CN106317505A - Three-dimensional graphene modified rubber composite material and preparation method thereof - Google Patents
Three-dimensional graphene modified rubber composite material and preparation method thereof Download PDFInfo
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
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- C08L7/00—Compositions of natural rubber
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Abstract
The invention relates to the technical field of materials and particularly discloses a three-dimensional graphene modified rubber composite material. The rubber composite material comprises the following components in parts by weight: 100 parts of rubber, 0.015 part of three-dimensional graphene, 0.5-5 parts of a sulfurizing reagent and 8-12 parts of a rubber compounding agent. Compared with existing rubber, the three-dimensional graphene modified rubber composite material has the advantages that the conductivity, the wear resistance, the heat resistance and the strength performance are greatly improved, the preparation process is simple, and the large-scale production is easily realized.
Description
Technical field
The present invention relates to field of material technology, be specifically related to a kind of rubber composite modified based on three-dimensional grapheme and
It is prepared.
Background technology
Rubber is the base stock of rubber industry, possesses the advantage such as light weight, corrosion-resistant, easy large-scale production, and can basis
Use the electrical and mechanical performance needing to regulate material, in field application such as tire, electronics industry, daily-use chemical industry and Aero-Space
The most extensive.Rubber is needed to have excellent antistatic, conduction or calorifics, mechanics and barrier properties for gases etc. with these application
Performance.
Compound rubber is using rubber as matrix, adds conduction, heat filling, thus give the certain conduction of rubber and
Heat conductivility.The electric conductivity of composite conducting rubber depends primarily on the electric conductivity of filler and filler in rubber matrix
Uniformly dispersed.Conventional filler has white carbon black, graphite, graphite fibre, metal-powder.Wherein, white carbon black is the conduction that application is most
Filler, when carbon black loading reaches marginal value, the electric conductivity of rubber is significantly improved.But when composite conducting rubber needs
Reach to need during the highest electrical property amounts of carbon black added can be very big, so can affect the viscosity of rubber base material and add
Work performance so that it is application is restricted.Nano-sized filler such as carbon fiber, CNT etc. can reach higher electricity with low loading
Performance, but agglomeration traits makes its difficulty reach good dispersion in the base, and there is Cost Problems and cause limiting its application
Development.
Meanwhile, rubber is the non-conductor of heat, and the heat of generation can not conduct in time, causes heat at rubber
Accumulated inside, the performance of goods can be reduced when temperature is too high, affect goods service life.Modified rubber is to improve material to lead
The effective way of hot property, and nano material with the molecular structure of its uniqueness and characteristic in terms of rubber reinforcement and functionalization great
Application potential.Affect at present nano material/rubber combined dispersion that two key factors are nano material and with matrix circle
The interaction in face.
Summary of the invention
In view of this, it is necessary to for above-mentioned problem, it is provided that a kind of both had good electric conductivity, there is again excellence
The rubber composite modified based on three-dimensional grapheme of mechanics, thermal property and machining property and preparation thereof.
For achieving the above object, the present invention takes techniques below scheme:
The rubber composite modified based on three-dimensional grapheme of the present invention, component includes by weight: 100 parts of rubber,
0.01-5 part three-dimensional grapheme, 0.5～5 part of vulcanizing agent, 8～12 parts of rubber chemicals.
Further, described rubber includes natural rubber, silicone rubber, butadiene-styrene rubber, butadiene rubber, butyl rubber, different
At least one in penta rubber, butadiene-isoprene rubber, nitrile rubber, EP rubbers, neoprene.
Further, described three-dimensional grapheme has the submicron three-dimensional connected porous network to a few micrometers.
Further, described vulcanizing agent includes in sulfur, peroxide, metal-oxide, sulfurous organic compound at least
A kind of.
Further, described rubber chemicals include: accelerating auxiliaries, accelerator, age resistor.
Further, at least one during described accelerating auxiliaries is zinc oxide or stearic acid；
Described accelerator includes diphenylguanidine, altax, Vulcanization accelerator TMTD, accelerant CZ, accelerant B Z, accelerant MBT
In at least one；
Described age resistor includes at least one in anti-aging agent RD, antioxidant 4010, age resistor 124, antioxidant D NP.
Further, described rubber chemicals are included by mass fraction: 2 parts of stearic acid, 5 parts of zinc oxide, 1～2 part of promotion
Agent, 1～3 part of age resistor.
The preparation method of present invention rubber composite based on three-dimensional grapheme modification, including:
Step 1) prepare graphene oxide by the Hummers method improved；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 1-2mg/ml, transfers to 160-200 DEG C of reaction 20-24h, washing in reactor afterwards, obtains three-dimensional reduction-oxidation graphite
Alkene hydrogel, lyophilization；
Step 3) by rubber, step 2) three-dimensional grapheme that obtains, rubber chemicals, vulcanizing agent be sequentially added into mill
In, mixing 10-30min at 40-90 DEG C, after elastomeric compound stands 16-24h, vulcanizing press vulcanizes, conditions of vulcanization is 140-
Vulcanize 10-40min at 170 DEG C, obtain the rubber composite that three-dimensional grapheme is modified.
Further, the Hummers method of described improvement prepares graphene oxide, is divided into pre-oxidation, aoxidizes and peel off；
Described pre-oxidation is: by native graphite that mass parts is 1 part, 3-10 part concentrated sulphuric acid, the K of 0.5-0.9 part2S2O8And
P2O5It is mixed and heated to 80 DEG C, reacts 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality；
Described it is oxidized to: at 0 DEG C, pre-oxidation graphite is mixed with the concentrated sulphuric acid of 6-20 part, is under agitation gradually added into 1-3
The KMnO of part4, control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, after stirring 2h, adds
20-50 part ultra-pure water, continues stirring 15min, is eventually adding 40-150 part ultra-pure water and terminates reaction.Then, 2 part 30% is added
H2O2, by mixture 10%HCl eccentric cleaning to remove unnecessary metal ion, the precipitation ultra-pure water obtained is centrifuged repeatedly
Cleaning to solution is neutrality；
Described stripping: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument of product 400w that will obtain,
13000rpm centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C.
Beneficial effects of the present invention:
The three-dimensional grapheme of the present invention has self supporting structure, it is to avoid agglomeration, has good dispersibility in rubber；
Three-dimensional grapheme has electricity, calorifics and the mechanical property of excellence, and the easiest and the present invention matrix is in close contact, and is greatly increased
The electric conductivity of rubber, wearability, thermostability and mechanical strength；Preparation technology of the present invention is simple, production cost is low, acyclic
Environment pollution, it is easy to accomplish large-scale industrial production.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this
Bright technical scheme is made the most clearly and completely to describe.It should be noted that described embodiment is only the present invention one
Section Example rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not doing
Go out the every other embodiment obtained under creative work premise, broadly fall into the scope of protection of the invention.
Embodiment 1:
Step 1) prepare graphene oxide by the Hummers method improved, it is divided into pre-oxidation, aoxidizes and peel off.
Pre-oxidation: by the native graphite that mass parts is 1 part, 6 parts of concentrated sulphuric acids, K of 0.7 part2S2O8And P2O5It is mixed and heated to
80 DEG C, react 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality.
Oxidation: at 0 DEG C, by pre-oxidation graphite and the concentrated sulphuric acid mixing of 9 parts, is under agitation gradually added into the KMnO of 3 parts4,
Control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, stirring 2h after, add 30 parts ultrapure
Water, continues stirring 15min, is eventually adding 60 parts of ultra-pure waters and terminates reaction.Then, 2 parts of 30%H are added2O2, mixture is used
10%HCl eccentric cleaning is to remove unnecessary metal ion.The precipitation ultra-pure water obtained be centrifuged repeatedly cleaning to solution in
Property.
Peel off: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument of product 400w that will obtain,
13000rpm centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 1.8mg/ml, transfers to 200 DEG C of reaction 20h, washing in reactor afterwards, obtains three-dimensional redox graphene water-setting
Glue, lyophilization；
Step 3) by 100 parts of butadiene rubbers, 0.1 part of three-dimensional grapheme, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of accelerator
CZ, 1.5 parts of anti-aging agent RDs, 1.5 parts of sulfur are sequentially added in mill, mixing 20min at 50 DEG C, after elastomeric compound stands 24h,
Vulcanize on vulcanizing press, conditions of vulcanization 151 DEG C, 25min, obtain the butadiene rubber composite that three-dimensional grapheme is modified.
Embodiment 2:
Step 1) prepare graphene oxide by the Hummers method improved, it is divided into pre-oxidation, aoxidizes and peel off.
Pre-oxidation: by the native graphite that mass parts is 1 part, 5 parts of concentrated sulphuric acids, K of 0.6 part2S2O8And P2O5It is mixed and heated to
80 DEG C, react 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality.
Oxidation: at 0 DEG C, by pre-oxidation graphite and the concentrated sulphuric acid mixing of 8 parts, is under agitation gradually added into the KMnO of 2 parts4,
Control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, stirring 2h after, add 30 parts ultrapure
Water, continues stirring 15min, is eventually adding 50 parts of ultra-pure waters and terminates reaction.Then, 2 parts of 30%H are added2O2, mixture is used
10%HCl eccentric cleaning is to remove unnecessary metal ion.The precipitation ultra-pure water obtained be centrifuged repeatedly cleaning to solution in
Property.
Peel off: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument of product 400w that will obtain,
13000rpm centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 1.5mg/ml, transfers to 180 DEG C of reaction 20h, washing in reactor afterwards, obtains three-dimensional redox graphene water-setting
Glue, lyophilization；
Step 3) by 100 parts of butadiene-styrene rubber, 0.2 part of three-dimensional grapheme, 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of accelerator
BZ, 1 part of anti-aging agent RD, 1 part of antioxidant 4010,1 part of sulfur are sequentially added in mill, and mixing 25min at 50 DEG C, elastomeric compound is quiet
After putting 18h, vulcanizing press vulcanizes, conditions of vulcanization 150 DEG C, 30min, obtain the modified butadiene-styrene rubber of three-dimensional grapheme multiple
Condensation material.
Embodiment 3
Step 1) prepare graphene oxide by the Hummers method improved, it is divided into pre-oxidation, aoxidizes and peel off.
Pre-oxidation: by the native graphite that mass parts is 1 part, 7 parts of concentrated sulphuric acids, K of 0.6 part2S2O8And P2O5It is mixed and heated to
80 DEG C, react 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality.
Oxidation: at 0 DEG C, by pre-oxidation graphite and the concentrated sulphuric acid mixing of 9 parts, is under agitation gradually added into the KMnO of 2 parts4,
Control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, after stirring 2h, adds 20-50 part and surpass
Pure water, continues stirring 15min, is eventually adding 100 parts of ultra-pure waters and terminates reaction.Then, 2 parts of 30%H are added2O2, mixture is used
10%HCl eccentric cleaning is to remove unnecessary metal ion.The precipitation ultra-pure water obtained be centrifuged repeatedly cleaning to solution in
Property.
Peel off: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument of product 400w that will obtain,
13000rpm centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 1.5mg/ml, transfers to 180 DEG C of reaction 24h, washing in reactor afterwards, obtains three-dimensional redox graphene water-setting
Glue, lyophilization；
Step 3) by 100 parts of nitrile rubbers, 0.4 part of three-dimensional grapheme, 5 parts of zinc oxide and 2 parts of stearic acid, 1 part of accelerator
TMTD and 0.5 part of accelerant MBT, 1 part of anti-aging agent RD and 1 part of antioxidant 4010,2 parts of sulfur are sequentially added in mill, 40 DEG C
Under mixing 20min, elastomeric compound stands after 16h, vulcanizes, conditions of vulcanization 170 DEG C, 16min on vulcanizing press, obtains three-dimensional stone
The nitile-butadiene rubber composite material that ink alkene is modified.
Embodiment 4
Step 1) prepare graphene oxide by the Hummers method improved, it is divided into pre-oxidation, aoxidizes and peel off.
Pre-oxidation: by the native graphite that mass parts is 1 part, 3 parts of concentrated sulphuric acids, 0.5 part of K2S2O8And P2O5It is mixed and heated to 80
DEG C, react 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality.
Oxidation: at 0 DEG C, by pre-oxidation graphite and the concentrated sulphuric acid mixing of 8 parts, is under agitation gradually added into 2 parts of KMnO4,
Mixture temperature is controlled below 20 DEG C during this.Mixture is warming up to 35 DEG C, after stirring 2h, adds 20 parts of ultra-pure waters,
Continue stirring 15min, be eventually adding 40 parts of ultra-pure waters and terminate reaction.Then, 2 parts of 30%H are added2O2, by mixture with 10%
HCl eccentric cleaning is to remove unnecessary metal ion.It is neutrality that the precipitation ultra-pure water obtained is centrifuged repeatedly cleaning to solution.
Peel off: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument of product 400w that will obtain,
13000rpm centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 1mg/ml, transfers to 160 DEG C of reaction 24h, washing in reactor afterwards, obtains three-dimensional redox graphene hydrogel,
Lyophilization；
Step 3) by 100 parts of natural rubbers, 0.6 part of three-dimensional grapheme, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of accelerator
TMTD, 1 part of accelerant CZ, 1 part of anti-aging agent RD, 1 part of antioxidant 4010,0.5 part of sulfur are sequentially added in mill, and 50 DEG C mixing
12min, after elastomeric compound stands 24h, vulcanizes on vulcanizing press, conditions of vulcanization 150 DEG C, 40min, obtains three-dimensional grapheme and change
The native rubber composite material of property.
Embodiment 5
Step 1) prepare graphene oxide by the Hummers method improved, it is divided into pre-oxidation, aoxidizes and peel off.
Pre-oxidation: by the native graphite that mass parts is 1 part, 9 parts of concentrated sulphuric acids, K of 0.9 part2S2O8And P2O5It is mixed and heated to
80 DEG C, react 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality.
Oxidation: at 0 DEG C, by pre-oxidation graphite and the concentrated sulphuric acid mixing of 10 parts, is under agitation gradually added into the KMnO of 3 parts4,
Control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, stirring 2h after, add 50 parts ultrapure
Water, continues stirring 15min, is eventually adding 90 parts of ultra-pure waters and terminates reaction.Then, 2 parts of 30%H are added2O2, mixture is used
10%HCl eccentric cleaning is to remove unnecessary metal ion.The precipitation ultra-pure water obtained be centrifuged repeatedly cleaning to solution in
Property.
Peel off: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument of product 400w that will obtain,
13000rpm centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 2mg/ml, transfers to 200 DEG C of reaction 22h, washing in reactor afterwards, obtains three-dimensional redox graphene hydrogel,
Lyophilization；
Step 3) by 100 parts of butadiene rubbers, 0.8 part of three-dimensional grapheme, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of accelerator
CZ, 1.5 parts of anti-aging agent RDs and 1 part of antioxidant 4010,3 parts of sulfur are sequentially added in mill, and at 60 DEG C, mixing 15min, mixing
After glue stands 24h, vulcanizing press vulcanizes, conditions of vulcanization 151 DEG C, 25min, obtain the suitable fourth rubber that three-dimensional grapheme is modified
Glue composite.
Embodiment 6
Step 1) prepare graphene oxide by the Hummers method improved, it is divided into pre-oxidation, aoxidizes and peel off.
Pre-oxidation: by the native graphite that mass parts is 1 part, 8 parts of concentrated sulphuric acids, K of 0.8 part2S2O8And P2O5It is mixed and heated to
80 DEG C, react 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality.
Oxidation: at 0 DEG C, by pre-oxidation graphite and the concentrated sulphuric acid mixing of 10 parts, is under agitation gradually added into the KMnO of 3 parts4,
Control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, stirring 2h after, add 35 parts ultrapure
Water, continues stirring 15min, is eventually adding 90 parts of ultra-pure waters and terminates reaction.Then, 2 parts of 30%H are added2O2, mixture is used
10%HCl eccentric cleaning is to remove unnecessary metal ion.The precipitation ultra-pure water obtained be centrifuged repeatedly cleaning to solution in
Property.
Peel off: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument, 13000rpm of the product 400w obtained
Centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 1.8mg/ml, transfers to 200 DEG C of reaction 24h, washing in reactor afterwards, obtains three-dimensional redox graphene water-setting
Glue, lyophilization；
Step 3) by 100 parts of butadiene-styrene rubber, 1 part of three-dimensional grapheme, 5 parts of zinc oxide and 2 parts of stearic acid, 1.5 parts of accelerator
BZ, 1 part of anti-aging agent RD and 1 part of antioxidant 4010,2.5 parts of sulfur are sequentially added in mill, and at 50 DEG C, mixing 30min, mixing
After glue stands 24h, vulcanizing press vulcanizes, conditions of vulcanization 150 DEG C, 30min, obtain the butylbenzene rubber that three-dimensional grapheme is modified
Glue composite.
Embodiment 7
Step 1) prepare graphene oxide by the Hummers method improved, it is divided into pre-oxidation, aoxidizes and peel off.
Pre-oxidation: by the native graphite that mass parts is 1 part, 10 parts of concentrated sulphuric acids, K of 0.9 part2S2O8And P2O5It is mixed and heated to
80 DEG C, react 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality.
Oxidation: at 0 DEG C, by pre-oxidation graphite and the concentrated sulphuric acid mixing of 20 parts, is under agitation gradually added into the KMnO of 3 parts4,
Control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, stirring 2h after, add 50 parts ultrapure
Water, continues stirring 15min, is eventually adding 150 parts of ultra-pure waters and terminates reaction.Then, 2 parts of 30%H are added2O2, mixture is used
10%HCl eccentric cleaning is to remove unnecessary metal ion.The precipitation ultra-pure water obtained be centrifuged repeatedly cleaning to solution in
Property.
Peel off: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument, 13000rpm of the product 400w obtained
Centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 2mg/ml, transfers to 200 DEG C of reaction 24h, washing in reactor afterwards, obtains three-dimensional redox graphene hydrogel,
Lyophilization；
Step 3) by 100 parts of nitrile rubbers, 2 parts of three-dimensional graphemes, 5 parts of zinc oxide and 1 part of stearic acid, 1 part of accelerator
TMTD and 1 part of MBT of accelerator, 1 part of anti-aging agent RD and 1 part of antioxidant 4010,4 parts of sulfur are sequentially added in mill, at 40 DEG C
Mixing 20min, after elastomeric compound stands 24h, vulcanizes on vulcanizing press, conditions of vulcanization 170 DEG C, 16min, obtains three-dimensional graphite
The nitile-butadiene rubber composite material that alkene is modified.
Embodiment 8
Step 1) prepare graphene oxide by the Hummers method improved, it is divided into pre-oxidation, aoxidizes and peel off.
Pre-oxidation: by the native graphite that mass parts is 1 part, 7 parts of concentrated sulphuric acids, K of 0.7 part2S2O8And P2O5It is mixed and heated to
80 DEG C, react 6h, clean with ultra-pure water and obtain pre-oxidizing graphite to neutrality.
Oxidation: at 0 DEG C, by pre-oxidation graphite and the concentrated sulphuric acid mixing of 10 parts, is under agitation gradually added into the KMnO of 3 parts4,
Control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, stirring 2h after, add 50 parts ultrapure
Water, continues stirring 15min, is eventually adding 80 parts of ultra-pure waters and terminates reaction.Then, 2 parts of 30%H are added2O2, mixture is used
10%HCl eccentric cleaning is to remove unnecessary metal ion.The precipitation ultra-pure water obtained be centrifuged repeatedly cleaning to solution in
Property.
Peel off: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument, 13000rpm of the product 400w obtained
Centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, dense
Degree is 2mg/ml, transfers to 180 DEG C of reaction 24h, washing in reactor afterwards, obtains three-dimensional redox graphene hydrogel,
Lyophilization；
Step 3) by 100 parts of natural rubbers, 3 parts of three-dimensional graphemes, 5 parts of zinc oxide and 2 parts of stearic acid, 1 part of accelerator
TMTD and 1 part of accelerant CZ, 1.5 parts of anti-aging agent RDs and 1 part of antioxidant 4010,1 part of sulfur and 0.5 part of cumyl peroxide depend on
In secondary addition mill, mixing 10min at 55 DEG C, after elastomeric compound stands 18h, vulcanizing press vulcanizes, conditions of vulcanization 150
DEG C, 40min, obtain the native rubber composite material that three-dimensional grapheme is modified.
Formula and preparation method used by comparative example 1,2,3,4 are identical with embodiment 1,2,3,4 respectively, and unique difference is wherein not add
Enter three-dimensional grapheme.
Table 1 is rubber composite and comparative example 1-4 of the modification of embodiment 1-8 preparation-obtained three-dimensional grapheme
Rubber carries out the performance parameter of contrast test:
The performance parameter of table 1 each embodiment gained rubber
As can be known from the above table, the preparation method of the present invention can increase substantially the electric conductivity of rubber, intensity, heat conductivity and resistance to
Mill property.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a rubber composite based on three-dimensional grapheme modification, it is characterised in that component includes by weight: 100 parts
Rubber, 0.01-10 part three-dimensional grapheme, 0.5～5 part of vulcanizing agent, 8～12 parts of rubber chemicals.
The rubber composite modified based on three-dimensional grapheme the most according to claim 1, it is characterised in that described rubber
Glue include natural rubber, silicone rubber, butadiene-styrene rubber, butadiene rubber, butyl rubber, isoprene rubber, butadiene-isoprene rubber, nitrile rubber,
At least one in EP rubbers, neoprene.
The rubber composite modified based on three-dimensional grapheme the most according to claim 1, it is characterised in that described three
Dimension Graphene has the submicron three-dimensional connected porous network to a few micrometers.
The rubber composite modified based on three-dimensional grapheme the most according to claim 1, it is characterised in that described sulfur
Agent includes at least one in sulfur, peroxide, metal-oxide, sulfurous organic compound.
The rubber composite modified based on three-dimensional grapheme the most according to claim 1, it is characterised in that described rubber
Compounding ingredient includes: accelerating auxiliaries, accelerator, age resistor.
The rubber composite modified based on three-dimensional grapheme the most according to claim 1, it is characterised in that described promotion
Auxiliary agent is at least one in zinc oxide or stearic acid；
Described accelerator includes in diphenylguanidine, altax, Vulcanization accelerator TMTD, accelerant CZ, accelerant B Z, accelerant MBT
At least one；
Described age resistor includes at least one in anti-aging agent RD, antioxidant 4010, age resistor 124, antioxidant D NP.
The rubber composite modified based on three-dimensional grapheme the most according to claim 6, it is characterised in that described rubber
Compounding ingredient is included by mass fraction: 2 parts of stearic acid, 5 parts of zinc oxide, 1～2 part of accelerator, 1～3 part of age resistor.
8. a preparation method for the rubber composite modified based on three-dimensional grapheme described in claim 1, its feature exists
In, including:
Step 1) prepare graphene oxide by the Hummers method improved；
Step 2) preparation of three-dimensional grapheme: by step 1) the graphene oxide ultrasonic disperse prepared is in ultra-pure water, concentration is
1-2mg/ml, transfers to 160-200 DEG C of reaction 20-24h, washing in reactor afterwards, obtains three-dimensional redox graphene water
Gel, lyophilization；
Step 3) by rubber, step 2) three-dimensional grapheme that obtains, rubber chemicals, vulcanizing agent be sequentially added in mill, 40-
Mixing 10-30min at 90 DEG C, after elastomeric compound stands 16-24h, vulcanizes on vulcanizing press, and conditions of vulcanization is 140-170 DEG C
Lower sulfuration 10-40min, obtains the rubber composite that three-dimensional grapheme is modified.
The preparation method of the rubber composite modified based on three-dimensional grapheme the most according to claim 8, its feature exists
In, including: the Hummers method of described improvement prepares graphene oxide, is divided into pre-oxidation, aoxidizes and peel off；
Described pre-oxidation is: by native graphite that mass parts is 1 part, 3-10 part concentrated sulphuric acid, the K of 0.5-0.9 part2S2O8And P2O5Mixed
Conjunction is heated to 80 DEG C, reacts 6h, cleans with ultra-pure water and obtains pre-oxidizing graphite to neutrality；
Described it is oxidized to: at 0 DEG C, pre-oxidation graphite is mixed with the concentrated sulphuric acid of 6-20 part, is under agitation gradually added into 1-3 part
KMnO4, control mixture temperature in the process below 20 DEG C.Mixture is warming up to 35 DEG C, after stirring 2h, adds 20-
50 parts of ultra-pure waters, continue stirring 15min, are eventually adding 40-150 part ultra-pure water and terminate reaction.Then, 2 parts of 30%H are added2O2,
By mixture 10%HCl eccentric cleaning to remove unnecessary metal ion, the precipitation ultra-pure water obtained is centrifuged repeatedly cleaning
It is neutrality to solution；
Described stripping: in order to peel off graphite oxide, the ultrasonic 30min of cell pulverization instrument of product 400w that will obtain,
13000rpm centrifuging and taking supernatant, carries out 24h and is dried, obtain dark brown graphene oxide at a temperature of 90 DEG C.
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