CN104072979B - A kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof - Google Patents
A kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof, be the stannic oxide/graphene nano band that the method for multi-walled carbon nano-tubes utilization oxidation is longitudinally cut into banded structure, then adopt solution manufacturing process that stannic oxide/graphene nano band and polymer are compounded to form to described film. Laminated film prepared by the present invention has excellent barrier property and mechanical property, and film can keep certain transparency, can be applied in widely the field of having relatively high expectations that intercepts. At present CNT both at home and abroad can large-scale production, greatly reduce the cost of preparing stannic oxide/graphene nano band, and the present invention only needs the seldom stannic oxide/graphene nano band of amount just can make the barrier of laminated film greatly improve, and its mechanical property is also greatly improved. Preparation technology of the present invention is simple, and strong operability is applicable to large-scale industrial production.
Description
Technical field
The invention belongs to macromolecule laminated film preparing technical field, be specifically related to a kind of stannic oxide/graphene nano band/poly-Compound laminated film and preparation method thereof.
Background technology
Desirable Graphene be a kind of two dimension of individual layer without limit structure, have high degree of crystallinity and semimetal electric property,Become study hotspot in energy storage material, electronic device, prepare composite, and Graphene has excellent impermeability,Also favored gradually in barrier material field at present, but the graphene film surface of preparing in reality often rises and falls and lacks with foldFall into, this will certainly affect its application at numerous areas. In recent years rise a kind of new carbon graphene nanobelt due toThere is the features such as unique high aspect ratio, low defect, form be controlled and become transparency electrode, the best in the fields such as barrier fillerCandidate.
Graphene nanobelt is that a kind of carbon atom is with sp2The thin fine strip shape material that hybridized orbit forms, can adopt CVDMethod, offset printing method, supercritical ultrasonics technology, to be longitudinally oxidized cutting carbon nanotubes legal system standby. CNT is mainly divided into single wall carbon nano-tubePipe and two kinds of multi-walled carbon nano-tubes, from known document, known tradition adopts longitudinal oxidation cutting single-wall carbon nanotubes to obtainGraphene nanobelt easily tangles and is unfavorable for using the edge of graphene nanobelt that utilizes multi-walled carbon nano-tubes cutting to obtainNeatly, banded structure defect is few, has excellent electronic transmission performance, mechanical performance, the transparency and impermeability, but its preparationCost compare costliness. Therefore, replace Graphene to receive by thering is equally the stannic oxide/graphene nano band that impermeability and price are lowerRice band, is applied in obstruct field, is the effective way addressing the above problem. In addition, due to the feature meeting of polymer itselfAllow some small-molecule substance infiltrations such as gas in the past, will certainly affect like this application of polymeric material in obstruct field, logicalCross the barrier that the stannic oxide/graphene nano band that adds high-barrier can improve polymer.
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 mechanicalnessCan, can be applied in widely the fields such as food, medicine packaging and electronic product surface encapsulation material. Preparation method of the present inventionScientific 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 is by vertical the method for multi-walled carbon nano-tubes utilization oxidationTo the stannic oxide/graphene nano band that cuts into banded structure, then adopt solution manufacturing process by stannic oxide/graphene nano band and poly-Compound is compounded to form described film.
The preparation of described stannic oxide/graphene nano band/polymer composite film comprises the steps:
1) by 15-20g polymer dissolution in the solvent of 40-60ml, swelling in the air dry oven of 80-100 DEG C12h；
2) 0.045-0.15g stannic oxide/graphene nano band is dissolved in the solvent of 10-20ml to the ultrasonic dispersion of 100W20-30min；
3) by polymer solution and the step 2 of step 1)) ultrasonic scattered stannic oxide/graphene nano band mixes,The ultrasonic dispersion of 100W 1-5h, then on machine mixer, stir 1-3h, form pasty state liquid;
4) on suction filtration machine, extract the air in pasty state liquid out, glass plate is placed on film applicator, then utilize wet filmPreparing device is coated with the film of 0.10 ± 0.01mm thickness, then glass plate is placed in the vacuum drying chamber of 60-65 DEG C and vacuumizes;After 10-20min, open vacuum drying chamber, solvent vapo(u)r emitted, then glass plate is dried in 70-80 DEG C after 4-8h,Under room temperature, cool, 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 20-30ml, mass fraction3PO4Solution joins 500ml, circle with magnet rotorIn end flask, then by dense 180-200ml H2SO4Join in round-bottomed flask, under the rotating speed of 300r/min, stir;
2) 1-1.5g multi-walled carbon nano-tubes is joined in the solution of step 1), stir 1-2h, then in 30minBy 6-9gKMnO4Divide 3 steps slowly to join in above-mentioned mixed liquor, then stir 15-30min;
3) by step 2) reaction system move in the oil bath pan of 55-65 DEG C, stirring reaction 2-6 under the rotating speed of 300r/minH, cools to room temperature, then pours into and contains 5-10mlH2O2Frozen water mixed liquor in the 24h that condenses, now solution becomes blackish greenLook, shows to react completely;
4) solution of step 3) is disperseed to 20-30min with 100W power ultrasonic, on poly tetrafluoroethylene, divide by qualityNumber is 10% HCl and the filtration of deionized water cyclic washing, and last 60 DEG C of vacuum drying 24h, obtain described graphene oxide and receiveRice band.
Described polymer is polyester-type thermoplastic polyurethane, polyether-type thermoplastic polyurethane, polyvinyl alcohol, polychlorostyrene secondAny one in alkene, polymethyl methacrylate, polyaniline, polyamide, polystyrene or polyethylene.
Described solvent is any one in N-N dimethyl formamide, oxolane, chloroform, toluene or water.
Tradition utilizes graphene oxide to prepare laminated film, because graphene oxide base part has a lot of defects, thereforeCan not play good iris action to small-molecule substance, and stannic oxide/graphene nano band only have the edge defectiveness of band, itsZone face can well contact with polymeric matrix, therefore, utilizes its laminated film of preparing and utilizes stannic oxide/graphene nano systemStandby laminated film is compared, and has better impermeable effect.
On the other hand, original multi-walled carbon nano-tubes is for strengthening polymer composites DeGrain, this be becauseMulti-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 banded structure,Because the two sides of stannic oxide/graphene nano band can well contact with polymeric matrix, contact area significantly increases, therebyCan obviously strengthen the performance of thin polymer film.
The invention has the advantages that:
(1) CNT has been realized large-scale industrial production both at home and abroad at present, makes the preparation of stannic oxide/graphene nano bandAlso be dirt cheap, meanwhile, the present invention only needs the seldom stannic oxide/graphene nano band of amount just can prepare barrier property and powerThe laminated film of learning excellent performance, makes it with low cost, and can be applied in widely and intercept the field of having relatively high expectations, and its preparationTechnique is simple, and 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 have certain thoroughlyBright property, can be applied in the fields such as food, medicine packaging and electronic product surface encapsulation material widely.
Brief description of the drawings
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 many wallsCNT, 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 many wallsCNT, 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.
Detailed description of the invention
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to following realityExecute example.
The preparation of stannic oxide/graphene nano band comprises the following steps:
1) H that is 85.8% by 20ml, mass fraction3PO4Solution joins 500ml, burns with the round bottom of magnet rotorIn bottle, then by dense 200ml H2SO4Join in round-bottomed flask, under the rotating speed of 300r/min, stir;
2) 1g multi-walled carbon nano-tubes is joined in the solution of step 1), stir 2h, then in 30min by 6gKMnO4Divide 3 steps slowly to join in above-mentioned mixed liquor, then stir 20min;
3) by step 2) reaction system move in the oil bath pan of 55 DEG C, under the rotating speed of 300r/min, stirring reaction 2h, putsCool to room temperature, then pour into and contain 5mlH2O2Frozen water mixed liquor in the 24h that condenses, now solution becomes blackish greenly, shows anti-Should be complete;
4) solution of step 3) is disperseed to 30min with 100W power ultrasonic, on poly tetrafluoroethylene, use mass fractionBe that 10% HCl and deionized water cyclic washing filter, last 60 DEG C of vacuum drying 24h, obtain described stannic oxide/graphene nanoBand.
Fig. 2 is the SEM figure of multi-walled carbon nano-tubes and prepared stannic oxide/graphene nano band, and Fig. 3 is multi-walled carbon nano-tubesTEM figure with prepared stannic oxide/graphene nano band.
Fig. 4 is the Raman comparison diagram of multi-walled carbon nano-tubes and prepared stannic oxide/graphene nano band, and in Fig. 4, many walls carbon is receivedMitron is at 1317cm-1And 1594cm-1Represent D and G peak, obtain the D peak 1326cm of stannic oxide/graphene nano band through cutting-1With G peak 1594cm-1With respect to the peak shape grow of multi-walled carbon nano-tubes, broaden, show that distortion of lattice and fault of construction increase, cardBright 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, and in Fig. 5, many walls carbon is receivedMitron locates to occur strong diffraction maximum and presents sharp-pointed shape in 2 θ=26.26 °, by Bragg equation can many walls carbon is receivedThe interlamellar spacing of mitron is 0.34nm. Stannic oxide/graphene nano band locates to occur strong diffraction maximum in 2 θ=9.06 °, corresponding interlayerApart from being 0.98nm, show that multi-walled carbon nano-tubes is successfully longitudinally cut into stannic oxide/graphene nano band; It is in 2 θ=26.26 °Place's peak shape is milder, 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, Fig. 6 multi-wall carbon nano-tubePipe is at 1043cm-1There is the Weak Absorption peak of C-OH at place, at 1580cm-1There is the characteristic absorption peak of C=C at place. Graphene oxide is receivedRice band is at 1225cm-1With 1725cm-1There is new absworption peak in place, corresponding C=O and C-O-C respectively, 3395cm-1Place is O-HFlexible absworption peak, 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) 15g polyester-type thermoplastic polyurethane is dissolved in 40mlN-N dimethyl formamide, the air blast of 80 DEG CSwelling 12h in drying box;
2) 0.045g stannic oxide/graphene nano band is dissolved in the N-N dimethyl formamide of 10ml to ultrasonic point of 100WLoose 20min;
3) by polymer solution and the step 2 of step 1)) ultrasonic scattered stannic oxide/graphene nano band mixes,The ultrasonic dispersion of 100W 1h, then on machine mixer, stir 3h, 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 sky in pasty state liquidGas, until do not have bubble in volumetric flask; Glass plate is placed on film applicator, then utilizes wet film preparing device to be coated with 0.09mmThe film of thickness, is then placed on glass plate in the vacuum drying chamber of 60 DEG C and vacuumizes; After 10min, open vacuum drying chamber, willSolvent vapo(u)r is emitted, and then glass plate after dry 8h, is cooled under room temperature in 70 DEG C, and film is taken off, and obtains described oxidationGraphene nanobelt-polymer composite film.
Embodiment 2
The preparation of stannic oxide/graphene nano band/polymer composite film, comprises the following steps:
1) 15g polyether-type thermoplastic polyurethane is dissolved in 60ml oxolane, in the air dry oven of 80 DEG CSwelling 12h;
2) 0.075g stannic oxide/graphene nano band is dissolved in the oxolane of 10ml to the ultrasonic dispersion 20 of 100Wmin；
3) by polymer solution and the step 2 of step 1)) ultrasonic scattered stannic oxide/graphene nano band mixes,The ultrasonic dispersion of 100W 3h, then on machine mixer, stir 2h, 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 sky in pasty state liquidGas, until do not have bubble in volumetric flask; Glass plate is placed on film applicator, then utilizes wet film preparing device to be coated with 0.09The film of mm thickness, is then placed on glass plate in the vacuum drying chamber of 62 DEG C and vacuumizes; After 15min, open vacuum drying chamber,Solvent vapo(u)r is emitted, then glass plate after dry 5h, is cooled under room temperature in 75 DEG C, film is taken off, obtain described oxygenFunctionalized graphene nanobelt-polymer composite film.
Embodiment 3
Do not add graphene oxide nanobelt, it is thin that all the other prepare pure polyester-type thermoplastic polyurethane according to the condition of embodiment 1Film, as a comparison experimental group 1.
Embodiment 4
Do not add graphene oxide nanobelt, it is thin that all the other prepare pure polyether-type thermoplastic polyurethane according to the condition of embodiment 2Film, as a comparison experimental group 2.
Embodiment 5
Step 2) 0.045g graphene oxide is dissolved in the N-N dimethyl formamide of 10ml to the ultrasonic dispersion of 100W20min; All the other prepare graphene oxide/polyester-type thermoplastic polyurethane laminated film according to the condition of embodiment 1, as a comparisonExperimental group 3.
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 sampleFor area 50cm2Disk, measuring accuracy: 0.01cc/m2.day.0.1MPa, vacuum: < 10Pa, temperature control mode adopts halfConductor bidirectional high-efficiency temperature control, finally gets the mean value of three sample OTR oxygen transmission rates 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, compared with simple thin polymer film, stannic oxide/graphene nano prepared by the present inventionThe OTR oxygen transmission rate of band/polymer composite film is lower, and mechanical property is better; And in the situation that raw material consumption is equal, oxidationThe barrier property of graphene nanobelt/polymer composite film is also better than graphene oxide/polymer composite film. Therefore, warpTest shows the functional of stannic oxide/graphene nano band/polymer composite film of the present invention, is applicable to intercept have relatively high expectationsField.
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 withModify, all should belong to covering scope of the present invention.
Claims (3)
1. a preparation method for stannic oxide/graphene nano band/polymer composite film, is characterized in that: by multi-walled carbon nano-tubesUtilize the method for oxidation longitudinally to cut into the stannic oxide/graphene nano band of banded structure, then adopt solution manufacturing process to be oxidizedGraphene nanobelt and polymer are compounded to form described film;
It specifically comprises the steps:
1) by after polymer dissolution is in solvent, swelling 12h in the air dry oven of 80-100 DEG C;
2) stannic oxide/graphene nano band is dissolved in solvent to the ultrasonic dispersion of 100W 20-30min;
3) by polymer solution and the step 2 of step 1)) ultrasonic scattered stannic oxide/graphene nano band mixes, 100WUltrasonic dispersion 1-5h, then on machine mixer, stir 1-3h, form pasty state liquid;
4) on suction filtration machine, extract the air in pasty state liquid out, glass plate is placed on film applicator, then utilize wet film preparationDevice is coated with the film of 0.10 ± 0.01mm thickness, then glass plate is placed in the vacuum drying chamber of 60-65 DEG C and vacuumizes, to goDesolventize; Then glass plate after dry 4-8h, is cooled under room temperature in 70-80 DEG C, film is taken off, obtain described oxidationGraphene nanobelt/polymer composite film;
The preparation method of described stannic oxide/graphene nano band comprises the following steps:
1) H that is 85.8% by mass fraction3PO4Solution joins in the round-bottomed flask with magnet rotor, then by dense H2SO4Join in round-bottomed flask, under the rotating speed of 300r/min, stir;
2) multi-walled carbon nano-tubes is joined in the solution of step 1), stir 1-2h, then by KMnO4Slowly join above-mentioned mixedClose in liquid, then stir 15-30min;
3) by step 2) reaction system move in the oil bath pan of 55-65 DEG C, stirring reaction 2-6h under the rotating speed of 300r/min,Cool to room temperature, then pour into and contain H2O2Frozen water mixed liquor in the 24h that condenses;
4) solution of step 3) is disperseed to 20-30min with 100W power ultrasonic, on poly tetrafluoroethylene, with mass fraction be10% HCl and deionized water cyclic washing filter, and last 60 DEG C of vacuum drying 24h, obtain described stannic oxide/graphene nanoBand.
2. the preparation method of stannic oxide/graphene nano band/polymer composite film according to claim 1, is characterized in that:Described polymer is polyester-type thermoplastic polyurethane, polyether-type thermoplastic polyurethane, polyvinyl alcohol, polyvinyl chloride, poly-methylAny one in methyl acrylate, polyaniline, polyamide, polystyrene or polyethylene.
3. the preparation method of stannic oxide/graphene nano band/polymer composite film according to claim 1, is characterized in that:Described solvent is any one in N-N dimethyl formamide, oxolane, chloroform, toluene or water.
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| PCT/CN2015/071165 WO2016008290A1 (en) | 2014-07-18 | 2015-01-21 | Oxidized graphene nano-ribbon/polymer composite film and preparation method therefor |
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| CN104072979B (en) * | 2014-07-18 | 2016-05-04 | 福州大学 | A kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof |
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| CN104448366B (en) * | 2014-12-17 | 2017-09-22 | 福州大学 | A kind of pipe lining high barrier TPU film and preparation method thereof |
| CN107530732B (en) * | 2015-01-14 | 2021-02-05 | 日东电工株式会社 | Graphene oxide barrier film |
| CN107189431A (en) * | 2015-04-23 | 2017-09-22 | 天津大学 | Polyimides anisotropic material |
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| US20110223405A1 (en) * | 2005-11-18 | 2011-09-15 | Northwestern University | Composite polymer film with graphene nanosheets as highly effective barrier property enhancers |
| KR101209293B1 (en) * | 2010-09-06 | 2012-12-06 | 동아대학교 산학협력단 | Gas barrier transparent polymer composite films |
| CN102115566A (en) * | 2011-01-06 | 2011-07-06 | 西安理工大学 | Preparation method for graphene oxide with high barrier property and polymer nanocomposite film |
| CN102604137B (en) * | 2012-03-12 | 2013-06-05 | 烟台大学 | Method for preparing anti-aging high-transparent polyurethane and graphene oxide composite microporous membrane material |
| CN102634106B (en) * | 2012-04-12 | 2014-02-19 | 上海交通大学 | Preparation method of graphene oxide nanobelt/polar rubber composite material |
| CN102827386B (en) * | 2012-08-21 | 2015-02-04 | 江苏大学 | Preparation method of polyether-ether-ketone/graphene oxide nano-composite film |
| CN103265714B (en) * | 2013-05-20 | 2015-04-22 | 西安理工大学 | Polyvinyl alcohol/graphene oxide composite film preparation method |
| CN103627139B (en) * | 2013-09-25 | 2015-10-28 | 杭州师范大学 | A kind of preparation method of functional graphene oxide/epoxy resin nano composites |
| CN104072979B (en) * | 2014-07-18 | 2016-05-04 | 福州大学 | A kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof |
| CN104212053A (en) * | 2014-09-18 | 2014-12-17 | 福州大学 | Waterproof and oxygen-insulating sealing film as well as preparation method and application thereof |
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