CN102634106B - Preparation method of graphene oxide nanobelt/polar rubber composite material - Google Patents
Preparation method of graphene oxide nanobelt/polar rubber composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a graphene oxide nanobelt/polar rubber composite material. The preparation method comprises the following steps of: preparing a graphene oxide nanobelt by adopting a method for oxidizing multi-wall carbon nanotubes through potassium permanganate, then performing dispersion and oxidation on the graphene oxide nanobelt with ultrasonic waves in an organic solvent, getting a graphene oxide nanobelt/polar rubber mixed solution through a solution co-mixing method, performing vacuum drying, then adding a vulcanizing agent, further mixing through a double-roll open mill, and forming through a plate vulcanizing press so as to prepare the graphene oxide nanobelt/polar rubber composite material. Compared with the prior art, the preparation method disclosed by the invention has the advantages of simple preparation process, lower reaction temperature, easiness in control, low energy consumption and low cost, and the obtained graphene oxide nanobelt/polar rubber composite material has good mechanical properties.
Description
Technical field
The present invention relates to a kind of preparation method of matrix material, especially relate to a kind of preparation method of stannic oxide/graphene nano band/polar rubber matrix material.
Background technology
Graphene is the carbon atomic layer of monatomic thickness, and it can regard the elementary cell of soccerballene, carbon nanotube, graphite as.Graphene, as a kind of nano material, has excellent mechanical property, thermal characteristics and absorption property, as high Young's modulus (about 1100GPa), thermal conductivity (about 5000J (mKs)
-1), carrier mobility (2 * 10
5cm
2(Vs)
-1) and specific surface area (calculated value 2630m
2g
-1) etc.But, because grapheme material itself lacks effective band gap, its application at electron device is restricted.Yet graphene nanobelt, because quantum confined effect and fringing effect have energy gap, has semiconducting behavior, the character of this uniqueness is shown great attention to it in recent years.
Graphene nanobelt, is on the basis of two-dimentional Graphene plane, the zonal structure forming through certain shearing.Graphene nanobelt can be prepared as raw material by carbon nanotube.The people such as the Jiao of Stanford University with the method for plasma etching multi-walled carbon nano-tubes prepare the controlled graphene nanobelt of high yield, the smooth of the edge, width (Nature, 2009,458,877-880).The people such as the Dmitry of Rice University with solution oxide legal system for productive rate approach 100% graphene nanobelt (Nature, 2009,458,872-876).The method is that condition has been created in the production in enormous quantities of graphene nanobelt, and this is also for laboratory broad scale research and industrial production are laid a good foundation.
Graphene nanobelt can be used as the mechanical property that reinforced filling improves plastics.0.2wt% stannic oxide/graphene nano band makes the tensile modulus of polyvinyl alcohol improve 35.6%, and maximum stress raising 41.9% (Journal of Physical Chemistry C, 2010,114,19621-19628).Compare with multi-wall carbon nano-tube, graphene nanobelt can more effectively improve the stress transfer efficiency of epoxy resin, thus improved Young's modulus and tensile strength (ACS Nano, 2010,4,7415-7420).Research shows that the graphene nanobelt being made by multi-walled carbon nano-tubes is a kind of high-performance reinforced filling of plastics composite, its performance Single Walled Carbon Nanotube that can match in excellence or beauty, and cost is than the low order of magnitude of Single Walled Carbon Nanotube.
Yet graphene nanobelt/rubber composite of having reported, only has silicon rubber at present.The people such as Ayrat Dimiev prepared low-loss high-k graphene nanobelt/silicon rubber composite material (ACS Applied Materials & Interfaces, 2011,3,4657-4661).Also have no at present the bibliographical information of graphene nanobelt/rubber composite mechanical property.Graphene nanobelt has unique geometry, and specific surface area is larger than multi-walled carbon nano-tubes, can increase the contact area with rubber matrix.In addition, stannic oxide/graphene nano band contains a large amount of oxy radicals, as hydroxyl, carboxyl, epoxy group(ing), can produce hydrogen bond and increase the interface binding power of filler and matrix, thereby can obtain good reinforcing effect in polar rubber matrix.
Summary of the invention
Object of the present invention is exactly that a kind of preparation method of stannic oxide/graphene nano band/polar rubber matrix material is provided in order to overcome the defect of above-mentioned prior art existence, adopt the method for potassium permanganate oxidation multi-walled carbon nano-tubes to prepare stannic oxide/graphene nano band, then with solution blended process, stannic oxide/graphene nano band and polar rubber are mixed, the method of disperseing by mechanical stirring and ultrasonic wave, makes stannic oxide/graphene nano band be homogeneously dispersed state.After vacuum-drying, add vulcanizing agent, further, by two roller mill mixing, vulcanizing press moulding, prepare stannic oxide/graphene nano band/polar rubber matrix material with good mechanical property.
Object of the present invention can be achieved through the following technical solutions:
The preparation method of stannic oxide/graphene nano band/polar rubber matrix material, comprises the following steps:
(1) preparation of stannic oxide/graphene nano band
Solution oxide method: carbon nanotube is oxidized with potassium permanganate in the vitriol oil, temperature is 55～80 ℃, reaction times is 2～5 hours, reaction conditions is preferably slowly warming up to 70 ℃, and keep 1 hour at 70 ℃, then in ice bath, add aqueous hydrogen peroxide solution to dilute, the concentration of hydrogen peroxide is 0.1～10wt%, preferred 1wt%, use again hydrochloric acid, deionized water carries out suction filtration and cleans to neutral, the concentration of hydrochloric acid is 1～15wt%, preferred 10wt%, wash number is 3 hydrochloric acid cleanings preferably, 3 washed with de-ionized water, then with freeze drier, be dried, to constant weight, Freeze Drying Equipment temperature is-70～-40 ℃, freeze-drying time is 5～10 days, obtain stannic oxide/graphene nano band.
Wherein, carbon nanotube type is single wall, double-walled or many walls, and due to price advantage, preferred multi-walled carbon nano-tubes; The consumption of the vitriol oil (98%) is 50～10000ml vitriol oil for 1g carbon nanotube, preferably 100～1000ml; The consumption of potassium permanganate is the 100wt%～500wt% of carbon nanotube consumption, for improving oxidisability, and preferred 400wt%～500wt%.
(2) preparation of stannic oxide/graphene nano band/polar rubber matrix material
A, solution blending: stannic oxide/graphene nano band is placed in to organic solvent mechanical stirring ultrasonic wave dispersion, churning time is 5～24 hours, preferably 8～15 hours, ultrasonic power is 50～450W, ultrasonic time is 0.5～3 hour, preferred ultrasonic power 90W, ultrasonic time 1～2 hour, obtains stannic oxide/graphene nano band dispersion liquid.Polar rubber is placed in to tetrahydrofuran (THF), by mechanical stirring, promotes it to dissolve, obtain polar rubber solution.Then stannic oxide/graphene nano band dispersion liquid and polar rubber solution are mixed, churning time is 10～24 hours, and ultrasonic time is 0.5～1 hour, and preferably churning time is 10～15 hours, ultrasonic time 0.5 hour.
Wherein, the add-on of stannic oxide/graphene nano band is 0.1～10 part, preferably 0.1～2 part; Polar rubber is at least one in ethylene vinyl acetate rubber, hydrogenated carboxylated nitrile rubber, paracril, hydrogenated nitrile-butadiene rubber; Organic solvent is tetrahydrofuran (THF), and DMF or other can be uniformly dispersed the solvent of stannic oxide/graphene nano band.
B, vacuum-drying: by stannic oxide/graphene nano band/polar rubber mixed solution cast film forming, with vacuum drying oven, be dried, to constant weight, temperature is 50～150 ℃, and the time is 6～24 hours, if solvent is tetrahydrofuran (THF), preferably 60 ℃, if solvent is DMF, preferably 90 ℃, obtain stannic oxide/graphene nano band/polar rubber film;
C, melt blending: use acetone solution vulcanizing agent, drip on above-mentioned stannic oxide/graphene nano band/polar rubber film, vulcanizing agent 1～5 weight part, treats acetone volatilization completely, mixing 2～5min in two roller mills at room temperature, slice.Bin aging carries out sulfidization molding after one day.
Wherein, vulcanizing agent is dicumyl peroxide.Vulcanizing agent, vulcanization aid are the technology that those skilled in the art are generally acknowledged, can be used in conjunction with, and its precondition is that these auxiliary agents do not have a negative impact to obtaining of the realization of object of the present invention and excellent results of the present invention.
D, sulfidization molding: with vulcanizing press, carry out compression molding, sulfide stress is 10～20MPa, preferably 15MPa, curing time is sulfurizing time, curing temperature is 150～180 ℃, preferably 170 ℃, prepares stannic oxide/graphene nano band/polar rubber matrix material.
Stannic oxide/graphene nano band/polar rubber matrix material can be used in the industries such as electric wire, automobile, aviation, oil.
Compared with prior art, tool of the present invention has the following advantages:
(1) method that the present invention adopts solution blending and melt blending to combine is dispersed in polar rubber stannic oxide/graphene nano band, obtains high-quality product;
(2) preparation technology of the present invention is simple, and temperature of reaction is lower, is easy to control, and energy consumption is low, and cost is low;
(3) the present invention only need add the stannic oxide/graphene nano band of low loading level (0.2～0.5 part) in polar rubber matrix, just can make the tensile strength of polar rubber improve 30～60%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
These embodiment are only not used in and limit the scope of the invention for the present invention is described.The person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Measurement of Material Mechanical Performance in the following example and comparative example is carried out on SANS-Power Test tension testing machine, and tensile strength is pressed GB/T 528-1998 test, test condition: rate of extension is 500mm/min, probe temperature is 23 ℃, tensile bars is dumbbell shape, long 7.5mm, wide 4mm.
Embodiment and comparative example material therefor are as follows:
Multi-walled carbon nano-tubes (MWNT): NC 7000, Nanocyl company, mean diameter is 9.5nm, and mean length is 1.5 μ m, and purity is 90%, and specific surface area is 250～300m
2/ g.
Ethylene vinyl acetate rubber (EVM): Levapren, German Lanxess GmbH company, mooney viscosity ML (1+4) 100 ℃=60, vinyl acetate between to for plastic (VA) content is 70wt%.
Hydrogenated carboxylated nitrile rubber (HXNBR): KA 8889, Therban XTVP company, mooney viscosity ML (1+4) 100 ℃=77 ± 7, acrylonitrile content is 33%, and carboxyl-content is 5%, and residual pair of key is 3.5%.
All the other materials are commercially available.
The formula that embodiment 1-4 and comparative example 1-2 press in table 1 and table 2 is carried out.
The formula (parts by weight) of table 1 stannic oxide/graphene nano band (uCNT)/EVM matrix material
Note: vulcanizing agent is dicumyl peroxide (DCP)
The formula (parts by weight) of table 2uCNT/HXNBR matrix material
Embodiment 1
2g multi-walled carbon nano-tubes and the 200ml vitriol oil are joined in beaker, stir 1 hour, then be placed in ice bath and slowly add 10g potassium permanganate, temperature remains on below 10 ℃, then at room temperature stir 1 hour, then in oil bath, heat, 55 ℃ are reacted 0.5 hour, 60 ℃ are reacted 1 hour, 65 ℃ are reacted 1 hour, and keep 1 hour at 70 ℃, then in ice bath, add 500ml aqueous hydrogen peroxide solution (containing 6ml 30% hydrogen peroxide) to dilute, use again 10wt% hydrochloric acid cleaning 3 times, washed with de-ionized water 3 times is to neutral, by the mixed fine microfiltration membrane that aperture is 0.45 μ m, carry out suction filtration, then with freeze drier, be dried, to constant weight, Freeze Drying Equipment temperature is-55 ℃, freeze-drying time is 7 days, obtain stannic oxide/graphene nano band.
Get 0.10g stannic oxide/graphene nano band and be placed in 100ml DMF mechanical stirring 2 hours, ultrasonic wave is disperseed 2 hours, and ultrasonic power is 90W, then stirs 10 hours, obtains stannic oxide/graphene nano band dispersion liquid.5g ethylene vinyl acetate rubber is placed in to 50ml tetrahydrofuran (THF), and mechanical stirring 24 hours, obtains ethylene vinyl acetate rubber solutions.Then stannic oxide/graphene nano band dispersion liquid and ethylene vinyl acetate rubber solutions are mixed, stir 4 hours, ultrasonic wave is disperseed 0.5 hour, then stirs 5 hours.Stannic oxide/graphene nano band/ethylene vinyl acetate rubber mix liquid with vacuum drying oven in 90 ℃ dry, to constant weight.With 0.5ml acetone solution 0.10g dicumyl peroxide, drip on stannic oxide/graphene nano band/ethylene vinyl acetate rubber film, treat acetone volatilization completely, mixing 2～5min in two roller mills at room temperature, slice.After bin aging one day, compression molding on vulcanizing press, sulfide stress is 15MPa, and curing time is 20min, and curing temperature is 170 ℃, prepares stannic oxide/graphene nano band/ethylene vinyl acetate rubber composite.Finally determine dumbbell shape sample for Mechanics Performance Testing.
Embodiment 2
The preparation method of the preparation of stannic oxide/graphene nano band and stannic oxide/graphene nano band/ethylene vinyl acetate rubber composite is identical with embodiment 1.
Different is that the stannic oxide/graphene nano band that embodiment 1 adds is 0.2 part, and embodiment 2 adds 0.5 part, the concrete steps of preparing stannic oxide/graphene nano band dispersion liquid are as follows: get 0.25g stannic oxide/graphene nano band and be placed in 250ml N, in dinethylformamide, mechanical stirring is 2 hours, ultrasonic wave is disperseed 2 hours, ultrasonic power is 90W, then stirs 10 hours, obtains stannic oxide/graphene nano band dispersion liquid.
Embodiment 3
The preparation method of the preparation of stannic oxide/graphene nano band and stannic oxide/graphene nano band/polar rubber matrix material is identical with embodiment 1.
The polar rubber that different is in embodiment 3 is hydrogenated carboxylated nitrile rubber, and concrete steps are as follows: 5g hydrogenated carboxylated nitrile rubber is placed in to 60ml tetrahydrofuran (THF), and mechanical stirring 24 hours, obtains hydrogenated carboxylated nitrile rubber solution.Then stannic oxide/graphene nano band dispersion liquid and hydrogenated carboxylated nitrile rubber solution are mixed to also vacuum-drying.With 0.5ml acetone solution 0.15g dicumyl peroxide, drip on stannic oxide/graphene nano band/hydrogenated carboxylated nitrile rubber film, further mixing slice, sulfidization molding, prepare stannic oxide/graphene nano band/hydrogenated carboxylated nitrile rubber matrix material.
Embodiment 4
The preparation method of the preparation of stannic oxide/graphene nano band and stannic oxide/graphene nano band/hydrogenated carboxylated nitrile rubber matrix material is identical with embodiment 3, and the preparation of stannic oxide/graphene nano band dispersion liquid is identical with embodiment 2.
Comparative example 1
5g ethylene vinyl acetate rubber is placed in to 50ml tetrahydrofuran (THF), mechanical stirring 28 hours, ultrasonic 0.5 hour, then stir 5 hours, obtain ethylene vinyl acetate rubber solutions.The condition of vacuum-drying, calendering process, sulfidization molding is identical with embodiment 1.
Comparative example 2
5g hydrogenated carboxylated nitrile rubber is placed in to 60ml tetrahydrofuran (THF), mechanical stirring 28 hours, ultrasonic 0.5 hour, then stir 5 hours, obtain ethylene vinyl acetate rubber solutions.The condition of vacuum-drying, calendering process, sulfidization molding is identical with embodiment 3.
The comparison of uCNT/EVM composite materials property prepared by table 3EVM and the present invention
The comparison of uCNT/HXNBR composite materials property prepared by table 4HXNBR and the present invention
From table 3 and table 4, in embodiment 1 and embodiment 2, only need add the stannic oxide/graphene nano band of low loading level (0.2 and 0.5 part), can make the tensile strength of acetic acid vinyl acetate rubber improve 30%, in embodiment 3 and embodiment 4, the tensile strength of hydrogenated carboxylated nitrile rubber has improved respectively 60% and 50% with respect to comparative example 2.Illustrate and adopt the preparation method of stannic oxide/graphene nano band/polar rubber of the present invention just can obtain good mechanical property under low sizing addition.
Embodiment 5
The preparation method of stannic oxide/graphene nano band/nitile-butadiene rubber composite material, comprises the following steps: the preparation of (1) stannic oxide/graphene nano band
Solution oxide method: multi-walled carbon nano-tubes is oxidized with potassium permanganate in the vitriol oil (98%), the consumption of potassium permanganate is 100% of carbon nanotube consumption, controlling temperature is 55 ℃, reaction times is 5 hours, then in ice bath, add aqueous hydrogen peroxide solution to dilute, the concentration of hydrogen peroxide is 0.1wt%, with hydrochloric acid, deionized water, carrying out suction filtration again cleans to neutral, the concentration of hydrochloric acid is 1wt%, then with freeze drier, be dried, to constant weight, Freeze Drying Equipment temperature is-70 ℃, freeze-drying time is 5 days, obtains stannic oxide/graphene nano band.
(2) preparation of stannic oxide/graphene nano band/nitile-butadiene rubber composite material
A, solution blending: the stannic oxide/graphene nano band of 0.1 weight part is placed in to tetrahydrofuran (THF) mechanical stirring ultrasonic wave dispersion, churning time is 5 hours, and control ultrasonic power is 450W, ultrasonic time is 3 hours, obtains stannic oxide/graphene nano band dispersion liquid.The paracril of 100 weight parts is placed in to tetrahydrofuran (THF), by mechanical stirring, promotes it to dissolve, obtain nitrile rubber solution.Then stannic oxide/graphene nano band dispersion liquid and nitrile rubber solution are mixed, controlling mechanical churning time is 10 hours, and the ultrasonic agitation time is 0.5 hour.
B, vacuum-drying: by stannic oxide/graphene nano band/paracril mixed solution cast film forming, with vacuum drying oven, be dried, to constant weight, bake out temperature is 50 ℃, and the time is 24 hours, obtains stannic oxide/graphene nano band/paracril film.
C, melt blending: use acetone solution dicumyl peroxide, dropping is on above-mentioned stannic oxide/graphene nano band/paracril film, and the add-on of dicumyl peroxide is 1 weight part, treats acetone volatilization completely, mixing 2min in two roller mills at room temperature, slice.Bin aging carries out sulfidization molding after one day.
D, sulfidization molding: with vulcanizing press, carry out compression molding, sulfide stress is 10MPa, and curing time is sulfurizing time, and curing temperature is 150 ℃, prepare stannic oxide/graphene nano band/nitile-butadiene rubber composite material, can be used in the industries such as automobile, aviation, oil.
Embodiment 6
The preparation method of stannic oxide/graphene nano band/hydrogenated nitrile-butadiene rubber composites, comprises the following steps:
(1) preparation of stannic oxide/graphene nano band
Solution oxide method: Single Walled Carbon Nanotube is oxidized with potassium permanganate in the vitriol oil, the consumption of potassium permanganate is 400% of carbon nanotube consumption, slowly be warming up to 70 ℃, reaction times is 3 hours, and keep again 1 hour at 70 ℃, then in ice bath, add the aqueous hydrogen peroxide solution of 1wt% to dilute, with hydrochloric acid, the deionized water of 10wt%, carry out suction filtration again and clean 3 times to neutral, then with freeze drier, be dried, to constant weight, Freeze Drying Equipment temperature is-50 ℃, and freeze-drying time is 8 days, obtains stannic oxide/graphene nano band.
(2) preparation of stannic oxide/graphene nano band/polar rubber matrix material
A, solution blending: the stannic oxide/graphene nano band of 1 weight part is placed in to tetrahydrofuran (THF) mechanical stirring ultrasonic wave and disperses, churning time is 8 hours, and to control ultrasonic power be 90W, within ultrasonic 1 hour, obtains stannic oxide/graphene nano band dispersion liquid.The hydrogenated nitrile-butadiene rubber glue of 100 weight parts is placed in to tetrahydrofuran (THF), by mechanical stirring, promotes it to dissolve, obtain hydrogenated nitrile-butadiene rubber solution.Then stannic oxide/graphene nano band dispersion liquid and hydrogenated nitrile-butadiene rubber solution are mixed, controlling mechanical churning time is 10 hours, and the ultrasonic agitation time is 0.5 hour.
B, vacuum-drying: by stannic oxide/graphene nano band/hydrogenated nitrile-butadiene rubber mixed solution cast film forming, with vacuum drying oven, be dried, to constant weight, temperature is 60 ℃, and the time is 12 hours, obtains stannic oxide/graphene nano band/hydrogenated nitrile-butadiene rubber film;
C, melt blending: use acetone solution dicumyl peroxide, dropping is on above-mentioned stannic oxide/graphene nano band/hydrogenated nitrile-butadiene rubber film, and the add-on of dicumyl peroxide is 2 weight parts, treats acetone volatilization completely, mixing 2～5min in two roller mills at room temperature, slice.Bin aging carries out sulfidization molding after one day.
D, sulfidization molding: with vulcanizing press, carry out compression molding, sulfide stress is 15MPa, and curing time is sulfurizing time, and curing temperature is 170 ℃, prepare stannic oxide/graphene nano band/hydrogenated nitrile-butadiene rubber composites, can be used in the industries such as electric wire, automobile, aviation, oil.
Embodiment 7
The preparation method of stannic oxide/graphene nano band/paracril/hydrogenated nitrile-butadiene rubber composites, comprises the following steps:
(1) preparation of stannic oxide/graphene nano band
Solution oxide method: carbon nanotube is oxidized with potassium permanganate in the vitriol oil, the consumption of potassium permanganate is 400% of carbon nanotube consumption, temperature is 70 ℃, and the reaction times is 5 hours, then in ice bath, adds the aqueous hydrogen peroxide solution of 1wt% to dilute, with hydrochloric acid, the deionized water of 10wt%, carry out suction filtration cleaning to neutral again, then with freeze drier, be dried, to constant weight, Freeze Drying Equipment temperature is-60 ℃, freeze-drying time is 6 days, obtains stannic oxide/graphene nano band.
(2) preparation of stannic oxide/graphene nano band/paracril/hydrogenated nitrile-butadiene rubber composites
A, solution blending: the stannic oxide/graphene nano band of 2 weight parts is placed in to DMF mechanical stirring ultrasonic wave dispersion, and churning time is 15 hours, and ultrasonic power is 200W, and ultrasonic time is 2 hours, obtains stannic oxide/graphene nano band dispersion liquid.Paracril/hydrogenated nitrile-butadiene rubber blend of 100 weight parts is placed in to tetrahydrofuran (THF), by mechanical stirring, promotes it to dissolve, obtain paracril/hydrogenated nitrile-butadiene rubber solution.Then stannic oxide/graphene nano band dispersion liquid and paracril/hydrogenated nitrile-butadiene rubber solution are mixed, controlling mechanical churning time is 15 hours, and the ultrasonic agitation time is 0.5 hour.
B, vacuum-drying: by stannic oxide/graphene nano band/paracril/hydrogenated nitrile-butadiene rubber mixed solution cast film forming, with vacuum drying oven, be dried, to constant weight, temperature is 90 ℃, time is 12 hours, obtains stannic oxide/graphene nano band/paracril/hydrogenated nitrile-butadiene rubber film;
C, melt blending: use acetone solution dicumyl peroxide, dropping is on above-mentioned stannic oxide/graphene nano band/polar rubber film, and the add-on of dicumyl peroxide is 5 weight parts, treats acetone volatilization completely, mixing 5min in two roller mills at room temperature, slice.Bin aging carries out sulfidization molding after one day.
D, sulfidization molding: with vulcanizing press, carry out compression molding, sulfide stress is 15MPa, curing time is sulfurizing time, curing temperature is 170 ℃, prepare stannic oxide/graphene nano band/paracril/hydrogenated nitrile-butadiene rubber composites, can be used in the industries such as electric wire, automobile, aviation, oil.
Embodiment 8
The preparation method of stannic oxide/graphene nano band/ethylene vinyl acetate rubber composite, comprises the following steps:
(1) preparation of stannic oxide/graphene nano band
Solution oxide method: carbon nanotube is oxidized with potassium permanganate in the vitriol oil, the consumption of potassium permanganate is 500% of carbon nanotube consumption, temperature is 80 ℃, and the reaction times is 2 hours, then in ice bath, adds the aqueous hydrogen peroxide solution of 10wt% to dilute, with hydrochloric acid, the deionized water of 15wt%, carry out suction filtration cleaning to neutral again, then with freeze drier, be dried, to constant weight, Freeze Drying Equipment temperature is-40 ℃, freeze-drying time is 10 days, obtains stannic oxide/graphene nano band.
(2) preparation of stannic oxide/graphene nano band/ethylene vinyl acetate rubber composite
A, solution blending: the stannic oxide/graphene nano band of 10 weight parts is placed in to tetrahydrofuran (THF) mechanical stirring ultrasonic wave dispersion, and churning time is 24 hours, and ultrasonic power is 50W, and ultrasonic time is 0.5 hour, obtains stannic oxide/graphene nano band dispersion liquid.The ethylene vinyl acetate rubber of 100 weight parts is placed in to tetrahydrofuran (THF), by mechanical stirring, promotes it to dissolve, obtain ethylene vinyl acetate rubber solutions.Then stannic oxide/graphene nano band dispersion liquid and ethylene vinyl acetate rubber solutions are mixed, controlling mechanical churning time is 24 hours, and the ultrasonic agitation time is 1 hour.
B, vacuum-drying: by stannic oxide/graphene nano band/ethylene vinyl acetate rubber mix liquid cast film forming, with vacuum drying oven, be dried, to constant weight, temperature is 150 ℃, time is 6 hours, obtains stannic oxide/graphene nano band/ethylene vinyl acetate rubber film;
C, melt blending: use acetone solution dicumyl peroxide, dropping is on above-mentioned stannic oxide/graphene nano band/polar rubber film, and the add-on of dicumyl peroxide is 5 weight parts, treats acetone volatilization completely, mixing 5min in two roller mills at room temperature, slice.Bin aging carries out sulfidization molding after one day.
D, sulfidization molding: with vulcanizing press, carry out compression molding, sulfide stress is 20MPa, curing time is sulfurizing time, curing temperature is 180 ℃, preferably 170 ℃, prepare stannic oxide/graphene nano band/ethylene vinyl acetate rubber composite, can be used in the industries such as electric wire, automobile, aviation, oil.
Claims (9)
1. a preparation method for stannic oxide/graphene nano band/polar rubber matrix material, is characterized in that, the method comprises the following steps:
(1) preparation of stannic oxide/graphene nano band
Solution oxide method: multi-walled carbon nano-tubes is oxidized with potassium permanganate in the vitriol oil, temperature is 55～80 ℃, reaction times is 2～5 hours, then in ice bath, with the aqueous hydrogen peroxide solution that concentration is 0.1～10wt%, dilute, by concentration, be that 1～10wt% hydrochloric acid, deionized water carry out suction filtration cleaning to neutral again, then with freeze drier, be dried, prepare stannic oxide/graphene nano band;
(2) preparation of stannic oxide/graphene nano band/polar rubber matrix material
A, solution blending: stannic oxide/graphene nano band is placed in to organic solvent, mechanical stirring is also disperseed by ultrasonic wave, churning time is 5～24 hours, ultrasonic power is 50～450W, ultrasonic time is 0.5～3 hour, obtain stannic oxide/graphene nano band dispersion liquid, polar rubber is placed in to tetrahydrofuran (THF), by mechanical stirring, promote its dissolving to obtain polar rubber solution, then stannic oxide/graphene nano band dispersion liquid and polar rubber solution are mixed, churning time is 10～24 hours, and ultrasonic time is 0.5～1 hour;
B, vacuum-drying: will prepare stannic oxide/graphene nano band/polar rubber mixed solution cast film forming through above-mentioned steps, with vacuum drying oven, be dried to constant weight, controlling drying temperature is 50～150 ℃, and the time is 6～24 hours, obtains stannic oxide/graphene nano band/polar rubber film;
C, melt blending: use acetone solution vulcanizing agent, drip on above-mentioned stannic oxide/graphene nano band/polar rubber film, vulcanizing agent 1～5 weight part, treats acetone volatilization completely, at normal temperatures slice after mixing 2～5min in two roller mills;
Sulfidization molding: carry out sulfidization molding with vulcanizing press, control sulfide stress is 10～20MPa, and curing time is sulfurizing time, and curing temperature is 150～180 ℃, prepares stannic oxide/graphene nano band/polar rubber matrix material.
2. the preparation method of a kind of stannic oxide/graphene nano band/polar rubber matrix material according to claim 1, is characterized in that, the consumption of the potassium permanganate described in step (1) is 100%～500wt% of multi-walled carbon nano-tubes consumption.
3. the preparation method of a kind of stannic oxide/graphene nano band/polar rubber matrix material according to claim 1, is characterized in that, the consumption of the potassium permanganate described in step (1) is preferably 400%～500wt% of multi-walled carbon nano-tubes consumption.
4. the preparation method of a kind of stannic oxide/graphene nano band/polar rubber matrix material according to claim 1, it is characterized in that, organic solvent described in a step of step (2) is the solvent that can be uniformly dispersed stannic oxide/graphene nano band, selects tetrahydrofuran (THF) or DMF.
5. the preparation method of a kind of stannic oxide/graphene nano band/polar rubber matrix material according to claim 1, it is characterized in that, the polar rubber described in a step of step (2) is at least one in ethylene vinyl acetate rubber, hydrogenated carboxylated nitrile rubber, paracril, hydrogenated nitrile-butadiene rubber.
6. the preparation method of a kind of stannic oxide/graphene nano band/polar rubber matrix material according to claim 1, it is characterized in that, the add-on of the stannic oxide/graphene nano band described in a step of step (2) is 0.1～10 weight part, and the add-on of polar rubber is 100 weight parts.
7. the preparation method of a kind of stannic oxide/graphene nano band/polar rubber matrix material according to claim 1, is characterized in that, the add-on of the stannic oxide/graphene nano band described in a step of step (2) is 0.1～2 weight part preferably.
8. the preparation method of a kind of stannic oxide/graphene nano band/polar rubber matrix material according to claim 1, is characterized in that, the vulcanizing agent described in the c step of step (2) is dicumyl peroxide.
9. the preparation method of a kind of stannic oxide/graphene nano band/polar rubber matrix material according to claim 1, it is characterized in that, the stannic oxide/graphene nano band/polar rubber matrix material preparing can be used in electric wire, automobile, aviation or petroleum industry.
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| CN102161785B (en) * | 2011-03-10 | 2013-02-13 | 四川大学 | Preparation method of graphene/polymer nano composite material |
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