CN115340713A - Graphene modified rubber composite material and preparation method thereof - Google Patents
Graphene modified rubber composite material and preparation method thereof Download PDFInfo
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- CN115340713A CN115340713A CN202110521446.9A CN202110521446A CN115340713A CN 115340713 A CN115340713 A CN 115340713A CN 202110521446 A CN202110521446 A CN 202110521446A CN 115340713 A CN115340713 A CN 115340713A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 229920001971 elastomer Polymers 0.000 title claims abstract description 61
- 239000005060 rubber Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 29
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 28
- 229920001194 natural rubber Polymers 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 230000003712 anti-aging effect Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 230000003311 flocculating effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000004200 microcrystalline wax Substances 0.000 claims description 6
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
- 238000005299 abrasion Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract description 3
- 230000017525 heat dissipation Effects 0.000 abstract description 3
- 230000003068 static effect Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005189 flocculation Methods 0.000 description 6
- 230000016615 flocculation Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002834 transmittance 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
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to a graphene modified rubber composition which comprises the following components in parts by weight: 80-95 parts of natural rubber, 5-20 parts of solution-polymerized styrene-butadiene rubber, 35-70 parts of reinforcing agent, 0.5-1.5 parts of graphene dispersion, 1-2 parts of lubricant and 1.5-2.5 parts of vulcanizing agent; the graphene dispersion comprises graphene and a dispersing agent, wherein the weight ratio of the graphene to the dispersing agent is (2-4): 1. according to the application, the problems of dispersibility and the like among materials are solved through the raw material selection, the formula and the processing technology of the sizing material, the strength of the material is improved by nearly 7%, the conductivity is 100 times, and the abrasion characteristic of the material is improved by nearly 1 time through the modification of graphene. The obtained composite material has the advantages of good heat dissipation, good static electricity conducting performance, high strength, good wear resistance, low oil consumption, low carbon emission and the like, and can be widely used for the upper tread, the lower tread and the like of an aircraft tire.
Description
Technical Field
The invention relates to the field of aircraft tires, in particular to an RGO modified rubber composite material special for aircraft tire treads and a preparation method thereof
Background
In the field of tire manufacturing, aircraft tires are known at the top of the industry pyramid, placing near stringent requirements on tire enterprises' development capabilities, skill levels, and manufacturing processes. The field of domestic civil aviation tires in China is always blank due to technical limitation. The radial aviation tire technology is an important component of the advanced aircraft manufacturing technology, is one of the important technical indexes of the aircraft advancement, develops the large aircraft tire with independent intellectual property rights, can break through monopoly of foreign technologies, fills up the technical blank of the domestic radial aviation tire, enables the domestic large aircraft to be used as safe and reliable 'Chinese core', and has great strategic significance in improving the international competitiveness of national industry.
Disclosure of Invention
The application provides a graphene modified rubber composition which comprises the following components in parts by weight:
the graphene dispersion comprises graphene and a dispersing agent, wherein the weight ratio of the graphene to the dispersing agent is (2-4): 1.
in one embodiment, the dispersant is polyvinylpyrrolidone, the lubricant is selected from stearic acid, and the vulcanizing agent is selected from sulfur.
In one embodiment, the reinforcing agent includes a combination of carbon black and white carbon, wherein the amount of carbon black is 10 to 30 parts and the amount of white carbon is 25 to 45 parts.
In one embodiment, the composition further comprises the following components in parts by weight:
in one embodiment, the accelerator comprises a combination of accelerator D and accelerator NS, the amount of accelerator D being from 0.2 parts to 0.6 parts, the amount of accelerator NS being from 1.2 parts to 1.8 parts; the auxiliary accelerator is selected from zinc oxide; the anti-aging agent comprises anti-aging agent 4020, anti-aging agent RD and microcrystalline wax, wherein the amount of the anti-aging agent 4020 is 1-2 parts, the amount of the anti-aging agent RD is 2-5 parts, and the amount of the microcrystalline wax is 1-2 parts.
The present application also provides a graphene-modified rubber composite material, which is manufactured from the graphene-modified rubber composition of the present application.
The application also provides a method for manufacturing the graphene modified rubber composite material, which comprises the following steps:
s1, preparing a graphene dispersion liquid: mixing graphene, a dispersing agent and deionized water, and homogenizing to obtain a graphene dispersion liquid;
s2, mixing and stirring the graphene dispersion liquid and natural latex, flocculating, and drying to obtain RGO natural rubber;
and S3, mixing the RGO natural rubber, the solution-polymerized styrene-butadiene rubber and an additive to obtain the graphene modified rubber composite material.
In one embodiment, S2 is the mixture of graphene dispersion and natural latex is added into calcium chloride aqueous solution for flocculation, and then the flocculate is heated to remove water, so as to obtain the RGO natural rubber; preferably, the concentration of the calcium chloride aqueous solution is 0.5% -1.5%; the heating temperature is 40-60 ℃.
In one embodiment, the mixing temperature is 140 to 150 ℃; after mixing, open mixing was also performed, with a two roll speed ratio of 1.0:1.2-1.0:2.0.
the present application further provides an aircraft tire made from the graphene-modified rubber composite of the present application.
The graphene has the advantages of high strength, good toughness, light weight, high light transmittance, good conductivity and the like, the problems of dispersibility and the like of materials are solved through raw material selection, a formula and a processing technology of the sizing material, the strength of the material is improved by nearly 7%, the conductivity is improved by nearly 100 times, and the abrasion characteristic of the material is improved by nearly 1 time through modification by the graphene. The obtained composite material has the advantages of good heat dissipation, good static electricity conducting performance, high strength, good wear resistance, low oil consumption, low carbon emission and the like, and can be widely used for the upper tread, the lower tread and the like of an aircraft tire.
Detailed Description
The application provides a graphene modified rubber composition, which comprises the following components in parts by weight:
the graphene dispersion comprises graphene and a dispersing agent, wherein the weight ratio of the graphene to the dispersing agent is (2-4): 1.
the graphene modified rubber composition provided by the application can be used for preparing aircraft tires, in particular aircraft tire treads.
The graphene-modified rubber composition of the present application includes natural rubber, which is an elastic solid obtained by subjecting natural latex collected from hevea brasiliensis to a processing step such as coagulation and drying. The natural rubber is a natural high molecular compound taking cis-1,4-polyisoprene as a main component, the rubber hydrocarbon (cis-1,4-polyisoprene) content of the natural rubber is more than 90 percent, and the natural rubber also contains a small amount of protein, fatty acid, sugar, ash and the like.
The graphene modified rubber composition comprises solution-polymerized styrene-butadiene rubber, which is an elastomer synthesized by anionic solution polymerization of styrene and butadiene under the initiation of organic lithium.
The graphene-modified rubber composition of the present application includes a reinforcing agent. In one embodiment, the reinforcing agent includes a combination of carbon black and white carbon, wherein the amount of carbon black is 10 to 30 parts and the amount of white carbon is 25 to 45 parts.
The graphene modified rubber composition comprises a graphene dispersion, wherein the graphene dispersion comprises graphene and a dispersing agent, and the weight ratio of the graphene to the dispersing agent is (2-4): 1. in one embodiment, the dispersant is polyvinylpyrrolidone. By combining the graphene and the dispersing agent, the graphene can be well dispersed in the dispersing agent, and further well dispersed in the graphene modified rubber composition.
The graphene-modified rubber composition of the present application contains a lubricant and a vulcanizing agent. In one embodiment, the lubricant is selected from stearic acid and the vulcanizing agent is selected from sulfur.
In one embodiment, the composition further comprises the following components in parts by weight:
in one embodiment, the accelerator comprises a combination of accelerator D and accelerator NS, the amount of accelerator D being from 0.2 parts to 0.6 parts and the amount of accelerator NS being from 1.2 parts to 1.8 parts.
In one embodiment, the co-promoter is selected from zinc oxide.
In one embodiment, the antioxidant comprises a combination of antioxidant 4020, antioxidant RD, and microcrystalline wax, wherein the amount of antioxidant 4020 is from 1 to 2 parts, the amount of antioxidant RD is from 2 to 5 parts, and the amount of microcrystalline wax is from 1 to 2 parts.
The anti-reversion agent may be PK900 or the like, and the scorch retarder may be CTP or the like.
The present application also provides a graphene-modified rubber composite material, which is manufactured from the graphene-modified rubber composition of the present application.
Specifically, the present application provides a method of manufacturing a graphene-modified rubber composite, comprising the steps of:
s1, preparing a graphene dispersion liquid: mixing graphene, a dispersing agent and deionized water, and homogenizing to obtain a graphene dispersion liquid;
s2, mixing and stirring the graphene dispersion liquid and natural latex, flocculating, and drying to obtain RGO natural rubber;
and S3, mixing the RGO natural rubber, the solution-polymerized styrene-butadiene rubber and an additive to obtain the graphene modified rubber composite material.
In the above method, the S1 step is to prepare a graphene dispersion. By preparing the graphene dispersion liquid in advance, graphene can be uniformly and well dispersed in the final graphene modified rubber composite material, so that the performance of the graphene modified rubber composite material is improved. Specifically, the following procedure may be adopted:
adding graphene powder, a dispersing agent and deionized water into a reactor, stirring and mixing uniformly, homogenizing the preliminarily obtained dispersion liquid by a homogenizer, and carrying out ultrasonic treatment by an ultrasonic machine to obtain the graphene dispersion liquid. In one embodiment, the stirring speed is controlled at 300-500r/min, the homogenization pressure is 700-1000bar, and the ultrasonic frequency is controlled at 400-600MHz. In one embodiment, the graphene: dispersing agent: the weight ratio of water is 2-4:1:100.
and then, placing the graphene dispersion liquid and the natural rubber latex into a reaction kettle, and stirring and fully mixing. Then flocculating and drying to prepare the RGO natural rubber.
And the flocculation is to add a mixture of the graphene dispersion liquid and the natural latex into a calcium chloride aqueous solution for flocculation, and then heat the flocculate to remove water, so as to obtain the RGO natural rubber. In one embodiment, the concentration of the aqueous calcium chloride solution is 0.5% to 1.5%; the heating temperature is 40-60 ℃. The dosage ratio of the mixture of the graphene dispersion liquid and the natural latex to the calcium chloride aqueous solution is (267.17-268.17): 1000. the floc may be heated in an oven to remove water, the oven heating temperature being 40 ℃ to 60 ℃.
And then, mixing the RGO natural rubber, solution polymerized styrene butadiene rubber and an additive to obtain the graphene modified rubber composite material. In one embodiment, the RGO natural rubber, the solution-polymerized styrene-butadiene rubber and the additive are prepared according to a proportion, conveyed into an internal mixer for fully mixing, conveyed into an open mill for tabletting and cooling to obtain the graphene modified rubber composite material. In one embodiment, the mixing temperature is 140-150 ℃, the mixing is carried out, and the open mixing processing condition is to keep the rotor to be filled with water and reduce the temperature. The speed ratio of two open rolls is 1.0:1.2-1.0:2.0.
therefore, the graphene modified rubber composite material special for the aircraft tire tread can be obtained. The graphene modified rubber composite material can be used for preparing aircraft tires, particularly aircraft tire treads.
According to the invention, a certain amount of graphene and a dispersant are pre-dispersed in a liquid solvent to form a graphene concentration dispersion liquid. Mixing the dispersion liquid with natural latex, flocculating to obtain RGO natural rubber raw rubber, and further processing to obtain the aircraft tire tread rubber material with excellent performance. The raw material selection, the formula and the processing technology of the rubber material solve the problems of dispersibility and the like among materials, and the composite material has the advantages of good heat dissipation, good static electricity conduction performance, high strength, good wear resistance, light weight, low oil consumption, low carbon emission and the like, and is widely applied to treads of aircraft tires and the like.
Example 1:
(1) Preparation of graphene dispersion
0.5 part of polyvinylpyrrolidone (PVP), 1 part of graphene powder and 50 parts of deionized water
Adding graphene powder, PVP and deionized water into a reactor, stirring and mixing uniformly, homogenizing the primarily obtained dispersion liquid by a homogenizer (1000bar, water cooling at 5 ℃) and carrying out ultrasonic treatment by an ultrasonic machine (100 Hz, 60 min) to obtain the graphene dispersion liquid.
(2) Preparation of RGO Natural rubber
And (3) placing the graphene dispersion liquid and the natural latex (85 parts) into a reaction kettle, and stirring and fully mixing for later use. The mixture was added to a calcium chloride solution (concentration 1%) for flocculation. Heating the flocculate (50 ℃ for X144 h) to remove water to obtain the RGO natural rubber.
(3) Preparation of graphene modified rubber composite material
The raw materials used were as follows:
the obtained RGO natural rubber and solution polymerized styrene butadiene rubber are proportioned and delivered to an internal mixer for first-stage mixing (150 ℃ discharging, rotor rotating speed 70 r/min), rubber discharging is carried out, and after the mixed rubber is cooled, second-stage mixing (150 ℃ discharging, rotor rotating speed 70 r/min) and rubber discharging are carried out. And (3) conveying the mixed rubber to an open mill, adding sulfur, an accelerator and other raw materials to obtain two films, and taking out the films and cooling to obtain the graphene modified rubber composite material.
The results of the tests on the materials obtained are given in the table below
| Test items | Unit | Test knotFruit |
| Mooney viscosity | 62 | |
| 100% elongation at break | MPa | 3.6 |
| 300% elongation at break | MPa | 15 |
| Tensile strength | MPa | 26.3 |
| Elongation at break | ％ | 483 |
| Bottom temperature rise of heat generated by compression | ℃ | 20 |
| Resistance (RC) | Ω | 10 3 |
| Akron abrasion | cm 3 /1.61km | 0.148 |
Example 2:
(1) Preparation of graphene dispersion
0.25 part of PVP, 1 part of graphene and 50 parts of deionized water
Adding graphene powder, PVP and deionized water into a reactor, stirring and mixing uniformly, homogenizing the primarily obtained dispersion liquid by a homogenizer (1000bar, water cooling at 5 ℃) and carrying out ultrasonic treatment by an ultrasonic machine (100 Hz, 60 min) to obtain the graphene dispersion liquid.
(2) Preparation of RGO Natural rubber
And (3) placing the graphene dispersion liquid and the natural latex (85 parts) into a reaction kettle, and stirring and fully mixing for later use. The mixture was added to a calcium chloride solution (concentration 1%) for flocculation. Heating the flocculate (50 ℃ for X144 h) to remove water to obtain the RGO natural rubber.
(3) Preparation of graphene modified rubber composite material
The raw materials used were as follows:
the obtained RGO natural rubber and the solution polymerized butadiene styrene rubber are proportioned and delivered into an internal mixer for first-stage mixing (150 ℃ discharge, rotor rotation speed 70 r/min), rubber discharge is carried out, and after the rubber mixture is cooled, second-stage mixing (150 ℃ discharge, rotor rotation speed 70 r/min) is carried out, and the rubber discharge is carried out. And (3) conveying the mixed rubber to an open mill, adding other raw materials such as sulfur, an accelerator and the like to obtain two films, and taking out the films and cooling to obtain the graphene modified rubber composite material.
The results of the tests on the materials obtained are given in the table below
Comparative example 1
The following components were used:
the natural rubber and the solution polymerized styrene-butadiene rubber are proportioned and delivered into an internal mixer for first-stage mixing (150 ℃ discharging, rotor rotating speed 70 r/min), rubber discharging is carried out, and after the mixed rubber is cooled, second-stage mixing (150 ℃ discharging, rotor rotating speed 70 r/min) is carried out for rubber discharging. And (3) conveying the mixed rubber to an open mill, adding raw materials such as sulfur, an accelerator and the like to obtain two films, and taking out the films and cooling to obtain the aircraft tire tread rubber composite material.
The results of the tests on the materials obtained are given in the table below
| Test items | Unit of | Test results |
| Mooney viscosity | M | 60 |
| 100% elongation at break | MPa | 3.3 |
| 300% elongation at break | MPa | 13.9 |
| Tensile strength | MPa | 24.5 |
| Elongation at break | ％ | 510 |
| Bottom temperature rise of heat generated by compression | ℃ | 20 |
| Resistance (RC) | Ω | 10 5 |
| Akron abrasion | cm 3 /1.61km | 0.290 |
Comparative example 2
(1) Preparation of graphene dispersion
0.25 part of PVP, 1 part of graphene and 50 parts of deionized water
Adding graphene powder, PVP and deionized water into a reactor, stirring and mixing uniformly, homogenizing the primarily obtained dispersion liquid by a homogenizer (1000bar, water cooling at 5 ℃) and carrying out ultrasonic treatment by an ultrasonic machine (100 Hz, 60 min) to obtain the graphene dispersion liquid.
(2) Preparation of RGO Natural rubber
And (3) placing the graphene dispersion liquid and the natural latex (85 parts) into a reaction kettle, and stirring and fully mixing for later use. The mixture was added to a calcium chloride solution (concentration 1%) for flocculation. Heating the flocculate (50 ℃ for X144 h) to remove water to obtain the RGO natural rubber.
(3) Preparation of graphene modified rubber composite material
The raw materials used were as follows:
the obtained RGO natural rubber and the solution polymerized butadiene styrene rubber are proportioned and delivered into an internal mixer for first-stage mixing (150 ℃ discharge, rotor rotation speed 70 r/min), rubber discharge is carried out, and after the rubber mixture is cooled, second-stage mixing (150 ℃ discharge, rotor rotation speed 70 r/min) is carried out, and the rubber discharge is carried out. And (3) conveying the mixed rubber to an open mill, adding other raw materials such as sulfur, an accelerator and the like to obtain two films, and taking out the films and cooling to obtain the graphene modified rubber composite material.
The results of the tests on the materials obtained are given in the table below
Claims (10)
1. The graphene modified rubber composition comprises the following components in parts by weight:
the graphene dispersion comprises graphene and a dispersing agent, wherein the weight ratio of the graphene to the dispersing agent is (2-4): 1.
2. the composition of claim 1, wherein the dispersant is polyvinylpyrrolidone, the lubricant is selected from stearic acid, and the vulcanizing agent is selected from sulfur.
3. The composition as recited in claim 1, wherein the reinforcing agent includes a combination of carbon black and white carbon, wherein an amount of the carbon black is 10-30 parts and an amount of the white carbon is 25-45 parts.
4. The composition of claim 1, wherein the composition further comprises the following components in parts by weight:
5. the composition of claim 4, wherein the accelerator comprises a combination of accelerator D and accelerator NS, the amount of accelerator D being from 0.2 parts to 0.6 parts, the amount of accelerator NS being from 1.2 parts to 1.8 parts; the auxiliary accelerator is selected from zinc oxide; the anti-aging agent comprises the combination of anti-aging agent 4020, anti-aging agent RD and microcrystalline wax, wherein the amount of the anti-aging agent 4020 is 1-2 parts, the amount of the anti-aging agent RD is 2-5 parts, and the amount of the microcrystalline wax is 1-2 parts.
6. A graphene-modified rubber composite made from the composition of any one of claims 1-6.
7. A method of making a graphene-modified rubber composite, comprising the steps of:
s1, preparing a graphene dispersion liquid: mixing graphene, a dispersing agent and deionized water, and homogenizing to obtain a graphene dispersion liquid;
s2, mixing and stirring the graphene dispersion liquid and natural latex, flocculating and drying to prepare RGO natural rubber;
and S3, mixing the RGO natural rubber, the solution-polymerized styrene-butadiene rubber and an additive to obtain the graphene modified rubber composite material.
8. The method of claim 7, wherein S2 is the RGO natural rubber obtained by flocculating a mixture of graphene dispersion and natural latex by adding calcium chloride aqueous solution and then heating the flocculate to remove water; preferably, the concentration of the calcium chloride aqueous solution is 0.5% -1.5%; the heating temperature is 40-60 ℃.
9. The process according to claim 7, wherein the mixing temperature is 140-150 ℃; after mixing, open mixing was also carried out, the roll ratio of two rolls was 1.0:1.2-1.0:2.0.
10. an aircraft tire made from the graphene-modified rubber composite of claim 6.
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| US20140319429A1 (en) * | 2011-11-18 | 2014-10-30 | Arkema France | Method for preparing a paste-like composition comprising carbon-based conductive fillers |
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