CN115304871B - Rubber material for automobile shock absorption and preparation method thereof - Google Patents
Rubber material for automobile shock absorption and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 79
- 239000005060 rubber Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 58
- 230000035939 shock Effects 0.000 title claims abstract description 41
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 38
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 22
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 22
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 21
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 21
- 229920001194 natural rubber Polymers 0.000 claims abstract description 21
- 239000006229 carbon black Substances 0.000 claims abstract description 20
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012188 paraffin wax Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- 238000013016 damping Methods 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 16
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920001967 Metal rubber Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- 241001247986 Calotropis procera Species 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/04—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam
- B29C35/049—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam using steam or damp
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a rubber material for automobile shock absorption, which comprises the following raw materials: butyl rubber, natural rubber, graphene oxide, sodium thiosulfate, hydrochloric acid, carbon black, magnesium oxide, paraffin, an anti-aging agent, a tackifier, a softener and an accelerator; the mass ratio of the butyl rubber, the natural rubber, the graphene oxide, the sodium thiosulfate, the hydrochloric acid, the carbon black, the magnesium oxide, the paraffin wax, the anti-aging agent, the tackifier, the softener and the accelerator is 40-60:15-35:1-5:0.01-0.26:0.03-0.37:6-12:2-6:1-5:2-4:1-3:1-3:1-2. The application discloses a preparation method of the rubber material for automobile shock absorption. The application not only improves the high temperature resistance, corrosion resistance and adhesion with metal of the rubber material, but also can protect metal or other matrixes from being corroded by various media, and prolongs the service life of the rubber lining.
Description
Technical Field
The application relates to the technical field of automobile shock absorption, in particular to a rubber material for automobile shock absorption and a preparation method thereof.
Background
With the rapid development of modern industry, vibration and noise have become serious problems in various fields, which can reduce operation accuracy, affect product quality, shorten product life, make high-precision instruments not work normally, and even endanger safety.
In the manufacture of automobiles, a damper is one of indispensable parts, which is mainly used for suppressing vibration and impact from road surfaces when a spring bounces after absorbing vibration, and plays an important role in comfort and steering stability of vehicles. The principle of the existing shock absorber bushing is that the vibration mechanical energy is converted into heat energy through an elastic support to be emitted to the surrounding environment, so that the vibration isolation effect can be achieved. The shock absorbing bushings are classified into a variety of types, including pure rubber shock absorbing bushings, metal rubber shock absorbing bushings, air spring shock absorbing bushings, etc., according to the material of the shock absorbing bushings.
Butyl rubber is a flexible polymer material with the largest damping coefficient and has high chemical stability. The butyl rubber has the advantages of remarkable high damping and no toxicity, is the most ideal material for the new generation of damping films, and comprehensively solves the problems of high damping factor, wide temperature range and other damping characteristics, good mechanical properties, high/low temperature aging resistance, low smoke, zero halogen, high flame retardance, sanitation, environmental protection and the like of the shock absorption lining for automobiles.
Because butyl rubber itself has advantages such as light in weight, shock resistance and easy absorption high frequency vibration, in addition to the development of rubber and metal bonding technique, metal rubber spring (i.e. rubber bush) that metal and rubber combined formed can effectively alleviate road unevenness to vibration and impact of car to the vibration is attenuated rapidly, improves the travelling comfort of driving, reduces the dynamic stress of each part of automobile body, extension vehicle life.
The traditional rubber lining is mainly made of natural rubber or styrene-butadiene rubber, and the hard rubber lining prepared by high-temperature vulcanization can only be suitable for general corrosive media and lower temperature environments (not more than 80 ℃). And are not applicable to higher temperature or highly corrosive media. Meanwhile, the shock absorption lining combined by metal and rubber has certain performance requirements on rubber, and the prior butyl rubber product has a large room for improvement in the aspects of corrosion resistance, aging resistance and high temperature resistance.
Disclosure of Invention
The application aims to solve the defects in the prior art, and provides a rubber material for automobile shock absorption and a preparation method thereof.
A rubber material for automobile shock absorption comprises the following raw materials: butyl rubber, natural rubber, graphene oxide, sodium thiosulfate, hydrochloric acid, carbon black, magnesium oxide, paraffin, an anti-aging agent, a tackifier, a softener and an accelerator; the mass ratio of the butyl rubber, the natural rubber, the graphene oxide, the sodium thiosulfate, the hydrochloric acid, the carbon black, the magnesium oxide, the paraffin wax, the anti-aging agent, the tackifier, the softener and the accelerator is 40-60:15-35:1-5:0.01-0.26:0.03-0.37:6-12:2-6:1-5:2-4:1-3:1-3:1-2.
Preferably, the anti-aging agent is anti-aging agent A or/and anti-aging agent NBC.
Preferably, the anti-aging agent comprises an anti-aging agent A and an anti-aging agent NBC according to the mass ratio of 1-2: 1-2.
Preferably, the tackifier is a phenolic tackifying resin.
Preferably, the softener is a polybutene-based softener.
Preferably, the accelerator is at least one of accelerator M, accelerator TMTD and accelerator TTTE.
The preparation method of the rubber material for automobile shock absorption comprises the following steps:
(1) Adding graphene oxide into deionized water, stirring for 10-20min, adding sodium thiosulfate solution, performing ultrasonic dispersion for 10-20min, dropwise adding hydrochloric acid in the ultrasonic dispersion process at the ultrasonic frequency of 10-18kHz, continuing ultrasonic treatment for 1-2h, centrifuging, washing, and drying to obtain a graphene oxide compound;
(2) Mixing butyl rubber and natural rubber uniformly, sequentially adding tackifier, carbon black, magnesium oxide and paraffin wax, continuously mixing for 5-15min, adding an anti-aging agent and graphene oxide compound, mixing for 2-10min, then adding a softener and an accelerator, mixing for 2-6min, and extruding and molding to obtain a blank;
(3) And (3) applying the blank on a metal matrix, introducing saturated steam at normal pressure, preserving heat for 5-15h at 50-60 ℃, adjusting the temperature to 100-120 ℃, preserving heat for 10-20min, cooling to room temperature, and drying to obtain the rubber material for automobile shock absorption.
Preferably, in the step (1), the ratio of deionized water to graphene oxide is 10-20:1-5.
Preferably, in step (1), the sodium thiosulfate solution has a concentration of 0.1 to 0.4mol/L.
Preferably, in step (1), the hydrochloric acid concentration is 1-2mol/L.
Butyl rubber is one type of synthetic rubber, which is synthesized from isobutylene and a small amount of isoprene. At present, butyl rubber has low vulcanization speed, needs to be matched with super accelerators, has high temperature and long curing time, has poor compatibility with other rubbers, and is difficult to use. The graphene oxide not only has a single-layer structure and an ultra-large specific surface area, but also contains abundant active oxygen-containing groups on the sheet layer, and the groups can form strong interface interaction with polar rubber molecular chains through hydrogen bonds or ionic bonds. However, butyl rubber is a nonpolar substance, and there is a problem that interface compatibility between graphene oxide and butyl rubber is poor.
According to the preparation method, the graphene oxide and the sodium thiosulfate are compounded, and under the action of hydrochloric acid, heterogeneous nucleation has lower activation energy than homogeneous nucleation, so that the obtained nano particles do not self-nucleate but tend to deposit between graphene oxide sheets, and meanwhile pi bonds on the obtained nano particles and the graphene oxide sheets act, so that the stability of the obtained graphene oxide composite is excellent.
The graphene oxide composite is further compounded with butyl rubber, graphene oxide nano particles participate in a cross-linking reaction between molecular chains of the butyl rubber, so that strong interface interaction is formed, graphene oxide is uniformly dispersed in the butyl rubber, meanwhile, as graphene oxide sheets are in a glass state, layered graphene oxide is dispersed in a rubber matrix material in a nano level, a rigid network structure is constructed and compounded with the rubber network structure, a high-strength barrier to penetrant molecules can be formed in the system, and the barrier effect is remarkable.
The layered graphene oxide can effectively restrict the movement of rubber molecular chains, further reduce the cavity between the rubber matrix and the layered graphene oxide, and effectively improve the mechanical property, corrosion resistance, high temperature resistance and processability of the butyl composite rubber material under the comprehensive action, so that the key technical difficulty of using the material in a rubber anti-corrosion lining is overcome.
In the vulcanizing process, a specific vulcanizing process is adopted, namely low-temperature long-time vulcanizing is matched with high-temperature short-time vulcanizing, steam is used as a heat carrier, and as the polar substance-graphene oxide compound still has good hydrophilicity, the saturated steam can realize quick heat conduction in a system, so that the vulcanizing speed can be effectively improved, the vulcanizing time can be reduced, the lining quality can be effectively ensured, the defects of swelling and falling are reduced, and the mechanical property of the product is excellent.
The preparation method of the application is simple and convenient, has short production period and is easy for industrial production, not only improves the high temperature resistance and corrosion resistance of the rubber material and the adhesiveness with metal, can protect metal or other matrixes from being corroded by various media, but also improves the service life of the rubber lining, so that the rubber corrosion-resistant lining material can be comprehensively applied to various important industries such as environmental protection, energy sources, papermaking, foods, electronics, petrochemical industry and the like, creates good economic benefit and social benefit, and fills the blank of the application of nano technology in the field in China.
Drawings
FIG. 1 is a graph showing the heat-air aging resistance of the rubber materials obtained in example 5 and comparative examples 1 to 2.
FIG. 2 is a graph showing the comparison of the hot corrosion resistance of the rubber materials obtained in example 5 and comparative examples 1 to 2.
Detailed Description
The application is further illustrated below in connection with specific embodiments.
Example 1
A rubber material for automobile shock absorption comprises the following raw materials: 40kg of butyl rubber, 15kg of natural rubber, 1kg of graphene oxide, 0.01kg of sodium thiosulfate, 0.03kg of hydrochloric acid, 6kg of carbon black, 2kg of magnesium oxide, 1kg of paraffin, 2kg of an anti-aging agent, 1kg of octyl phenol tackifying resin (CAS: 26678-93-3), 1kg of a poly 1-butene softener, 0.3kg of an accelerator M and 0.7kg of an accelerator TMTD.
The anti-aging agent comprises an anti-aging agent A and an anti-aging agent NBC according to the mass ratio of 1: 2.
The preparation method of the rubber material for automobile shock absorption comprises the following steps:
(1) Adding graphene oxide into deionized water, and stirring at a high speed for 10min, wherein the ratio of the deionized water to the graphene oxide is 10:1, stirring at 1000r/min, adding sodium thiosulfate solution with the concentration of 0.1mol/L, performing ultrasonic dispersion for 10min, dropwise adding hydrochloric acid with the concentration of 1mol/L into the solution under the ultrasonic action at the ultrasonic frequency of 10kHz, continuing ultrasonic treatment for 1h, centrifuging, washing with deionized water, and drying to obtain a graphene oxide compound;
(2) Adding butyl rubber and natural rubber into an internal mixer, uniformly mixing, sequentially adding octyl phenolic tackifying resin, carbon black, magnesium oxide and paraffin wax, continuously mixing for 5min, adding an anti-aging agent and graphene oxide compound, mixing for 2min, then adding a poly-1-butene softener, an accelerator M and an accelerator TMTD, mixing for 2min, and feeding into an extruder for extrusion molding to obtain a blank;
(3) And (3) applying the blank on a metal matrix, introducing saturated steam at normal pressure, preserving heat for 5 hours at 50 ℃, adjusting the temperature to 100 ℃, preserving heat for 10 minutes, cooling to room temperature, and drying to obtain the rubber material for automobile shock absorption.
Example 2
A rubber material for automobile shock absorption comprises the following raw materials: 60kg of butyl rubber, 35kg of natural rubber, 5kg of graphene oxide, 0.26kg of sodium thiosulfate, 0.37kg of hydrochloric acid, 12kg of carbon black, 6kg of magnesium oxide, 5kg of paraffin, 4kg of an anti-aging agent, 3kg of octyl phenolic tackifying resin, 3kg of a poly 1-butene softener, 0.5kg of an accelerator M and 1.5kg of an accelerator TTTE.
The anti-aging agent comprises an anti-aging agent A and an anti-aging agent NBC according to the mass ratio of 2: 1.
The preparation method of the rubber material for automobile shock absorption comprises the following steps:
(1) Adding graphene oxide into deionized water, and stirring at a high speed for 20min, wherein the ratio of the deionized water to the graphene oxide is 20:5, adding sodium thiosulfate solution with the concentration of 0.4mol/L at the stirring speed of 2000r/min, performing ultrasonic dispersion for 20min, dropwise adding hydrochloric acid with the concentration of 2mol/L into the solution under the ultrasonic action at the ultrasonic frequency of 18kHz, continuing ultrasonic treatment for 2h, centrifuging, washing with deionized water, and drying to obtain the graphene oxide compound;
(2) Adding butyl rubber and natural rubber into an internal mixer, uniformly mixing, sequentially adding octyl phenolic tackifying resin, carbon black, magnesium oxide and paraffin wax, continuously mixing for 15min, adding an anti-aging agent and graphene oxide compound, mixing for 10min, then adding a poly-1-butene softener, an accelerator M and an accelerator TTTE, mixing for 6min, and feeding into an extruder for extrusion molding to obtain a blank;
(3) And (3) applying the blank on a metal matrix, introducing saturated steam at normal pressure, preserving heat for 15 hours at 60 ℃, adjusting the temperature to 120 ℃, preserving heat for 20 minutes, cooling to room temperature, and drying to obtain the rubber material for automobile shock absorption.
Example 3
A rubber material for automobile shock absorption comprises the following raw materials: 45kg of butyl rubber, 30kg of natural rubber, 2kg of graphene oxide, 0.2528kg of sodium thiosulfate, 0.0365kg of hydrochloric acid, 10kg of carbon black, 3kg of magnesium oxide, 4kg of paraffin, 2.5kg of an anti-aging agent, 2.5kg of octyl phenolic tackifying resin, 1.5kg of a poly-1-butene softener, 0.9kg of an accelerator TMTD and 0.9kg of an accelerator TTTE.
The anti-aging agent comprises an anti-aging agent A and an anti-aging agent NBC according to the mass ratio of 1.3: 1.8.
The preparation method of the rubber material for automobile shock absorption comprises the following steps:
(1) Adding graphene oxide into deionized water, and stirring at a high speed for 13min, wherein the ratio of deionized water to graphene oxide is 18:2, adding sodium thiosulfate solution with the concentration of 0.2mol/L at the stirring speed of 1800r/min, performing ultrasonic dispersion for 17min, dropwise adding hydrochloric acid with the concentration of 1.7mol/L into the solution under the ultrasonic action at the ultrasonic frequency of 12kHz, continuing ultrasonic treatment for 1.2h, centrifuging, washing with deionized water, and drying to obtain the graphene oxide compound;
(2) Adding butyl rubber and natural rubber into an internal mixer, uniformly mixing, sequentially adding octyl phenolic tackifying resin, carbon black, magnesium oxide and paraffin wax, continuously mixing for 12min, adding an anti-aging agent and graphene oxide compound, mixing for 4min, then adding a poly-1-butene softener, an accelerator TMTD and an accelerator TTTE, mixing for 5min, and sending into an extruder for extrusion molding to obtain a blank;
(3) And (3) applying the blank on a metal matrix, introducing saturated steam at normal pressure, preserving heat for 12 hours at 52 ℃, adjusting the temperature to 105 ℃, preserving heat for 17 minutes, cooling to room temperature, and drying to obtain the rubber material for automobile shock absorption.
Example 4
A rubber material for automobile shock absorption comprises the following raw materials: 55kg of butyl rubber, 20kg of natural rubber, 4kg of graphene oxide, 0.0158kg of sodium thiosulfate, 0.365kg of hydrochloric acid, 8kg of carbon black, 5kg of magnesium oxide, 2kg of paraffin, 3.5kg of an anti-aging agent, 1.5kg of octyl phenolic tackifying resin, 2.5kg of a poly-1-butene softener and 1.2kg of an accelerator TMTD.
The anti-aging agent comprises an anti-aging agent A and an anti-aging agent NBC according to the mass ratio of 1.7: 1.2.
The preparation method of the rubber material for automobile shock absorption comprises the following steps:
(1) Adding graphene oxide into deionized water, and stirring at a high speed for 17min, wherein the ratio of the deionized water to the graphene oxide is 12:4, adding sodium thiosulfate solution with the concentration of 0.3mol/L at the stirring speed of 1200r/min, performing ultrasonic dispersion for 13min, dropwise adding hydrochloric acid with the concentration of 1.3mol/L into the solution under the ultrasonic action at the ultrasonic frequency of 16kHz, continuing ultrasonic treatment for 1.8h, centrifuging, washing with deionized water, and drying to obtain the graphene oxide compound;
(2) Adding butyl rubber and natural rubber into an internal mixer, uniformly mixing, sequentially adding octyl phenolic tackifying resin, carbon black, magnesium oxide and paraffin wax, continuously mixing for 8min, adding an anti-aging agent and graphene oxide compound, mixing for 8min, then adding a poly-1-butene softener and an accelerator TMTD, mixing for 3min, and feeding into an extruder for extrusion molding to obtain a blank;
(3) And (3) applying the blank on a metal matrix, introducing saturated steam at normal pressure, preserving heat for 8 hours at 58 ℃, adjusting the temperature to 115 ℃, preserving heat for 13 minutes, cooling to room temperature, and drying to obtain the rubber material for automobile shock absorption.
Example 5
A rubber material for automobile shock absorption comprises the following raw materials: 50kg of butyl rubber, 25kg of natural rubber, 3kg of graphene oxide, 0.1343kg of sodium thiosulfate, 0.2kg of hydrochloric acid, 9kg of carbon black, 4kg of magnesium oxide, 3kg of paraffin, 3kg of an anti-aging agent, 2kg of octyl phenolic tackifying resin, 2kg of poly 1-butene softener and 1.5kg of accelerator M.
The anti-aging agent comprises an anti-aging agent A and an anti-aging agent NBC according to the mass ratio of 1: 1.
The preparation method of the rubber material for automobile shock absorption comprises the following steps:
(1) Adding graphene oxide into deionized water, and stirring at a high speed for 15min, wherein the ratio of deionized water to graphene oxide is 15:3, adding sodium thiosulfate solution with the concentration of 0.25mol/L at the stirring speed of 1500r/min, performing ultrasonic dispersion for 15min, dropwise adding hydrochloric acid with the concentration of 1.5mol/L into the solution under the ultrasonic action at the ultrasonic frequency of 14kHz, continuing ultrasonic treatment for 1.5h, centrifuging, washing with deionized water, and drying to obtain the graphene oxide compound;
(2) Adding butyl rubber and natural rubber into an internal mixer, uniformly mixing, sequentially adding octyl phenolic tackifying resin, carbon black, magnesium oxide and paraffin wax, continuously mixing for 10min, adding an anti-aging agent and graphene oxide compound, mixing for 6min, then adding a poly-1-butene softener and an accelerator M, mixing for 4min, and feeding into an extruder for extrusion molding to obtain a blank;
(3) And (3) applying the blank on a metal matrix, introducing saturated steam at normal pressure, preserving heat for 10 hours at 55 ℃, adjusting the temperature to 110 ℃, preserving heat for 15 minutes, cooling to room temperature, and drying to obtain the rubber material for automobile shock absorption.
Comparative example 1
A rubber material for automobile shock absorption comprises the following raw materials: 50kg of butyl rubber, 25kg of natural rubber, 3kg of graphene oxide, 0.33kg of sulfur, 9kg of carbon black, 4kg of magnesium oxide, 3kg of paraffin, 3kg of anti-aging agent, 2kg of octyl phenolic tackifying resin, 2kg of poly 1-butene softener and 1.5kg of accelerator M.
The anti-aging agent comprises an anti-aging agent A and an anti-aging agent NBC according to the mass ratio of 1: 1.
The preparation method of the rubber material for automobile shock absorption comprises the following steps:
(1) Adding butyl rubber and natural rubber into an internal mixer, uniformly mixing, sequentially adding octyl phenolic tackifying resin, carbon black, magnesium oxide and paraffin, continuously mixing for 10min, adding an anti-aging agent and graphene oxide, mixing for 6min, then adding a poly-1-butene softener, sulfur and an accelerator M, mixing for 4min, and feeding into an extruder for extrusion molding to obtain a blank;
(2) And (3) applying the blank on a metal matrix, introducing saturated steam at normal pressure, preserving heat for 10 hours at 55 ℃, adjusting the temperature to 110 ℃, preserving heat for 15 minutes, cooling to room temperature, and drying to obtain the rubber material for automobile shock absorption.
The adhesive strength between the rubber materials obtained in example 5 and comparative example 1 and the metal matrix was measured with reference to GB/T7760-2003 method for measuring adhesive strength of vulcanized rubber or thermoplastic rubber with hard sheet by 90 DEG peel. The adhesive strength of the rubber material obtained in example 5 was 9.93N/mm, whereas the adhesive strength of the rubber material obtained in comparative example 1 was only 6.76N/mm.
Comparative example 2
Commercial butyl liners were used.
The rubber materials obtained in example 5 and comparative examples 1 to 2 were subjected to mechanical property test by being prepared into corresponding shapes according to standards, and the results are as follows:
from the above table, it can be seen that: the rubber material obtained in the embodiment 5 has the best mechanical property and the minimum compression set, which shows that the graphene oxide in the rubber material obtained in the application can be uniformly dispersed in a butyl rubber system, so that the mechanical property of the rubber system is enhanced, the cavity between a rubber matrix and layered graphene oxide is reduced, and the material defects are reduced.
The rubber materials obtained in example 5 and comparative examples 1 to 2 were subjected to a heat-resistant air aging test at 170℃for 70 hours with reference to GB/T3512-2001 accelerated hot air aging and heat resistance test of vulcanized rubber or thermoplastic rubber. As shown in FIG. 1, the change rates of the rubber material obtained in example 5 are all the lowest, and the rubber material obtained in the application has good high-temperature resistance and ageing resistance.
Referring to GB/T1690-2006 test method for liquid resistance of vulcanized rubber or thermoplastic rubber, IRM1101# oil is used as a test medium, the rubber materials obtained in example 5 and comparative examples 1-2 are completely immersed in the test medium at 150℃for 70 hours, and then the hardness change rate and the volume change rate of each sample are taken out and tested. The results are shown in FIG. 2. The rubber material obtained in the embodiment 5 has the lowest change rate, and has good high-temperature resistance and corrosion resistance, and can protect metals or other matrixes from being corroded by various media.
The application considers that: the graphene oxide composite and the butyl rubber are compounded, and the graphene oxide nano particles participate in a cross-linking reaction between molecular chains of the butyl rubber, so that strong interface interaction is formed, graphene oxide is uniformly dispersed in the butyl rubber, meanwhile, the graphene oxide lamellar layer is in a glass state, so that the lamellar graphene oxide is dispersed in a rubber matrix material in a nano level, a rigid network structure is constructed and is compounded with the flexible rubber network structure, a high-strength barrier to penetrant molecules can be formed in a system, and the barrier effect is remarkable. The layered graphene oxide can effectively restrict the movement of rubber molecular chains, further reduce the holes between the rubber matrix and the layered graphene oxide, and effectively improve the corrosion resistance and high temperature resistance of the butyl composite rubber material under the comprehensive action. Meanwhile, the application adopts a specific vulcanization process, can effectively ensure the quality of the lining, reduce the defects of bulge and falling off, and has excellent mechanical properties.
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme of the present application and the inventive concept thereof, and should be covered by the scope of the present application.
Claims (8)
1. The rubber material for automobile shock absorption is characterized by comprising the following raw materials: butyl rubber, natural rubber, graphene oxide, sodium thiosulfate, hydrochloric acid, carbon black, magnesium oxide, paraffin, an anti-aging agent, a tackifier, a softener and an accelerator; the mass ratio of the butyl rubber, the natural rubber, the graphene oxide, the sodium thiosulfate, the hydrochloric acid, the carbon black, the magnesium oxide, the paraffin wax, the anti-aging agent, the tackifier, the softener and the accelerator is 40-60:15-35:1-5:0.01-0.26:0.03-0.37:6-12:2-6:1-5:2-4:1-3:1-3:1-2;
the tackifier is phenolic tackifying resin; the softener is polybutene softener;
compounding graphene oxide with sodium thiosulfate, wherein heterogeneous nucleation has lower activation energy than homogeneous nucleation under the action of hydrochloric acid, so that the obtained nano particles do not self-nucleate but tend to deposit between graphene oxide sheets, and pi bonds on the obtained nano particles and the graphene oxide sheets act, so that the stability of the obtained graphene oxide composite is excellent;
the graphene oxide composite is further compounded with butyl rubber, graphene oxide nano particles participate in a cross-linking reaction between butyl rubber molecular chains, so that strong interface interaction is formed, graphene oxide is uniformly dispersed in the butyl rubber, meanwhile, as graphene oxide sheets are in a glass state, layered graphene oxide is dispersed in a rubber matrix material in a nano level, a rigid network structure is constructed and compounded with the rubber network structure, and a high-strength barrier for penetrant molecules is formed in the system;
and the layered graphene oxide can effectively restrict the movement of a rubber molecular chain, so that the cavity between the rubber matrix and the layered graphene oxide is further reduced.
2. The rubber material for automobile vibration damping according to claim 1, wherein the anti-aging agent is an anti-aging agent a or/and an anti-aging agent NBC.
3. The rubber material for automobile shock absorption according to claim 1, wherein the anti-aging agent is prepared from an anti-aging agent A and an anti-aging agent NBC in a mass ratio of 1-2: 1-2.
4. The rubber material for automobile vibration damping according to claim 1, wherein the accelerator is at least one of accelerator M, accelerator TMTD and accelerator TTTE.
5. A method for producing a rubber material for automobile vibration damping according to any one of claims 1 to 4, comprising the steps of:
(1) Adding graphene oxide into deionized water, stirring for 10-20min, adding sodium thiosulfate solution, performing ultrasonic dispersion for 10-20min, dropwise adding hydrochloric acid in the ultrasonic dispersion process at the ultrasonic frequency of 10-18kHz, continuing ultrasonic treatment for 1-2h, centrifuging, washing, and drying to obtain a graphene oxide compound;
(2) Mixing butyl rubber and natural rubber uniformly, sequentially adding tackifier, carbon black, magnesium oxide and paraffin wax, continuously mixing for 5-15min, adding an anti-aging agent and graphene oxide compound, mixing for 2-10min, then adding a softener and an accelerator, mixing for 2-6min, and extruding and molding to obtain a blank;
(3) And (3) applying the blank on a metal matrix, introducing saturated steam at normal pressure, preserving heat for 5-15h at 50-60 ℃, adjusting the temperature to 100-120 ℃, preserving heat for 10-20min, cooling to room temperature, and drying to obtain the rubber material for automobile shock absorption.
6. The method for preparing a rubber material for automobile shock absorption according to claim 5, wherein in the step (1), the ratio of deionized water to graphene oxide is 10-20:1-5.
7. The method for producing a rubber material for automobile vibration damping according to claim 5, wherein in the step (1), the sodium thiosulfate solution concentration is 0.1 to 0.4mol/L.
8. The method for producing a rubber material for automobile vibration damping according to claim 5, wherein in the step (1), the hydrochloric acid concentration is 1 to 2mol/L.
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