CN104072979A - Oxidized graphene nano-ribbon/polymer composite film and preparation method thereof - Google Patents

Oxidized graphene nano-ribbon/polymer composite film and preparation method thereof Download PDF

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CN104072979A
CN104072979A CN201410342652.3A CN201410342652A CN104072979A CN 104072979 A CN104072979 A CN 104072979A CN 201410342652 A CN201410342652 A CN 201410342652A CN 104072979 A CN104072979 A CN 104072979A
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graphene nano
stannic oxide
nano band
film
composite film
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CN104072979B (en
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郑玉婴
樊志敏
林锦贤
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福州大学
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    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
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    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract

The invention discloses an oxidized graphene nano-ribbon/polymer composite film and a preparation method thereof. The preparation method comprises the following steps: longitudinally cutting a multi-walled carbon nano-tube into oxidized graphene nano-ribbons of strip-shaped structures through oxidation; compounding the oxidized graphene nano-ribbons with a polymer to form the film. The composite film prepared according to the invention is excellent in barrier property and mechanical property, and has a certain fixed degree of transparency, thereby being widely applied to the field with higher barrier requirements. At present, mass production of multi-walled carbon nano-tubes is realized in domestic and foreign countries, so that the preparation cost of the oxidized graphene nano-ribbon is greatly reduced. The barrier property and mechanical property of the composite film can be greatly improved only with few oxidized graphene nano-ribbons. The preparation method is simple, high in operability, and is suitable for large-scale industrialized production.

Description

A kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof
Technical field
The invention belongs to polymer laminated film preparing technical field, be specifically related to a kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof.
Background technology
Desirable Graphene is that a kind of two dimension of individual layer is without limit structure, have high degree of crystallinity and semi-metal electric property, in energy storage material, electron device, prepare composite, become study hotspot, and Graphene has excellent pressuretightness, in barrier material field, also favored gradually at present, but the graphene film surface of preparing in reality is often with fold fluctuating defect, and this will certainly affect it in the application of numerous areas.A kind of new carbon graphene nanobelt rising in recent years becomes transparency electrode, the optimal candidate in the fields such as barrier filler owing to having the features such as unique high aspect ratio, low defect, form be controlled.
Graphene nanobelt is that a kind of carbon atom is with sp 2the thin fine strip shape material that hybridized orbital forms, can adopt CVD method, planography method, supersonic method, longitudinally oxygen cutting carbon nanotube legal system is standby.Carbon nanotube is mainly divided into two kinds of Single Walled Carbon Nanotube and multi-walled carbon nano-tubes, from known document, known tradition adopts the graphene nanobelt that longitudinal oxygen cutting Single Walled Carbon Nanotube obtains easily tangle and be unfavorable for using, utilize neat in edge of graphene nanobelt that multi-walled carbon nano-tubes cutting obtains, zonal structure defect is few, there is excellent electronic transmission performance, mechanical property, the transparency and pressuretightness, but its preparation cost is more expensive.Therefore, by having equally the stannic oxide/graphene nano band that pressuretightness and price are lower, replacing graphene nanobelt, be applied in obstruct field, is the effective way addressing the above problem.In addition, due to the feature of polymkeric substance itself, can allow some small-molecule substances infiltrations such as gas in the past, will certainly affect like this application of polymer materials in obstruct field, by adding the stannic oxide/graphene nano band of high-barrier, can improve the barrier of polymkeric substance.
Summary of the invention
The object of the present invention is to provide a kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof, stannic oxide/graphene nano band/the polymer composite film making through the inventive method has excellent barrier property and mechanical property, can be applied in widely the fields such as food, drug packaging and electronic product surface encapsulation material.Preparation method of the present invention is scientific and reasonable, technique is simple, workable, be applicable to large-scale industrial production.
For achieving the above object, the present invention adopts following technical scheme:
A kind of stannic oxide/graphene nano band/polymer composite film, be the method for multi-walled carbon nano-tubes utilization oxidation longitudinally to be cut into the stannic oxide/graphene nano band of zonal structure, then adopt solution manufacturing process that stannic oxide/graphene nano band and polymkeric substance are compounded to form to described film.
The preparation of described stannic oxide/graphene nano band/polymer composite film comprises the steps:
1) by 15-20 g polymer dissolution in the solvent of 40-60 ml, swelling 12h in the air dry oven of 80-100 ℃;
2) 0.045-0.15 g stannic oxide/graphene nano band is dissolved in the solvent of 10-20 ml to the ultrasonic dispersion of 100 W 20-30 min;
3) by polymers soln and the step 2 of step 1)) ultrasonic scattered stannic oxide/graphene nano band mixes, the ultrasonic dispersion of 100 W 1-5 h, then on machine mixer, stir 1-3 h, form pasty state liquid;
4) on suction filtration machine, extract the air in pasty state liquid out, sheet glass is placed on film applicator, then utilize wet film preparing device to be coated with the film of 0.10 ± 0.01mm thickness, then sheet glass is placed in the vacuum drying oven of 60-65 ℃ and vacuumizes; After 10-20 min, open vacuum drying oven, solvent vapo(u)r is emitted, then sheet glass after dry 4-8 h, is cooled under room temperature in 70-80 ℃, film is taken off, obtain described stannic oxide/graphene nano band-polymer composite film.
The preparation of described stannic oxide/graphene nano band comprises the following steps:
1) H that is 85.8% by 20-30 ml, massfraction 3pO 4solution joins in 500 ml, the round-bottomed flask with magnet rotor, then by the dense H of 180-200 ml 2sO 4join in round-bottomed flask, under the rotating speed of 300r/min, stir;
2) 1-1.5 g multi-walled carbon nano-tubes is joined in the solution of step 1), stirs 1-2 h, then in 30min by 6-9 g KMnO 4divide 3 steps slowly to join in above-mentioned mixed solution, then stir 15-30 min;
3) by step 2) reaction system move in the oil bath pan of 55-65 ℃, under the rotating speed of 300r/min, stirring reaction 2-6 h, cools to room temperature, then pours into and contains 5-10 ml H 2o 2frozen water mixed solution in 24 h that condense, now solution becomes blackish greenly, shows to react completely;
4) solution of step 3) is disperseed to 20-30 min with 100 W power ultrasonics, the HCl that is 10% with massfraction on poly tetrafluoroethylene and deionized water repetitive scrubbing filter, and last 60 ℃ of vacuum-drying 24 h, obtain described stannic oxide/graphene nano band.
Described polymkeric substance is any one in polyester type thermoplastic polyurethane, polyether-type thermoplastic polyurethane, polyvinyl alcohol, polyvinyl chloride, polymethylmethacrylate, polyaniline, polymeric amide, polystyrene or polyethylene.
Described solvent is any one in N-N dimethyl formamide, tetrahydrofuran (THF), trichloromethane, toluene or water.
Tradition utilizes graphene oxide to prepare laminated film, because graphene oxide base part has a lot of defects, therefore to small-molecule substance, can not play good iris action, and stannic oxide/graphene nano band only has the edge defectiveness of band, its zone face can well contact with polymeric matrix, therefore, utilize its laminated film of preparing to compare with utilizing laminated film prepared by stannic oxide/graphene nano, there is better impermeable effect.
On the other hand, original multi-walled carbon nano-tubes is for strengthening polymer composites DeGrain, this is because multi-walled carbon nano-tubes only has the Surface Contact of tubulose, and it is longitudinally cut into after the stannic oxide/graphene nano band of zonal structure, because the two sides of stannic oxide/graphene nano band can well contact with polymeric matrix, contact area significantly increases, thereby can obviously strengthen the performance of polymeric film.
the invention has the advantages that:
(1) carbon nanotube has been realized large-scale industrial production both at home and abroad at present, the preparation of stannic oxide/graphene nano band is also dirt cheap, simultaneously, the stannic oxide/graphene nano band that the present invention only need seldom measure just can prepare the laminated film of barrier property and mechanical property excellence, make it with low cost, can be applied in widely and intercept the field of having relatively high expectations, and its preparation technology is simple, strong operability, is applicable to large-scale industrial production.
(2) laminated film that prepared by the present invention not only has excellent barrier property and mechanical property, also has certain transparency, can be applied in widely the fields such as food, drug packaging and electronic product surface encapsulation material.
Accompanying drawing explanation
Fig. 1 is the obstruct principle schematic of stannic oxide/graphene nano band/polymer composite film.
Fig. 2 is the SEM figure of the prepared stannic oxide/graphene nano band of multi-walled carbon nano-tubes and the present invention, and wherein, A is multi-walled carbon nano-tubes, and B is stannic oxide/graphene nano band.
Fig. 3 is the TEM figure of the prepared stannic oxide/graphene nano band of multi-walled carbon nano-tubes and the present invention, and wherein, A is multi-walled carbon nano-tubes, and B is stannic oxide/graphene nano band.
Fig. 4 is the Raman comparison diagram of the prepared stannic oxide/graphene nano band of multi-walled carbon nano-tubes and the present invention.
Fig. 5 is the XRD comparison diagram of the prepared stannic oxide/graphene nano band of multi-walled carbon nano-tubes and the present invention.
Fig. 6 is the infrared comparison diagram of the prepared stannic oxide/graphene nano band of multi-walled carbon nano-tubes and the present invention.
Embodiment
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to the following example.
The preparation of stannic oxide/graphene nano band comprises the following steps:
1) H that is 85.8% by 20 ml, massfraction 3pO 4solution joins in 500 ml, the round-bottomed flask with magnet rotor, then by the dense H of 200 ml 2sO 4join in round-bottomed flask, under the rotating speed of 300r/min, stir;
2) 1 g multi-walled carbon nano-tubes is joined in the solution of step 1), stirs 2 h, then in 30min by 6 g KMnO 4divide 3 steps slowly to join in above-mentioned mixed solution, then stir 20 min;
3) by step 2) reaction system move in the oil bath pan of 55 ℃, under the rotating speed of 300r/min, stirring reaction 2 h, cool to room temperature, then pour into and contain 5 ml H 2o 2frozen water mixed solution in 24 h that condense, now solution becomes blackish greenly, shows to react completely;
4) solution of step 3) is disperseed to 30 min with 100 W power ultrasonics, the HCl that is 10% with massfraction on poly tetrafluoroethylene and deionized water repetitive scrubbing filter, and last 60 ℃ of vacuum-drying 24 h, obtain described stannic oxide/graphene nano band.
Fig. 2 is the SEM figure of multi-walled carbon nano-tubes and prepared stannic oxide/graphene nano band, and to be multi-walled carbon nano-tubes scheme with the TEM of prepared stannic oxide/graphene nano band Fig. 3.
Fig. 4 is the Raman comparison diagram of multi-walled carbon nano-tubes and prepared stannic oxide/graphene nano band, and in Fig. 4, multi-walled carbon nano-tubes is at 1317 cm -1with 1594 cm -1represent D and G peak, through cutting, obtain D peak 1326 cm of stannic oxide/graphene nano band -1with G peak 1594 cm -1with respect to the peak shape grow of multi-walled carbon nano-tubes, broaden, show that lattice distortion and textural defect increase, and prove that multi-walled carbon nano-tubes is opened.
Fig. 5 is the XRD comparison diagram of multi-walled carbon nano-tubes and prepared stannic oxide/graphene nano band, in Fig. 5, multi-walled carbon nano-tubes is located to occur strong diffraction peak and presents sharp-pointed shape in 2 θ=26.26 °, and the interlamellar spacing that can be obtained multi-walled carbon nano-tubes by Bragg equation is 0.34 nm.Stannic oxide/graphene nano band locates to occur strong diffraction peak in 2 θ=9.06 °, corresponding interlamellar spacing is 0.98 nm, shows that multi-walled carbon nano-tubes is successfully longitudinally cut into stannic oxide/graphene nano band; It is milder that it locates peak shape in 2 θ=26.26 °, shows the basic all oxidized stannic oxide/graphene nano bands that cuts into of multi-walled carbon nano-tubes.
Fig. 6 is the infrared comparison diagram of multi-walled carbon nano-tubes and prepared stannic oxide/graphene nano band, and Fig. 6 multi-walled carbon nano-tubes is at 1043 cm -1there is the Weak Absorption peak of C-OH at place, at 1580 cm -1there is the charateristic avsorption band of C=C at place.Stannic oxide/graphene nano band is at 1225 cm -1with 1725 cm -1there is new absorption peak in place, the corresponding C=O of difference and C-O-C, 3395 cm -1place, for the flexible absorption peak of O-H, shows that multi-walled carbon nano-tubes substantially all cuts into banded stannic oxide/graphene nano band.
embodiment 1
The preparation of stannic oxide/graphene nano band/polymer composite film, comprises the following steps:
1) 15 g polyester type thermoplastic polyurethanes are dissolved in 40 ml N-N dimethyl formamides to swelling 12h in the air dry oven of 80 ℃;
2) 0.045 g stannic oxide/graphene nano band is dissolved in the N-N dimethyl formamide of 10 ml to the ultrasonic dispersion of 100 W 20min;
3) by polymers soln and the step 2 of step 1)) ultrasonic scattered stannic oxide/graphene nano band mixes, the ultrasonic dispersion of 100 W 1h, then on machine mixer, stir 3 h, form pasty state liquid;
4) pasty state liquid is poured in the low capacity bottle with suction pipe, then on suction filtration machine, extracted out the air in pasty state liquid, until there is no bubble in volumetric flask; Sheet glass is placed on film applicator, then utilizes wet film preparing device to be coated with the film of 0.09mm thickness, then sheet glass is placed in the vacuum drying oven of 60 ℃ and vacuumizes; After 10 min, open vacuum drying oven, solvent vapo(u)r is emitted, then sheet glass after dry 8 h, is cooled under room temperature in 70 ℃, film is taken off, obtain described stannic oxide/graphene nano band-polymer composite film.
embodiment 2
The preparation of stannic oxide/graphene nano band/polymer composite film, comprises the following steps:
1) 15 g polyether-type thermoplastic polyurethanes are dissolved in 60 ml tetrahydrofuran (THF)s to swelling 12h in the air dry oven of 80 ℃;
2) 0.075 g stannic oxide/graphene nano band is dissolved in the tetrahydrofuran (THF) of 10 ml to ultrasonic dispersion 20 min of 100 W;
3) by polymers soln and the step 2 of step 1)) ultrasonic scattered stannic oxide/graphene nano band mixes, ultrasonic dispersion 3 h of 100 W, then on machine mixer, stir 2 h, form pasty state liquid;
4) pasty state liquid is poured in the low capacity bottle with suction pipe, then on suction filtration machine, extracted out the air in pasty state liquid, until there is no bubble in volumetric flask; Sheet glass is placed on film applicator, then utilizes wet film preparing device to be coated with the film of 0.09 mm thickness, then sheet glass is placed in the vacuum drying oven of 62 ℃ and vacuumizes; After 15 min, open vacuum drying oven, solvent vapo(u)r is emitted, then sheet glass after dry 5 h, is cooled under room temperature in 75 ℃, film is taken off, obtain described stannic oxide/graphene nano band-polymer composite film.
embodiment 3
Do not add graphene oxide nano belt, all the other prepare pure polyester type thermoplastic polyurethane film according to the condition of embodiment 1, and experimental group 1 as a comparison.
embodiment 4
Do not add graphene oxide nano belt, all the other prepare pure polyether-type thermoplastic polyurethane film according to the condition of embodiment 2, and experimental group 2 as a comparison.
embodiment 5
Step 2) 0.045 g graphene oxide is dissolved in the N-N dimethyl formamide of 10 ml to the ultrasonic dispersion of 100 W 20min; All the other prepare graphene oxide/polyester type thermoplastic polyurethane laminated film according to the condition of embodiment 1, and experimental group 3 as a comparison.
performance test:
(1) OTR oxygen transmission rate test
According to national standard GB/T 1038-2000, the film that embodiment is made carries out oxygen and sees through test; Film sample is area 50cm 2disk, measuring accuracy: 0.01 cc/m 2.day.0.1MPa, vacuum tightness: <10 Pa, temperature control mode adopts semi-conductor bidirectional high-efficiency temperature control, finally gets the mean value of three sample OTR oxygen transmission rate of each sample.
(2) laminated film Mechanics Performance Testing
According to national standard GB/T 528-2009, the film that embodiment is made carries out tensile property test.
Test result is in Table 1.
Table 1 the performance test results
Visible by the contrast of table 1 result, to compare with simple polymeric film, the OTR oxygen transmission rate of stannic oxide/graphene nano band/polymer composite film prepared by the present invention is lower, and mechanical property is better; And in the situation that raw material consumption is equal, the barrier property of stannic oxide/graphene nano band/polymer composite film is also better than graphene oxide/polymer composite film.Therefore, the results showed and be applicable to intercept the field of having relatively high expectations by the functional of stannic oxide/graphene nano band/polymer composite film of the present invention.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (5)

1. a stannic oxide/graphene nano band/polymer composite film, it is characterized in that: the method for multi-walled carbon nano-tubes utilization oxidation is longitudinally cut into the stannic oxide/graphene nano band of zonal structure, then adopt solution manufacturing process that stannic oxide/graphene nano band and polymkeric substance are compounded to form to described film.
2. a preparation method for stannic oxide/graphene nano band/polymer composite film as claimed in claim 1, is characterized in that: comprise the steps:
After polymer dissolution is in solvent, swelling 12h in the air dry oven of 80-100 ℃;
2) stannic oxide/graphene nano band is dissolved in solvent to the ultrasonic dispersion of 100 W 20-30 min;
3) by polymers soln and the step 2 of step 1)) ultrasonic scattered stannic oxide/graphene nano band mixes, the ultrasonic dispersion of 100 W 1-5 h, then on machine mixer, stir 1-3 h, form pasty state liquid;
4) on suction filtration machine, extract the air in pasty state liquid out, sheet glass is placed on film applicator, then utilize wet film preparing device to be coated with the film of 0.10 ± 0.01mm thickness, then sheet glass is placed in the vacuum drying oven of 60-65 ℃ and vacuumizes, to remove solvent; Then sheet glass after dry 4-8 h, is cooled under room temperature in 70-80 ℃, film is taken off, obtain described stannic oxide/graphene nano band/polymer composite film.
3. the preparation method of stannic oxide/graphene nano band/polymer composite film according to claim 2, is characterized in that: the preparation method of described stannic oxide/graphene nano band comprises the following steps:
The H that is 85.8% by massfraction 3pO 4solution joins in the round-bottomed flask with magnet rotor, then by dense H 2sO 4join in round-bottomed flask, under the rotating speed of 300r/min, stir;
Multi-walled carbon nano-tubes is joined in the solution of step 1), stir 1-2 h, then by KMnO 4slowly join in above-mentioned mixed solution, then stir 15-30 min;
By step 2) reaction system move in the oil bath pan of 55-65 ℃, under the rotating speed of 300r/min, stirring reaction 2-6 h, cools to room temperature, then pours into and contains H 2o 2frozen water mixed solution in 24 h that condense;
The solution of step 3) is disperseed to 20-30 min with 100 W power ultrasonics, and the HCl that is 10% with massfraction on poly tetrafluoroethylene and deionized water repetitive scrubbing filter, and last 60 ℃ of vacuum-drying 24 h, obtain described stannic oxide/graphene nano band.
4. the preparation method of stannic oxide/graphene nano band/polymer composite film according to claim 2, is characterized in that: described polymkeric substance is any one in polyester type thermoplastic polyurethane, polyether-type thermoplastic polyurethane, polyvinyl alcohol, polyvinyl chloride, polymethylmethacrylate, polyaniline, polymeric amide, polystyrene or polyethylene.
5. the preparation method of stannic oxide/graphene nano band/polymer composite film according to claim 2, is characterized in that: described solvent is any one in N-N dimethyl formamide, tetrahydrofuran (THF), trichloromethane, toluene or water.
CN201410342652.3A 2014-07-18 2014-07-18 A kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof CN104072979B (en)

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