the graphene, and on one hand, the polyester long fiber has the characteristics of high rigidity, high toughness, good creep resistance, fatigue resistance and the like; on the other hand, the graphene is combined on the surface of the rubber macromolecules to form a lubricating layer, so that heat generated by mutual friction among the rubber macromolecules is reduced, the elastic deformation maintaining capacity of the rubber macromolecules is improved, the rebound resilience of a rubber product is improved, and the creep property of a rubber material is improved; meanwhile, polyester long fibers are inserted among the lamellar graphene, so that the rebound resilience and creep resistance of the rubber material are improved while the high damping characteristic of the rubber is endowed.
In conclusion, the modified polytetrafluoroethylene damping rubber pad has a reasonable formula, improves the wear resistance and creep resistance of the rubber material under the combined action of the modified polytetrafluoroethylene and the damping agent, and prolongs the service life of the automobile damping rubber pad.
In a specific embodiment, the modified polytetrafluoroethylene comprises the following raw materials in parts by weight: 100 parts of polytetrafluoroethylene, 3-15 parts of methacrylic acid, 2-6 parts of zinc oxide and 4-6 parts of polybutadiene grafted maleic anhydride;
the preparation method of the modified polytetrafluoroethylene comprises the following steps: plasma treatment, adding methacrylic acid, supercritical treatment at 35-40Mpa and 50-70 deg.c for 3-5min, zinc oxide grafting, polybutadiene grafting maleic anhydride grafting, and stirring to react.
By adopting the technical scheme, the surface of the polytetrafluoroethylene is modified by adopting plasma treatment, so that the reactivity of the polytetrafluoroethylene is improved; under the action of supercritical pressurization, the methacrylic acid permeates and is protected on the surface of the polytetrafluoroethylene; after zinc oxide is added, methacrylic acid reacts with zinc oxide in situ, in-situ generated zinc methacrylate is coated on the surface of polytetrafluoroethylene, polybutadiene grafted maleic anhydride is added, and under the stirring action, the polybutadiene grafted maleic anhydride is embedded between the zinc methacrylates and fully reacts with the zinc methacrylates. The surface of the modified polytetrafluoroethylene is coated with zinc methacrylate and polybutadiene grafted maleic anhydride, so that the modified polytetrafluoroethylene has good compatibility with rubber, and the wear resistance of rubber products is improved.
In a specific embodiment, the rubber is present in a mass ratio of (3-5): 1 and a modified natural rubber.
By adopting the technical scheme, the natural rubber is a nonpolar macromolecule, the molecular structure contains unsaturated double bonds, oxidation, addition and other reactions are easy to perform, the ageing resistance is poor, and the ageing resistance is improved by modifying the natural rubber; the natural rubber forms partial crystallization when deformed under the action of stress, so that the natural rubber has self-reinforcing effect, higher mechanical strength, excellent elasticity, maximum elongation at break up to 1000%, rebound rate up to 70-80% in the range of 0-100 ℃, small hysteresis loss of the natural rubber, low heat generation after multiple deformation and good flexibility resistance.
In a specific embodiment, the modified natural rubber is prepared as follows: mixing natural rubber with tetrahydrofuran to obtain a mixture, adding 3-hydrophobic-1-propanol and dimethyl azodiisobutyrate into the tetrahydrofuran solution to form a mixed solution, dripping the mixed solution into the mixture to react to form a mixture, adding the tetrahydrofuran solution containing 2, 6-di-tert-butyl-4-methylphenol into the mixture after the reaction, evaporating to remove the tetrahydrofuran, and separating the solution.
By adopting the technical scheme, as the carbon-carbon unsaturated double bond is contained on the natural rubber molecular chain, 3-solvophobic-1-propanol is adopted as a modifier, the natural rubber molecular chain contains a plurality of hydroxyl groups through solvophobic-alkene electric shock reaction, and thioether groups with a hydroperoxide decomposition function are also introduced on the natural rubber molecular chain when the hydroxyl groups are introduced, so that the capture of peroxy free radicals is promoted, the ageing resistance of the natural rubber is improved, and meanwhile, the active groups interact with the active groups on polytetrafluoroethylene, so that the reactive points are increased, the probability of crosslinking of the molecular chain is increased, and the integral strength of a rubber product is improved.
In a specific embodiment, the adjuvants include a vulcanizing agent and a vulcanization accelerator; the vulcanizing agent is one or more of sulfur, maleic amide derivatives, peroxide vulcanizing agents, metal oxide vulcanizing agents and amine vulcanizing agents; the vulcanization accelerator is one or more of vulcanization accelerator DM, vulcanization accelerator TMTD and vulcanization accelerator NOBS.
By adopting the technical scheme, the vulcanizing agent can lead the molecular structure of vulcanized rubber to carry out chemical crosslinking reaction, so that the linear molecular structure generates a three-dimensional porous structure, the ductility is reduced, and the ductility compressive strength of the rubber is improved; the vulcanization accelerator can accelerate the vulcanization reaction, shorten the vulcanization time, reduce the vulcanization temperature, reduce the consumption of vulcanizing agent, improve the physical and mechanical properties of vulcanized rubber, improve the vulcanization production efficiency and the quality of vulcanized rubber, ensure that the product has uniform vulcanization degree and reduce the product cost.
In a specific embodiment, the vulcanizing agent is a peroxide-based vulcanizing agent.
By adopting the technical scheme, the peroxide vulcanizing agent can react with methacrylic acid coated on the surface of the polytetrafluoroethylene to form a cross-linking bond, so that the combination property of the polytetrafluoroethylene and the rubber is improved.
In a specific embodiment, the vulcanization accelerator is present in a mass ratio of (0.5-2): 1 and a vulcanization accelerator TMTD.
By adopting the technical scheme, the vulcanization accelerator DM and the vulcanization accelerator TMTD have good synergistic effect, the vulcanization accelerator DM and the vulcanization accelerator TMTD can accelerate the vulcanization process of rubber, reduce the vulcanization temperature, shorten the time required for the rubber to reach positive vulcanization, ensure that the positive vulcanization period has a longer time, avoid the deterioration of the vulcanized rubber performance, and improve the sludge mechanical property of the rubber.
In a specific embodiment, the auxiliary agent further comprises carbon black, which is one or more of carbon black N234, carbon black N339, carbon black N550, carbon black N660, preferably carbon black N550.
By adopting the technical scheme, carbon black can form a proper amount of carbon black net structure in the rubber, so that the friction heat generation in the rubber is reduced, the thermo-oxidative aging is slowed down, and the aging resistance of the rubber is improved; and as the particle size of the carbon black is reduced, the dosage of the carbon black is increased, the carbon black network structure formed in the rubber is increased, under the vibration condition, stress concentration is more easily formed in the rubber system to promote the breakage of a rubber macromolecular chain, and the damping vibration performance of the rubber shock pad is damaged, so that the addition amount and the particle size of the carbon black are required to be moderate, and the active effect on rubber products can be achieved.
In a second aspect, the application provides a method for preparing an automobile rubber shock pad, which adopts the following technical scheme:
a process for preparing the shock-absorbing pad of rubber for car includes such steps as banburying rubber at 70-100 deg.C for 1-2min, adding modified polytetrafluoroethylene and damping agent, banburying for 6-10min, adding assistant, banburying for 1-3min, and sulfurizing at 160-180 deg.C for 20-30 min.
According to the technical scheme, the modified polytetrafluoroethylene and the damping agent can be more uniformly dispersed in the rubber by adopting step-by-step banburying, and then the auxiliary agent is added to carry out a crosslinking reaction, so that the fluidity of the reaction sizing material is improved, and the whole preparation method is simple, easy to control and convenient to realize.
In summary, the application has the following beneficial effects:
1. according to the application, the polytetrafluoroethylene is modified by methacrylic acid and polybutadiene grafted maleic anhydride, so that the compatibility of the polytetrafluoroethylene and rubber is improved, and the wear resistance of the rubber pad is improved; meanwhile, by adding the damping agent and utilizing the synergistic effect of the polyester long fiber and the graphene, the creep property of the rubber pad is improved;
2. according to the application, the natural rubber is modified through the hydrophobic-alkene electric shock reaction, so that the ageing resistance of the natural rubber is improved, and simultaneously, the introduced active groups interact with the active groups on the polytetrafluoroethylene, so that the reactive points are increased, the probability of crosslinking of molecular chains is increased, and the overall strength of a rubber product is improved;
3. the peroxide vulcanizing agent selected by the application can react with methacrylic acid coated on the surface of polytetrafluoroethylene to form a cross-linking bond, so that the bonding property of polytetrafluoroethylene and rubber is improved.
Detailed Description
The present application will be described in further detail with reference to examples and examples.
Preparation example
Preparation example 1
The application discloses a modified polytetrafluoroethylene which is prepared from 100g of polytetrafluoroethylene, 3g of methacrylic acid, 2g of zinc oxide and 4g of polybutadiene grafted maleic anhydride.
The application also discloses a preparation method of the modified polytetrafluoroethylene, which comprises the following steps:
and (3) carrying out plasma treatment on polytetrafluoroethylene by adopting argon plasma at the frequency of 12Nhz for 180 seconds, then adding methacrylic acid, carrying out supercritical treatment in nitrogen fluid at the temperature of 70 ℃ under the pressure of 35Mpa for 3 minutes, adding zinc oxide and polybutadiene grafted maleic anhydride, and stirring at the speed of 2000r/min for 6 minutes to obtain the modified polytetrafluoroethylene.
Preparation example 2
The application discloses a modified polytetrafluoroethylene which is prepared from 100g of polytetrafluoroethylene, 15g of methacrylic acid, 6g of zinc oxide and 6g of polybutadiene grafted maleic anhydride.
The application also discloses a preparation method of the modified polytetrafluoroethylene, which comprises the following steps:
and (3) carrying out plasma treatment on polytetrafluoroethylene by adopting argon plasma at the frequency of 12NHz for 180 seconds, then adding methacrylic acid, carrying out supercritical treatment in nitrogen fluid at the temperature of 50 ℃ under the pressure of 40Mpa for 5 minutes, adding zinc oxide and polybutadiene grafted maleic anhydride, and stirring at the speed of 3000r/min for 3 minutes to obtain the modified polytetrafluoroethylene.
Preparation example 3
The application discloses a preparation method of modified natural rubber, which comprises the following steps:
s10, adding 15g of natural rubber and 10ml of tetrahydrofuran into a reaction kettle, and magnetically stirring for 30min to form a mixture;
s20, dropwise adding 20ml of tetrahydrofuran solution containing 1g of 3-hydrophobic-1-propanol and 0.4g of dimethyl azodiisobutyrate into the mixture at 65 ℃ for reacting for 100min to form a mixture;
s30, adding 3ml of tetrahydrofuran solution containing 0.1g of 2, 6-di-tert-butyl-4-methylphenol into the mixture, and stopping heating and stirring; removing tetrahydrofuran by rotary evaporation, and separating with methanol.
Examples
Examples 1 to 14
As shown in Table 1, the main difference between examples 1 to 14 is the difference in the raw material ratio of the automobile rubber shock pad.
The following description will take example 1 as an example. The embodiment of the application discloses an automobile rubber shock pad, which is prepared from 45Kg of natural rubber, 15Kg of modified natural rubber, 10Kg of modified polytetrafluoroethylene, 5Kg of polyester long fiber, 5Kg of graphene powder, 3.5Kg of peroxide vulcanizing agent, 0.5Kg of vulcanization accelerator DM0.5Kg and 1Kg of vulcanization accelerator TMTD; wherein the modified natural rubber is obtained in preparation example 3, and the modified polytetrafluoroethylene is obtained in preparation example 1.
The embodiment of the application also discloses a preparation method of the automobile rubber shock pad, which comprises the following steps: the specific process is as follows: mixing natural rubber and modified rubber at 100deg.C, banburying for 1min, adding modified polytetrafluoroethylene, polyester long fiber and graphene powder, banburying for 6min, adding peroxide vulcanizing agent, vulcanization accelerator DM and vulcanization accelerator TMTD, banburying for 1min, and vulcanizing at 160deg.C for 20 min.
Table 1 the raw material ratios of the automobile rubber shock pad in examples 1 to 14
The preparation method of the automobile rubber shock pad of the embodiment 14 comprises the following steps: mixing natural rubber and modified rubber at 70 ℃, banburying for 2min, adding modified polytetrafluoroethylene, polyester long fiber and graphene powder, continuously banburying for 10min, adding peroxide vulcanizing agent, vulcanization accelerator DM, vulcanization accelerator TMTD and carbon black N550, banburying for 3min, and vulcanizing at 180 ℃ for 30 min.
Example 15
This example is substantially the same as example 14 except that the modified polytetrafluoroethylene was obtained in preparation example 2.
Example 16
This example is substantially the same as example 8, except that sulfur is used as the vulcanizing agent, and in other examples, one or more of a maleamide derivative, a metal oxide vulcanizing agent, and an amine vulcanizing agent may be used.
Comparative example
Comparative example 1
This comparative example differs from example 1 in that modified polytetrafluoroethylene and a damping agent are not added.
Comparative example 2
This comparative example differs from example 4 in that the modified polytetrafluoroethylene was replaced with an equivalent amount of polytetrafluoroethylene.
Comparative example 3
This comparative example differs from example 6 in that the polyester long fiber was replaced with an equivalent amount of graphene powder.
Comparative example 4
This comparative example differs from example 6 in that the graphene powder was replaced with an equivalent amount of polyester long fibers.
Comparative example 5
This example differs from example 1 in that the modified natural rubber is replaced with an equivalent amount of natural rubber.
Performance test
The automobile rubber shock-absorbing pads in examples 1 to 16 and comparative examples 1 to 5 above were subjected to performance test, and the test results are shown in Table 2.
1. Physical and mechanical properties: hardness was measured according to GB/T531-1999 standard; tensile properties were measured according to GB/T528-1998 at a test temperature of 25℃and a traction speed of 500mm/min.
2. Wear resistance: the abrasion volume was tested on an electronic tensile machine according to GB/T529-2008.
3. Creep resistance: the percent creep was measured according to GB 20688.2-2006.
4. Ageing resistance: according to GB3512-83 standard, hot air aging performance was measured at 70℃for 48 hours, characterized by the rate of change of tensile strength.
Table 2 table of performance test data for examples 1-16 and comparative examples 1-5
Referring to table 2, in combination with examples 1 to 5 and comparative example 5, it can be seen that changing the addition amount of rubber and the mass ratio of natural rubber to modified natural rubber within an appropriate range has more excellent aging resistance than without adding modified rubber; according to the application, 3-solenoxy-1-propanol is adopted as a modifier, a solenoxy-alkene electric shock reaction is utilized to enable a natural rubber molecular chain to contain a plurality of hydroxyl groups, and thioether groups with a hydroperoxide decomposition function are also introduced into the natural rubber molecular chain while the hydroxyl groups are introduced, so that the capture of peroxy free radicals is promoted, the ageing resistance of natural rubber is improved, and meanwhile, the active groups interact with the active groups on polytetrafluoroethylene, so that the reactive points are increased, the probability of crosslinking of the molecular chain is increased, and the integral strength of a rubber product is improved.
Referring to table 2, in combination with examples 4, 6 and 7 and comparative example 2, it can be seen that the rubber products obtained after modification of polytetrafluoroethylene have excellent abrasion resistance. According to the application, the zinc acrylate and polybutadiene grafted maleic anhydride and polytetrafluoroethylene have strong acting force, so that the polytetrafluoroethylene surface is provided with a plurality of active groups, the modified polytetrafluoroethylene has good compatibility with rubber, and is easy to disperse in a natural rubber substrate, so that uniform mixing and dispersion are realized in the natural rubber substrate, and the wear resistance of a rubber product is improved.
Referring to table 2, in combination with examples 6, 8 and 9 and comparative examples 3 and 4, it can be seen that the creep resistance effect of polyester long fiber and graphene powder added alone as a damping agent to a rubber mat system is not as good as that of the two added together; the polyester long fiber has the characteristics of high rigidity, high toughness, good creep resistance, fatigue resistance and the like; the graphene can be combined on the surface of the rubber macromolecules after being added to form a lubricating layer, so that heat generated by mutual friction among the rubber macromolecules is reduced, the elastic deformation capacity of the rubber macromolecules is improved, the rebound resilience of a rubber product is improved, and the creep property of a rubber material is improved; meanwhile, the polyester long fibers are inserted among the lamellar graphenes, so that the rebound resilience and creep resistance of the rubber material are improved while the high damping characteristic of the rubber is endowed, and the high damping characteristic of the rubber and the creep resistance of the rubber material have good synergistic effect.
Referring to Table 2, in combination with examples 8, 10-13 and example 16, it can be seen that the mechanical properties of the rubber article can be improved by selecting peroxide-based vulcanizing agent as compared with sulfur; the peroxide vulcanizing agent can react with methacrylic acid coated on the surface of the polytetrafluoroethylene to form a cross-linking bond, so that the combination property of the polytetrafluoroethylene and the rubber is improved, and the mechanical property of the rubber product is further improved.
The addition amount of the vulcanizing agent and the vulcanizing accelerator and the mass ratio of the vulcanizing accelerator DM to the vulcanizing accelerator TMTD are changed within a proper range, and the prepared rubber product has good mechanical properties, wear resistance, creep resistance and aging resistance; the vulcanizing agent can lead the molecular structure chain of vulcanized rubber to have chemical crosslinking reaction, lead the linear molecular structure to generate a three-dimensional porous structure, reduce the ductility and improve the ductility compressive strength of the rubber; the vulcanization accelerator can accelerate the vulcanization reaction, shorten the vulcanization time, reduce the vulcanization temperature, reduce the consumption of vulcanizing agent, improve the physical and mechanical properties of vulcanized rubber, improve the vulcanization production efficiency and the quality of vulcanized rubber, ensure that the product has uniform vulcanization degree and reduce the product cost.
Referring to Table 2, in combination with examples 12 and 14, it can be seen that the application can improve the aging resistance of rubber products by adding carbon black to the rubber system; the carbon black can form a proper amount of carbon black net structure in the rubber, so that the friction heat generation in the rubber is reduced, the thermal oxidation aging is slowed down, and the ageing resistance of the rubber product is improved.
Referring to table 2, in combination with example 1 and comparative example 1, it can be seen that the present application improves the abrasion resistance and creep resistance of rubber products by adding modified polytetrafluoroethylene and a damping agent to the rubber system. The polytetrafluoroethylene is modified by methacrylic acid and polybutadiene grafted maleic anhydride, so that the compatibility of the polytetrafluoroethylene and rubber is improved, and the wear resistance of the rubber pad is improved; meanwhile, by adding the damping agent and utilizing the synergistic effect of the polyester long fiber and the graphene, the creep property of the rubber pad is improved.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (9)
1. An automobile rubber shock pad which is characterized in that: the composite material is prepared from the following raw materials in parts by weight: 60-70 parts of rubber, 10-20 parts of modified polytetrafluoroethylene, 10-20 parts of damping agent and 5-10 parts of auxiliary agent;
the modified polytetrafluoroethylene is formed by coating and modifying zinc methacrylate and polybutadiene grafted maleic anhydride;
the damping agent is a mixture of polyester long fibers and graphene powder.
2. The automotive rubber cushion according to claim 1, wherein: the modified polytetrafluoroethylene is prepared from the following raw materials in parts by weight: 100 parts of polytetrafluoroethylene, 3-15 parts of methacrylic acid, 2-6 parts of zinc oxide and 4-6 parts of polybutadiene grafted maleic anhydride;
the preparation method of the modified polytetrafluoroethylene comprises the following steps: plasma treatment, adding methacrylic acid, supercritical treatment at 35-40Mpa and 50-70 deg.c for 3-5min, zinc oxide grafting, polybutadiene grafting maleic anhydride grafting, and stirring to react.
3. The automotive rubber cushion according to claim 1, wherein: the mass ratio of the rubber is (3-5): 1 and a modified natural rubber.
4. The automotive rubber cushion according to claim 3, wherein: the preparation method of the modified natural rubber comprises the following steps: mixing natural rubber with tetrahydrofuran to obtain a mixture, adding 3-hydrophobic-1-propanol and dimethyl azodiisobutyrate into the tetrahydrofuran solution to form a mixed solution, dripping the mixed solution into the mixture to react to form a mixture, adding the tetrahydrofuran solution containing 2, 6-di-tert-butyl-4-methylphenol into the mixture after the reaction, evaporating to remove the tetrahydrofuran, and separating the solution.
5. The automotive rubber cushion according to claim 1, wherein: the auxiliary agent comprises a vulcanizing agent and a vulcanization accelerator; the vulcanizing agent is one or more of sulfur, maleic amide derivatives, peroxide vulcanizing agents, metal oxide vulcanizing agents and amine vulcanizing agents; the vulcanization accelerator is one or more of vulcanization accelerator DM, vulcanization accelerator TMTD and vulcanization accelerator NOBS.
6. The automotive rubber cushion according to claim 5, wherein: the vulcanizing agent is a peroxide vulcanizing agent.
7. The automotive rubber cushion according to claim 5, wherein: the vulcanization accelerator is prepared from the following components in percentage by mass (0.5-2): 1 and a vulcanization accelerator TMTD.
8. The automotive rubber cushion according to claim 5, wherein: the auxiliary agent also comprises carbon black, and the carbon black is one or more of carbon black N234, carbon black N339, carbon black N550 and carbon black N660.
9. The method for producing an automobile rubber shock pad as claimed in any one of claims 1 to 8, characterized in that: mixing rubber at 70-100deg.C for 1-2min, adding modified polytetrafluoroethylene and damping agent, mixing for 6-10min, adding adjuvants, mixing for 1-3min, and vulcanizing at 160-180deg.C for 20-30 min.
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