CN105801943A - Tread rubber composite material containing modified graphene oxide compound and preparation method of tread rubber composite material containing modified graphene oxide compound - Google Patents
Tread rubber composite material containing modified graphene oxide compound and preparation method of tread rubber composite material containing modified graphene oxide compound Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the field of rubber composite material preparation, in particular to a tread rubber composite material containing a modified graphene oxide compound and a preparation method of the tread rubber composite material containing the modified graphene oxide compound.The composite material comprises, by weight, 100 parts of matrix rubber, 30-70 parts of high-dispersion white carbon black, 2-6 parts of a silane coupling agent, 5-25 parts of carbon black, 2-8 parts of a plasticizer, 1-3 parts of an activating agent, 1-3 parts of an anti-ageing agent, 1-3 parts of a vulcanization accelerator, 1-2 parts of common sulfur and 0.1-0.3 part of a scorch retarder.The matrix rubber is mixed rubber formed by proportional mixing of natural rubber, polybutadiene rubber and butadiene styrene rubber, and the natural rubber in the matrix rubber is added in two times.The modified graphene oxide compound is further added to the composite material and formed by part of the natural rubber in the matrix rubber, graphene oxide and a graphene oxide modifying agent.Due to addition of the modified graphene oxide compound, tensile strength, stress at definite elongation, hardness, abrasion resistance and the like of the tread rubber composite material are evidently improved.
Description
Technical field
The present invention relates to field of rubber technology, be specifically related to a kind of tread rubber composite containing modified graphene oxide complex and
Preparation method.
Background technology
Tire plays in running car and bears load, shock absorbing, transmission driving force and brake force, offer steer ability
Effect, is one of most important parts of automobile.Tire tread directly contact face, in addition to protection carcass, also should have wear-resisting
Damaging and belt cutting-resisting property, and can conduct pull strength and the brake force of wheel, the vibration of buffering ground conduction and impact, tread rubber is
Exclusively for balance wear away, draw, handle and resistance to rolling and configure.Tread rubber must useful effect under multiple driving conditions,
And meet client to tire high abrasion, high rolling resistance durable, low, the expectation of environmental protection.
Graphene is to be passed through sp by monolayer carbon atom2A kind of new material with carbon element of hydridization tightly packed one-tenth bi-dimensional cellular shape crystal structure.Stone
Ink alkene combines the architectural feature of carbon nanotube conducting and clay layer, for development high-performance, multifunctional tire tread rubber composite wood
Material provides new direction.But the inert state in the surface of Graphene, the interaction with other media is weak, and graphene sheet layer it
Between there is stronger Van der Waals force, cause its most hydrophilic the most not oleophylic, it is impossible to well with rubber matrix be combined, in rubber-based
Body is also easy to reunite.Graphene oxide prepares the intermediate product during Graphene as oxidation-reduction method, has possessed graphite
The mechanical property that alkene is excellent.During industrialization at present produces, it is limited to the process conditions of tire, graphene oxide and compound the one of rubber
As select use mechanical blending method, although direct mechanical be blended simple, but be difficult to by graphene oxide peel off and dispersed
In rubber matrix, and during mechanical blending, high shear force can smash graphene oxide lamella.Earlier application CN105482201A
Disclose a kind of high-performance tire containing graphene oxide, although it improves graphene oxide dispersive property in rubber, but
Being to improve while dispersive property, the performance such as wear-resisting improving tire tread glue is also the most necessary.Due to graphene oxide
The existence of a large amount of oxygen-containing functional group of sheet surfaces, the surface modification for Graphene provides possibility, carries out surface of graphene oxide
Modification, to improve its processability and to strengthen its research with the interaction of rubber matrix and strengthening tyre performance most important simultaneously.
Summary of the invention
The present invention is directed to deficiency of the prior art, overcome Graphene in existing graphene composite material to disperse in rubber matrix tired
Difficult, the problem of interface interaction difference, it is provided that a kind of graphene oxide dispersive property is good and excellent in mechanical performance, high abrasion containing modified
The tread rubber composite of graphene oxide complex and preparation method.
For solving above-mentioned technical problem, the tread rubber composite containing modified graphene oxide complex that the present invention provides, according to
Parts by weight include following components: base rubber 100 parts, high-dispersion white carbon black 30-70 part, silane coupler 2-6 part, charcoal
Black 5-25 part, plasticizer 2-8 part, activating agent 1-3 part, age resistor 1-3 part, vulcanization accelerator 1-3 part, common sulfur 1-2
Part, antiscorching agent 0.1-0.3 part.Described base rubber is that natural rubber, butadiene rubber and butadiene-styrene rubber form according to a certain percentage
Epoxy glue.In base rubber, natural rubber is divided into two parts to be separately added into.
Described composite is also added into modified graphene oxide complex, and this modified graphene oxide complex is by base rubber
A part for natural rubber is constituted with graphene oxide and graphene oxide modifying agent.The addition of graphene oxide is 1-8 part,
The mass fraction accounting for graphene oxide complex is 25wt%, and remainder is natural rubber；Remaining natural rubber and suitable fourth rubber
Glue, butadiene-styrene rubber join in composite as base rubber, and graphene oxide modifying agent accounts for the mass fraction of graphene oxide
It is 12%.
Described modified graphene oxide complex preparation method comprises the following steps:
(1) preparation of graphene oxide suspension: graphite oxide powder ultrasonic is scattered in deionized water, obtains mass concentration
For the graphene oxide suspension of 0.5-5mg/ml, ultrasonic power is 300-1000W, and the ultrasonic time is 30-60 minute, super
Acoustic frequency is 10-20KHz；
(2) preparation of graphene oxide complex: account for the ratio that complex mass fraction is 25wt% according to graphene oxide, will
The natural rubber latex corresponding with graphene oxide amount joins in above-mentioned graphene oxide suspension, continues ultrasonic 15-30 minute,
Successively through flocculating, washing, being dried, prepare graphene oxide and the complex of natural rubber, described flocculation is for add compounded latex
Enter the CaCl to 1-2wt%2In aqueous solution；
(3) preparation of modified graphene oxide complex: in the graphene oxide of step (2) and the complex of natural rubber
Adding and account for the modifying agent that graphene oxide mass fraction is 12%, blend glue stuff reacts 2-10 minute at 130-160 DEG C,
Obtain modified graphene oxide complex.
Described graphene oxide modifying agent is gamma-mercaptopropyltriethoxysilane KH580, γ-(methacryloxypropyl) propyl group trimethoxy
Base silane KH570, mercaptopropyl trimethoxysilane A189, VTES A151, double-[γ-(triethoxysilicane)
Propyl group] mixture of one or more compositions in tetrasulfide Si-69.
In described modified graphene oxide complex, the lamellar spacing of graphene oxide is 1-3nm, and width is 0.1-1 μm.
Described white carbon black is N330 or N234；Described plasticizer is aromatic naphtha or paraffin oil；Described activating agent is that zinc oxide is with hard
Fat acid, the two ratio is 1:1；Described age resistor be in age resistor 6PPD, anti-aging agent RD or microwax any one or two
Kind；Described vulcanization accelerator is any one in aniline fluid bed, vulcanization accelerator TBBS or accelerator D PG；
Described antiscorching agent is anti-scorching agent CTP.
The preparation method of tread rubber composite is as follows: mixed with base rubber, now by above-mentioned modified graphene oxide complex
Base rubber be remaining natural rubber and butadiene rubber, the mixture of butadiene-styrene rubber, be blended into high-dispersion white carbon black, silane
Coupling agent, white carbon black, plasticizer, activating agent, age resistor, vulcanization accelerator, common sulfur, antiscorching agent, mixing, in banburying
In machine mixing uniformly, obtain tread rubber composite.
The invention has the beneficial effects as follows: graphene oxide first carries out emulsion blending with natural rubber latex, then carries out table with modifying agent
Face is modified, last with rubber matrix, the process advan of filler, each compounding ingredient mechanical blending in raising graphene oxide in rubber-based
Dispersibility in body, the interface cohesion of oxidation reinforced Graphene and rubber matrix so that the hot strength of tread rubber composite,
The performances such as stress at definite elongation, hardness and wearability are significantly improved.Compared with adding unmodified graphene oxide composite material, modified
Graphene oxide complex is more conducive to improve the physical and mechanical properties of tread rubber composite, and variety classes modifying agent is prepared into
The modified graphene oxide complex arrived is different to the raising degree of properties of rubber.
Detailed description of the invention
The detailed description of the invention of the present invention is as follows:
The mass fraction of each component of embodiment 1 tread rubber composite is:
Natural rubber matrix 25 parts；Butadiene rubber matrix 25 parts；Butadiene-styrene rubber matrix 50 parts；High-dispersion white carbon black 50 parts；
Silane coupler 4 parts；White carbon black 5 parts；Plasticizer 3 parts；Zinc oxide 1.5 parts；Stearic acid 1.5 parts；1.5 parts of age resistor；Sulfur
Change accelerator 2 parts；Common 1.5 parts of sulfur；Antiscorching agent 0.1 part.
Described composite is additionally added modified graphene oxide complex, and this modified graphene oxide complex is by sky in base rubber
So a part for rubber is constituted with graphene oxide and graphene oxide modifying agent, and the addition of graphene oxide is 5 parts, accounts for
The mass fraction of graphene oxide complex is 25wt%, and in complex, remainder is natural rubber；Remaining natural rubber is then
Joining in composite with butadiene rubber, butadiene-styrene rubber as base rubber, graphene oxide modifying agent is γ-mercapto propyl group three second
TMOS KH580 0.3 part and γ-(methacryloxypropyl) propyl trimethoxy silicane KH570 0.3 part.
The preparation method of tread rubber composite: be scattered in deionized water by graphite oxide powder ultrasonic, mass concentration is
1mg/ml, ultrasonic power is 600W, and the time is 60 minutes, and frequency is 10KHz, obtains graphene oxide suspension.By oxygen
Functionalized graphene accounts for the ratio of the 25wt% of complex, is the natural rubber latex of 50% by the solid content corresponding with graphene oxide amount
Join in the suspension of graphene oxide, continue ultrasonic 30 minutes, compounded latex is joined the CaCl of 1wt%2Aqueous solution
In, successively through flocculating, washing, be dried, obtain the complex of graphene oxide and natural rubber.To above-mentioned graphene oxide and
The complex of natural rubber adds modifying agent KH580 and KH570, reacts 5 minutes in 140 DEG C after mixing, i.e. can be changed
Property graphene oxide complex.By modified graphene oxide complex and remaining natural rubber and butadiene rubber and butadiene-styrene rubber,
High-dispersion white carbon black, silane coupler, white carbon black, plasticizer, zinc oxide, stearic acid, age resistor, vulcanization accelerator, commonly
Sulfur, antiscorching agent is mixing uniformly, obtains tread rubber composite, and Tread Compound Property is shown in Table 1.
The mass fraction of each component of embodiment 2 tread rubber composite is:
Natural rubber matrix 20 parts；Butadiene rubber matrix 30 parts；Butadiene-styrene rubber matrix 50 parts；High-dispersion white carbon black 50 parts；
Silane coupler 4 parts；White carbon black 5 parts；Plasticizer 3 parts；Zinc oxide 1.5 parts；Stearic acid 1.5 parts；1.5 parts of age resistor；Sulfur
Change accelerator 2 parts；Common 1.5 parts of sulfur；Antiscorching agent 0.1 part.
Described composite is additionally added modified graphene oxide complex, and this modified graphene oxide complex is by sky in base rubber
So a part for rubber is constituted with graphene oxide and graphene oxide modifying agent, and the addition of graphene oxide is 5 parts, accounts for
The mass fraction of graphene oxide complex is 25wt%, and in complex, remainder is natural rubber；Remaining natural rubber is then
Joining in composite with butadiene rubber, butadiene-styrene rubber as base rubber, graphene oxide modifying agent is vinyl three ethoxy
Base silane A151 0.3 part；Mercaptopropyl trimethoxysilane A189 0.3 part.
The preparation method of tread rubber composite: be scattered in deionized water by graphite oxide powder ultrasonic, mass concentration is
2mg/ml, ultrasonic power is 800W, and the time is 40 minutes, and frequency is 10KHz, obtains graphene oxide suspension.By oxygen
Functionalized graphene accounts for the ratio of the 25wt% of complex, is the natural rubber latex of 50% by the solid content corresponding with graphene oxide amount
Join in the suspension of graphene oxide, continue ultrasonic 20 minutes, compounded latex is joined the CaCl of 1wt%2Aqueous solution
In, successively through flocculating, washing, be dried, obtain the complex of graphene oxide and natural rubber.To above-mentioned graphene oxide and
The complex of natural rubber adds modifier A 151 and A189, reacts 6 minutes in 130 DEG C after mixing, i.e. available modification
Graphene oxide complex.By modified graphene oxide complex and remaining natural rubber and butadiene rubber and butadiene-styrene rubber,
High-dispersion white carbon black, silane coupler, white carbon black, plasticizer, zinc oxide, stearic acid, age resistor, vulcanization accelerator, commonly
Sulfur, antiscorching agent is mixing uniformly, obtains tread rubber composite, and Tread Compound Property is shown in Table 1.
The mass fraction of each component of embodiment 3 tread rubber composite is:
Natural rubber matrix 25 parts；Butadiene rubber matrix 30 parts；Butadiene-styrene rubber matrix 45 parts；High-dispersion white carbon black 50 parts；
Silane coupler 4 parts；White carbon black 5 parts；Plasticizer 3 parts；Zinc oxide 1.5 parts；Stearic acid 1.5 parts；1.5 parts of age resistor；Sulfur
Change accelerator 2 parts；Common 1.5 parts of sulfur；Antiscorching agent 0.1 part.
Described composite is additionally added modified graphene oxide complex, and this modified graphene oxide complex is by sky in base rubber
So a part for rubber is constituted with graphene oxide and graphene oxide modifying agent, and the addition of graphene oxide is 5 parts, accounts for
The mass fraction of graphene oxide complex is 25wt%, and in complex, remainder is natural rubber；Remaining natural rubber is then
Joining in composite with butadiene rubber, butadiene-styrene rubber as base rubber, graphene oxide modifying agent is double-[γ-(three ethoxies
Base silicon) propyl group] tetrasulfide Si-69 0.3 part；VTES A151 0.3 part.
The preparation method of tread rubber composite: be scattered in deionized water by graphite oxide powder ultrasonic, mass concentration is
3mg/ml, ultrasonic power is 700W, and the time is 50 minutes, and frequency is 15KHz, obtains graphene oxide suspension.By oxygen
Functionalized graphene accounts for the ratio of the 25wt% of complex, is the natural rubber latex of 50% by the solid content corresponding with graphene oxide amount
Join in the suspension of graphene oxide, continue ultrasonic 25 minutes, compounded latex is joined the CaCl of 2wt%2Aqueous solution
In, successively through flocculating, washing, be dried, obtain the complex of graphene oxide and natural rubber.To above-mentioned graphene oxide and
The complex of natural rubber adds modifying agent Si-69 and A151, reacts 4 minutes in 160 DEG C after mixing, i.e. available modification
Graphene oxide complex.By modified graphene oxide complex and remaining natural rubber and butadiene rubber and butadiene-styrene rubber,
High-dispersion white carbon black, silane coupler, white carbon black, plasticizer, zinc oxide, stearic acid, age resistor, vulcanization accelerator, commonly
Sulfur, antiscorching agent is mixing uniformly, obtains tread rubber composite, and Tread Compound Property is shown in Table 1.
The mass fraction of each component of embodiment 4 tread rubber composite is:
Natural rubber matrix 20 parts；Butadiene rubber matrix 30 parts；Butadiene-styrene rubber matrix 50 parts；High-dispersion white carbon black 30 parts；
Silane coupler 2 parts；White carbon black 5 parts；Plasticizer 2 parts；Zinc oxide 0.5 part；Stearic acid 0.5 part；1 part of age resistor；Sulfuration
Accelerator 1 part；Common 1 part of sulfur；Antiscorching agent 0.1 part.
Described composite is additionally added modified graphene oxide complex, and this modified graphene oxide complex is by sky in base rubber
So a part for rubber is constituted with graphene oxide and graphene oxide modifying agent, and the addition of graphene oxide is 3 parts, accounts for
The mass fraction of graphene oxide complex is 25wt%, and in complex, remainder is natural rubber；Remaining natural rubber is then
Joining in composite with butadiene rubber, butadiene-styrene rubber as base rubber, graphene oxide modifying agent is double-[γ-(three ethoxies
Base silicon) propyl group] tetrasulfide Si-69 0.12 part；VTES A151 0.12 part, modifying agent mercapto propyl group trimethoxy
Base silane A189 0.12 part.
The preparation method of tread rubber composite: be scattered in deionized water by graphite oxide powder ultrasonic, mass concentration is
3mg/ml, ultrasonic power is 800W, and the time is 40 minutes, and frequency is 15KHz, obtains graphene oxide suspension.By oxygen
Functionalized graphene accounts for the ratio of the 25wt% of complex, is the natural rubber latex of 50% by the solid content corresponding with graphene oxide amount
Join in the suspension of graphene oxide, continue ultrasonic 15 minutes, compounded latex is joined the CaCl of 1.5wt%2Aqueous solution
In, successively through flocculating, washing, be dried, obtain the complex of graphene oxide and natural rubber.To above-mentioned graphene oxide and
The complex of natural rubber adds modifying agent Si-69, A151 and A189, reacts 8 minutes in 150 DEG C after mixing,
To modified graphene oxide complex.By modified graphene oxide complex and remaining natural rubber and butadiene rubber and butylbenzene
Rubber, high-dispersion white carbon black, silane coupler, white carbon black, plasticizer, zinc oxide, stearic acid, age resistor, vulcanization accelerator,
Common sulfur, antiscorching agent is mixing uniformly, obtains tread rubber composite, and Tread Compound Property is shown in Table 1.
The mass fraction of each component of embodiment 5 tread rubber composite is:
Natural rubber matrix 15 parts；Butadiene rubber matrix 25 parts；Butadiene-styrene rubber matrix 60 parts；High-dispersion white carbon black 70 parts；
Silane coupler 6 parts；White carbon black 25 parts；Plasticizer 8 parts；Zinc oxide 1.5 parts；Stearic acid 1.5 parts；3 parts of age resistor；Sulfur
Change accelerator 3 parts；Common 2 parts of sulfur；Antiscorching agent 0.3 part.
Described composite is additionally added modified graphene oxide complex, and this modified graphene oxide complex is by sky in base rubber
So a part for rubber is constituted with graphene oxide and graphene oxide modifying agent, and the addition of graphene oxide is 1 part, accounts for
The mass fraction of graphene oxide complex is 25wt%, and in complex, remainder is natural rubber；Remaining natural rubber is then
Joining in composite with butadiene rubber, butadiene-styrene rubber as base rubber, graphene oxide modifying agent is γ-(metering system
Acyl-oxygen) propyl trimethoxy silicane KH570 0.12 part.
The preparation method of tread rubber composite: be scattered in deionized water by graphite oxide powder ultrasonic, mass concentration is
0.5mg/ml, ultrasonic power is 300W, and the time is 50 minutes, and frequency is 20KHz, obtains graphene oxide suspension.Press
Graphene oxide accounts for the ratio of the 25wt% of complex, is the natural rubber latex of 50% by the solid content corresponding with graphene oxide amount
Breast joins in the suspension of graphene oxide, continues ultrasonic 15 minutes, compounded latex joins the CaCl of 1wt%2Water-soluble
In liquid, successively through flocculating, washing, be dried, obtain the complex of graphene oxide and natural rubber.To above-mentioned graphene oxide
With addition modifying agent KH570 in the complex of natural rubber, react 10 minutes in 130 DEG C after mixing, i.e. can get modified oxidized
Graphene complex.By modified graphene oxide complex and remaining natural rubber and butadiene rubber and butadiene-styrene rubber, high score
Scattered white carbon, silane coupler, white carbon black, plasticizer, zinc oxide, stearic acid, age resistor, vulcanization accelerator, common sulfur,
Antiscorching agent is mixing uniformly, obtains tread rubber composite, and Tread Compound Property is shown in Table 1.
The mass fraction of each component of embodiment 6 tread rubber composite is:
Natural rubber matrix 25 parts；Butadiene rubber matrix 30 parts；Butadiene-styrene rubber matrix 45 parts；High-dispersion white carbon black 60 parts；
Silane coupler 5 parts；White carbon black 20 parts；Plasticizer 5 parts；Zinc oxide 0.7 part；Stearic acid 0.7 part；1.8 parts of age resistor；
Vulcanization accelerator: 1.8 parts；Common 1 part of sulfur；Antiscorching agent 0.2 part.
Described composite is additionally added modified graphene oxide complex, and this modified graphene oxide complex is by sky in base rubber
So a part for rubber is constituted with graphene oxide and graphene oxide modifying agent, and the addition of graphene oxide is 8 parts, accounts for
The mass fraction of graphene oxide complex is 25wt%, and in complex, remainder is natural rubber；Remaining natural rubber is then
Joining in composite with butadiene rubber, butadiene-styrene rubber as base rubber, graphene oxide modifying agent is γ-mercapto propyl group three second
TMOS KH580 0.96 part.
The preparation method of tread rubber composite: be scattered in deionized water by graphite oxide powder ultrasonic, mass concentration is
5mg/ml, ultrasonic power is 1000W, and the time is 40 minutes, and frequency is 15KHz, obtains graphene oxide suspension.Press
Graphene oxide accounts for the ratio of the 25wt% of complex, is the natural rubber latex of 50% by the solid content corresponding with graphene oxide amount
Breast joins in the suspension of graphene oxide, continues ultrasonic 20 minutes, compounded latex joins the CaCl of 2wt%2Water-soluble
In liquid, successively through flocculating, washing, be dried, obtain the complex of graphene oxide and natural rubber.To above-mentioned graphene oxide
With addition modifying agent KH580 in the complex of natural rubber, react 2 minutes in 140 DEG C after mixing, i.e. can get modified oxidized
Graphene complex.By modified graphene oxide complex and remaining natural rubber and butadiene rubber and butadiene-styrene rubber, high score
Scattered white carbon, silane coupler, white carbon black, plasticizer, zinc oxide, stearic acid, age resistor, vulcanization accelerator, common sulfur,
Antiscorching agent is mixing uniformly, obtains tread rubber composite, and Tread Compound Property is shown in Table 1.
The mass fraction of each component of comparative example tread rubber composite is:
Natural rubber matrix 20 parts；Butadiene rubber matrix 20 parts；Butadiene-styrene rubber matrix 60 parts；High-dispersion white carbon black 50 parts；
Silane coupler 4 parts；White carbon black 5 parts；Plasticizer 3 parts；Zinc oxide 1.5 parts；Stearic acid 1.5 parts；1.5 parts of age resistor；Sulfur
Change accelerator: 2 parts；Common 1.5 parts of sulfur；Antiscorching agent 0.1 part.
Described composite is additionally added graphene oxide complex, and this complex is by the part of natural rubber in base rubber and oxygen
Functionalized graphene is constituted, and the addition of graphene oxide is 5 parts, and the mass fraction accounting for graphene oxide complex is 25wt%, multiple
In compound, remainder is natural rubber；Remaining natural rubber then joins as base rubber with butadiene rubber, butadiene-styrene rubber
In composite.
The preparation method of tread rubber composite: be scattered in deionized water by graphite oxide powder ultrasonic, mass concentration is
4mg/ml, ultrasonic power is 1000W, and the time is 30 minutes, and frequency is 15KHz, obtains graphene oxide suspension.Press
Graphene oxide accounts for the ratio of the 25wt% of complex, is the natural rubber latex of 50% by the solid content corresponding with graphene oxide amount
Breast joins in the suspension of graphene oxide, continues ultrasonic 15 minutes, compounded latex joins the CaCl of 1wt%2Water-soluble
In liquid, successively through flocculating, washing, be dried, obtain the complex of graphene oxide and natural rubber.Graphene oxide is combined
Thing and remaining natural rubber and butadiene rubber and butadiene-styrene rubber, high-dispersion white carbon black, silane coupler, white carbon black, plasticizer,
Zinc oxide, stearic acid, age resistor, vulcanization accelerator, common sulfur, antiscorching agent is mixing uniformly, obtains tread rubber composite,
Tread Compound Property is shown in Table 1.
Table 1 Tread Compound Property
| Performance | Hot strength | 300% stress at definite elongation | Elongation at break | Hardness | Wearability |
| Unit | MPa | MPa | % | Shao Er A | cm3/1.61km |
| Embodiment 1 | 16.8 | 7.1 | 550 | 67 | 0.20 |
| Embodiment 2 | 16.5 | 6.6 | 576 | 65 | 0.23 |
| Embodiment 3 | 17.3 | 7.9 | 503 | 69 | 0.18 |
| Embodiment 4 | 16.7 | 6.7 | 571 | 66 | 0.22 |
| Embodiment 5 | 16.4 | 6.5 | 587 | 65 | 0.24 |
| Embodiment 6 | 17.5 | 8.2 | 431 | 70 | 0.17 |
| Comparative example | 16.3 | 6.5 | 602 | 65 | 0.25 |
Compared with adding unmodified graphene oxide with comparative example, modifying agent carries out surface modification to graphene oxide and is more beneficial for carrying
The performances such as hot strength, stress at definite elongation, hardness and the wearability of high tread rubber composite, and variety classes modifying agent is to oxygen
Functionalized graphene modified effect is different, and the degree causing graphene oxide composite material performance to improve is different, and then is improved degree
Different tread rubber composites.
Claims (10)
1. containing the tread rubber composite of modified graphene oxide complex, it is characterised in that include following components according to parts by weight:
Base rubber 100 parts, high-dispersion white carbon black 30-70 part, silane coupler 2-6 part, white carbon black 5-25 part, plasticizer 2-8 part,
Activating agent 1-3 part, age resistor 1-3 part, vulcanization accelerator 1-3 part, common sulfur 1-2 part, antiscorching agent 0.1-0.3 part；
Described base rubber is the epoxy glue that natural rubber, butadiene rubber and butadiene-styrene rubber form according to a certain percentage；
In base rubber, natural rubber is divided into two parts to be separately added into；
Described composite is also added into modified graphene oxide complex, and this modified graphene oxide complex is by base rubber
A part for natural rubber is constituted with graphene oxide and graphene oxide modifying agent；The addition of graphene oxide is 1-8 part,
The mass fraction accounting for graphene oxide complex is 25wt%, and remainder is natural rubber；Remaining natural rubber and suitable fourth rubber
Glue, butadiene-styrene rubber join in composite as base rubber, and graphene oxide modifying agent accounts for the mass fraction of graphene oxide
It is 12%.
Tread rubber composite the most according to claim 1, it is characterised in that prepared by described modified graphene oxide complex
Method comprises the following steps:
(1) preparation of graphene oxide suspension: graphite oxide powder ultrasonic is scattered in deionized water, obtains mass concentration
For the graphene oxide suspension of 0.5-5mg/ml, ultrasonic power is 300-1000W, and the ultrasonic time is 30-60 minute, super
Acoustic frequency is 10-20KHz；
(2) preparation of graphene oxide complex: account for the ratio that complex mass fraction is 25wt% according to graphene oxide, will
The natural rubber latex corresponding with graphene oxide amount joins in above-mentioned graphene oxide suspension, continues ultrasonic 15-30 minute,
Successively through flocculating, washing, being dried, prepare graphene oxide and the complex of natural rubber, described flocculation is for add compounded latex
Enter the CaCl to 1-2wt%2In aqueous solution；
(3) preparation of modified graphene oxide complex: in the graphene oxide of step (2) and the complex of natural rubber
Adding and account for the modifying agent that graphene oxide mass fraction is 12%, blend glue stuff reacts 2-10 minute at 130-160 DEG C,
Obtain modified graphene oxide complex.
Tread rubber composite the most according to claim 2, it is characterised in that described graphene oxide modifying agent is γ-mercapto propyl group
Triethoxysilane KH580, γ-(methacryloxypropyl) propyl trimethoxy silicane KH570, mercaptopropyl trimethoxysilane
One or more in A189, VTES A151, double-[γ-(triethoxysilicane) propyl group] tetrasulfide Si-69.
Tread rubber composite the most according to claim 3, it is characterised in that aoxidize in described modified graphene oxide complex
The lamellar spacing of Graphene is 1-3nm, and width is 0.1-1 μm.
Tread rubber composite the most according to claim 1, it is characterised in that described white carbon black is N330 or N234；Described increasing
Moulding agent is aromatic naphtha or paraffin oil.
Tread rubber composite the most according to claim 1, it is characterised in that described activating agent is zinc oxide and stearic acid, two
Person's ratio is 1:1.
Tread rubber composite the most according to claim 1, it is characterised in that described age resistor is age resistor 6PPD, age resistor
Any one or two kinds in RD or microwax.
Tread rubber composite the most according to claim 1, it is characterised in that described vulcanization accelerator be aniline fluid bed,
Any one in vulcanization accelerator TBBS or accelerator D PG.
Tread rubber composite the most according to claim 1, it is characterised in that described antiscorching agent is anti-scorching agent CTP.
10. the preparation method of the arbitrary described tread rubber composite of claim 1 to 9, it is characterised in that by modified graphene oxide
Complex mixes with base rubber, and base rubber now is the mixing of remaining natural rubber, butadiene rubber and butadiene-styrene rubber
Thing, is blended into high-dispersion white carbon black, silane coupler, white carbon black, plasticizer, activating agent, age resistor, vulcanization accelerator, general
Logical sulfur, antiscorching agent, mixing, in banbury mixing uniformly, obtain tread rubber composite.
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