CN106335235B - A kind of graphene gas barrier stacking film and preparation method thereof - Google Patents
A kind of graphene gas barrier stacking film and preparation method thereof Download PDFInfo
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- CN106335235B CN106335235B CN201610698156.0A CN201610698156A CN106335235B CN 106335235 B CN106335235 B CN 106335235B CN 201610698156 A CN201610698156 A CN 201610698156A CN 106335235 B CN106335235 B CN 106335235B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract
A kind of graphene gas barrier stacking film and preparation method thereof, belong to field of polymer composite material, including at least one lamination unit being stacked, each lamination unit includes the hydrogen bond receptor organic layer, graphene layer and hydrogen bond donor organic layer being successively disposed adjacent, hydrogen bond is formed between hydrogen bond receptor organic layer and hydrogen bond donor organic layer, the hydrogen bond receptor organic layer of adjacent lamination unit is adjacent with hydrogen bond donor organic layer.Preparation method is that the opposite both side surface of graphene layer is respectively set to hydrogen bond receptor organic layer and hydrogen bond donor organic layer formation lamination unit, at least one lamination unit is stacked, and the hydrogen bond receptor organic layer of adjacent lamination unit is adjacent with hydrogen bond donor organic layer.The barrier property that film is laminated in this graphene gas barrier is good, and preparation is simple.
Description
Technical field
The present invention relates to field of polymer composite material, and in particular to a kind of graphene gas barrier stacking film and its system
Preparation Method.
Background technique
Separating polymer has become more and more important in polymeric food packaging, Key works Drug packing, industrial application, very
It is extremely also widely used in terms of electronic equipment, such as the application in terms of organic light emitting display (OLED) encapsulating material.
Graphene is to be constituted by one layer with the periodically closelypacked carbon atom of benzene ring structure (i.e. hexagonal honeycomb structure)
A kind of two-dimentional carbon material, with a thickness of 0.335nm, the thickness of only one single layer of carbon atom.Due to the special structure of graphene
Excellent barrier property, including the smallest helium of molecular diameter are made it have, therefore, graphene is in OLED, flexible solar electricity
There is potential extensive use in the fields such as pond, military project.But due to the limitation of current graphene growth and transfer techniques, graphene growth
There can be many crystal boundaries in the process, will appear defect, fold or breakage in substrate transfer process, therefore, in the crystalline substance of graphene
Boundary, defect and breakage provide path for passing freely through for gas, greatly reduce the barrier property of graphene, existing skill
In art, the graphene barrier film of preparation needs to shift graphene more than ten times, shifts every time to obtain higher barrier property
Graphene at 1-5 layers, production process is complicated, higher cost.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene gas barriers, and film, the barrier property of this graphene barrier film is laminated
It is greatly improved.
Another object of the present invention is to provide a kind of preparation method of graphene gas barrier stacking film, this preparation methods
Simply, while barrier film production process is shortened.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of graphene gas barrier stacking film, including at least one lamination unit being stacked, often
A lamination unit includes the hydrogen bond receptor organic layer, graphene layer and hydrogen bond donor organic layer being successively disposed adjacent, hydrogen bond receptor
Hydrogen bond is formed between organic layer and hydrogen bond donor organic layer, hydrogen bond receptor organic layer and the hydrogen bond donor of adjacent lamination unit have
Machine layer is adjacent.
The present invention proposes a kind of preparation method of graphene gas barrier stacking film comprising: by the opposite of graphene layer
Both side surface hydrogen bond receptor organic layer and hydrogen bond donor organic layer be respectively set form lamination unit, at least one stacking is single
Member is stacked, and the hydrogen bond receptor organic layer of adjacent lamination unit is adjacent with hydrogen bond donor organic layer.
Graphene gas barrier stacking film of the embodiment of the present invention and preparation method thereof, passes through hydrogen bond receptor organic layer and hydrogen
Hydrogen bond is formed between key donor organic layer can carry out the breakage and defect that graphene occurs in growth and transfer process
Effective repairing, effectively shortens the microcosmic distance between graphene and graphene, reduces the probability of gas transverse leakage, improves
The barrier property of graphene reduces the cost of graphene barrier film while shortening barrier film production process.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is that the structural schematic diagram of film is laminated in the graphene gas barrier of the embodiment of the present invention 1；
Fig. 2 is that the structural schematic diagram of film is laminated in the graphene gas barrier of the embodiment of the present invention 3；
Fig. 3 is that the structural schematic diagram of film is laminated in the graphene gas barrier of the embodiment of the present invention 4；
Fig. 4 is that the structural schematic diagram of film is laminated in the graphene gas barrier of the embodiment of the present invention 5；
Fig. 5 is that the structural schematic diagram of film is laminated in the graphene gas barrier of the embodiment of the present invention 6；
Fig. 6 is that the structural schematic diagram of film is laminated in the graphene gas barrier of the embodiment of the present invention 7.
Appended drawing reference is summarized as follows: 100- graphene gas barrier stacking film, 110- basal layer, 200- hierarchical element,
201- hydrogen bond receptor organic layer, 202- graphene layer, 203- hydrogen bond donor organic layer, the first hierarchical element of 210-, 220- second
Hierarchical element, 300- protective film.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Graphene gas barrier stacking film of the embodiment of the present invention and preparation method thereof is specifically described below.
The present invention provides a kind of graphene gas barrier stacking film, including at least one lamination unit being stacked, example
It can also be successively lamination unit-lamination unit, each lamination unit from top to bottom if product structure can be lamination unit
Including the hydrogen bond receptor organic layer, graphene layer and hydrogen bond donor organic layer being successively disposed adjacent, hydrogen bond receptor organic layer and hydrogen
Hydrogen bond is formed between key donor organic layer, the hydrogen bond receptor organic layer of adjacent lamination unit is adjacent with hydrogen bond donor organic layer,
Such as product structure successively can be hydrogen bond donor organic layer-graphene layer-hydrogen bond receptor organic layer-hydrogen bond from top to bottom
Donor organic layer-graphene layer-hydrogen bond receptor organic layer, hydrogen bond receptor organic layer can by epoxy resin, vinylacetate,
In polyvinylidene fluoride resin, polyurethane, acrylate, methacrylate, modification acrylate and urethane acrylate
One or more are made, it is preferable that and hydrogen bond receptor organic layer is made of one kind in urethane acrylate and modification acrylate,
Such as hydrogen bond receptor organic layer is made of epoxy resin, can also be made of polyurethane, it can also be for by acrylate and methyl
The mixture of acrylate is made.Epoxy resin has good physical and chemical performance, has to metal and non-metal material surface
There is excellent adhesion strength；Polyurethane is main chain containing-one quasi polymer of NHCOO-constitutional repeating unit, is had good viscous
Conjunction property；Acrylate is that the general name of the esters of acrylic acid and its homologue has good caking property, water resistance；Methacrylic acid
Ester, modification acrylate and urethane acrylate all have good adhesiveness.
Hydrogen bond donor organic layer can be by polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer, modified second
One or more of alkene-ethenol copolymer is made, such as hydrogen bond donor organic layer is made of polyvinyl alcohol, can also be by
Ethylene-vinyl alcohol copolymer is made, and can also be made of the mixture of the pure and mild ethylene-vinyl alcohol copolymer of modified poly ethylene,
Preferably, hydrogen bond donor organic layer is by polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer, ethene improved-second
One of enol copolymer is made.Polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer, ethene improved-second
Enol copolymer can form the interaction of hydrogen bond with hydrogen bond receptor organic layer, and having the function of vapour lock, there are also preferable bondings simultaneously
Property.
Hydrogen bond donor organic layer can also be by polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer and modification
At least one of ethylene-vinyl alcohol copolymer and the mixture of polyvinylidene chloride are made, polyvinylidene chloride barrier property compared with
It is good, polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer and modified ethylene vinyl alcohol copolymer any one with
Hydrogen bond receptor organic layer can all generate the interaction of hydrogen bond, therefore be mixed to form hydrogen bond donor organic layer with polyvinylidene chloride
Its barrier property is enhanced, such as hydrogen bond donor organic layer is made of the mixture of polyvinyl alcohol and polyvinylidene chloride, it can also
It is made with the mixture by modified ethylene vinyl alcohol copolymer and polyvinylidene chloride, it can also be by ethylene vinyl alcohol copolymer
The mixture of object, modified ethylene vinyl alcohol copolymer and polyvinylidene chloride is made.
Hydrogen bond donor organic layer and the organic interlayer of hydrogen bond receptor can form hydrogen bond, and hydrogen bond receptor organic layer has with hydrogen bond donor
Machine layer forms hydrogen bond with the very big atom containing lone electron pair of electronegativity by the proton on highly polar key, and hydrogen bond is between change
A kind of intermolecular force between key and Van der Waals force is learned, since graphene during the growth process can be defective, in graphene
Fold and damaged appearance are had in transfer process, these can all influence the barrier property of graphene, and hydrogen bond donor organic layer is being repaired
While mending graphene defect, by the defect on graphene with hydrogen bond receptor organic layer by the interaction of hydrogen bond, effectively
Ground reduces graphene interfloor distance, reduces the probability of gas transverse leakage, enhances its barrier property.
Graphene can be grown by chemical vapour deposition technique (CVD) and be obtained, and CVD method is by one or more gaseous materials
It imported into a reaction chamber to chemically react, the method for generating the new material of one kind and being deposited on substrate surface, but not only
It is limited to this, can also be grown and be obtained by other methods, such as oxidation-reduction method.Graphene is by one layer with benzene ring structure (i.e. six
Angular honeycomb structure) a kind of periodical two-dimentional carbon material for constituting of closelypacked carbon atom, due to the special structure of graphene
Make it have excellent barrier property.Every layer of graphene layer may include one or more layers graphene sample layer, that is to say every layer
Graphene layer can be formed by the graphene sample layer heap repeatedly shifted is folded, and preferred graphene sample layer is 1~5 layer, adjacent
Graphene sample layer by heat discharge adhesive tape transfer.
Film, which is laminated, in graphene gas barrier to include basal layer, and at least side of basal layer is provided at least one layer
Folded unit, such as product structure are followed successively by least one lamination unit-basal layer from top to bottom, can also be at least one layer
The hydrogen bond receptor organic layer of folded at least one lamination unit of unit-basal layer-, basal layer and adjacent lamination unit bonds,
Which adds the binding forces of graphene layer and basal layer, reduce the micro interface distance between graphene layer and basal layer,
Reduce the probability of gas transverse leakage.Preferably, basal layer is organic film, and organic film includes polyethylene film, polypropylene
In film, polyester film, polystyrene film, polyamide film, polycarbonate membrane and polyvinyl acetal resin film
One kind, above-mentioned film is light, flexible, easy processing, air-tightness are good, can effectively stop oxygen, vapor etc..Such as substrate
Layer can be polyethylene film, is also possible to polyester film, can also be polypropylene film.
It can also include protective film that film, which is laminated, in graphene gas barrier, and the outermost hydrogen bond of at least one lamination unit supplies
The surface far from graphene layer adjacent thereto of body is bonded with protective film, such as product structure is followed successively by protection from top to bottom
At least one lamination unit of film-, or at least one lamination unit-basal layer of protective film-can also be protection
At least one lamination unit-protective film of at least one lamination unit-basal layer-of film-.Preferably, protective film can be poly-
Ethylene protective film, polypropylene protective film, polyester protective film, polystyrene protective film, polyamide protective film, polycarbonate protective film
With polyvinyl acetal resin protective film etc..
What graphene gas barrier stacking film provided by the invention graphene can occur in growth and transfer process
Damaged and defect is effectively repaired, and the microcosmic distance between graphene and graphene is effectively shortened, and reduces gas transverse
The probability of leakage improves the barrier property of graphene.
The present invention also provides the preparation methods of above-mentioned graphene gas barrier stacking film, by the opposite two sides of graphene layer
Hydrogen bond receptor organic layer is respectively set in surface and hydrogen bond donor organic layer forms lamination unit, at least one lamination unit is laminated
Setting, and the hydrogen bond receptor organic layer of adjacent lamination unit is adjacent with hydrogen bond donor organic layer.
Such as can be prepared in the following ways, it is organic that hydrogen bond receptor is smeared first on graphene sample layer side
Layer, it is preferable that the mode of smearing can be one in spin coating, spraying, blade coating, cup painting, curtain coating, dip-coating, flow coat, cutter painting or bar painting
Kind.Wherein smear condition at normal temperature, smearing pressure is 0.1-10kg, and preferably 1-5kg, coating layer thickness is 15-300 μm, preferably
25-188μm.Then the copper on graphene is eroded, it is preferable that use FeCl3、HNO3、(NH4)2S2O8Solution is corroded.So
Hydrogen bond donor organic layer is smeared in graphene-structured layer other side afterwards, forms a lamination unit, it is preferable that the side of smearing
Formula can be one kind in spin coating, spraying, cup painting, curtain coating, dip-coating or flow coat, and coating thickness is 15-300 μm, preferably 25-
188μm.At least one lamination unit can also be stacked, the hydrogen bond receptor organic layer and hydrogen bond donor of adjacent lamination unit
Organic layer is adjacent.The side of the hydrogen bond receptor organic layer side of at least one above-mentioned lamination unit and basal layer can also be glued
It closes；Above-mentioned at least one lamination unit can also be set in basal layer two sides, the hydrogen bond receptor organic layer side of lamination unit with
Basal layer bonding, wherein hydrogen bond receptor organic layer and the coating layer thickness of hydrogen bond donor organic layer are preferably when being provided with basal layer
2-100 μm, more preferably 2-10 μm；Protective film can also be covered in the hydrogen bond donor organic layer side of at least one lamination unit,
It is greater than 50g/25mm preferably under the viscosity room temperature of protective film.
The preparation method reduces the cost of graphene barrier film while shortening barrier film production process.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Graphene sample is grown using CVD method, smears epoxy resin by the way of spraying in graphene sample side,
The condition of spraying is to smear pressure 1kg, and coating layer thickness is 15 μm, then passes through FeCl3Solution corrosion falls in graphene sample
Copper smears polyvinyl alcohol on the graphene sample other side by the way of spin coating, obtains graphene gas barrier stacking film,
The condition of middle spin coating is that coating layer thickness is 15 μm.The structure such as Fig. 1 for the graphene gas barrier stacking film 100 that the present embodiment obtains
It is shown, it is followed successively by hydrogen bond donor organic layer 203, graphene layer 202 and hydrogen bond receptor organic layer 201 from top to bottom.
Embodiment 2
Graphene sample is grown using CVD method, smears vinyl acetate by the way of spraying in graphene sample side
Ester, the condition of spraying are to smear pressure 1kg, and coating layer thickness is 188 μm, then passes through FeCl3Solution corrosion falls graphene sample
On copper, the mixture of polyvinyl alcohol and polyvinylidene chloride is smeared by the way of spin coating on the graphene sample other side,
Graphene gas barrier stacking film is obtained, it is 188 μm that wherein the condition of spin coating, which is coating layer thickness, the graphite obtained with embodiment 1
The structure that film is laminated in alkene gas barrier is identical.
Embodiment 3
Graphene sample is grown using CVD method, polyurethane is smeared by the way of blade coating in graphene sample side, scrapes
The condition of painting is to smear pressure 5kg, and coating layer thickness is 100 μm, then passes through (NH4)2S2O8Solution corrosion falls on graphene
Copper is transferred on polyethylene film by polyurethane, and second is smeared by the way of dip-coating on the graphene sample other side
Alkene-ethenol copolymer obtains graphene gas barrier stacking film, and it is 100 μm that wherein the condition of dip-coating, which is coating layer thickness,.This
Embodiment obtains the structure of graphene gas barrier stacking film 100 as shown in Fig. 2, being followed successively by hydrogen bond donor organic layer from top to bottom
203, graphene layer 202, hydrogen bond receptor organic layer 201 and basal layer 110.
Embodiment 4
Graphene sample is grown using CVD method, smears acrylate by the way of cup painting in graphene sample side,
The condition that cup applies is to smear pressure 10kg, and coating layer thickness is 300 μm, then passes through (NH4)2S2O8Solution corrosion falls on graphene
Copper, modified ethylene vinyl alcohol copolymer is smeared by the way of flow coat in the graphene sample other side, the condition of flow coat is
Coating layer thickness is 300 μm, and the polystyrene that viscosity is 80g/25mm is finally covered on modified ethylene vinyl alcohol copolymer and is protected
Cuticula protective film obtains graphene gas barrier stacking film, and the present embodiment obtains the structure of graphene gas barrier stacking film 100
As shown in figure 3, it is organic to be followed successively by protective film 300, hydrogen bond donor organic layer 203, graphene layer 202 and hydrogen bond receptor from top to bottom
Layer 201.
Embodiment 5
Graphene sample is grown using CVD method, smears first by the way of curtain coating in first layer graphene sample side
Base acrylate, the condition of curtain coating are to smear pressure 1kg, and coating layer thickness is 25 μm, then passes through FeCl3Solution corrosion falls graphite
Copper on alkene smears polyvinyl alcohol and ethene improved-ethylene on the first layer graphene sample other side by the way of spin coating
The mixture of alcohol copolymer, the condition of spin coating are that coating layer thickness is 25 μm, then in second layer graphene sample side curtain coating
Mode smear methacrylate, the condition of curtain coating is to smear pressure 1kg, and coating layer thickness is 25 μm, then passes through FeCl3It is molten
Corrosion falls the copper in second layer graphene sample, passes through methacrylic acid transesterify second layer graphene sample to polyvinyl alcohol
On the mixture of modified ethylene vinyl alcohol copolymer, on the other side of second layer graphene sample by the way of spin coating
The mixture for smearing polyvinyl alcohol and modified ethylene vinyl alcohol copolymer obtains graphene gas barrier stacking film, the item of spin coating
Part is that coating layer thickness is 25 μm.The structure for the graphene gas barrier stacking film 100 that the present embodiment obtains is as shown in figure 4, from upper
The first hierarchical element 210 and the second hierarchical element 220 are followed successively by under.
Embodiment 6
Graphene sample is grown using CVD method, smears modified propylene by the way of bar painting in graphene sample side
Acid esters, the condition that bar applies are to smear pressure 0.1kg, and coating layer thickness is 2 μm, then passes through HNO3Solution corrosion falls graphene sample
On copper, pass through the graphene in modified acroleic acid transesterify graphene sample to polyester film two sides, in polyester film two sides
Modified polyvinylalcohol is smeared on the other side of sample by the way of curtain coating, the condition of curtain coating is that coating layer thickness is 2 μm.This implementation
The structure for the graphene gas barrier stacking film that example obtains as shown in figure 5, be followed successively by the first hierarchical element 210, base from top to bottom
Bottom 110 and the second hierarchical element 220.
Embodiment 7
Graphene sample is grown using CVD method, smears modified propylene by the way of spin coating in graphene sample side
Acid esters, the condition of spin coating are to smear pressure 0.1kg, and coating layer thickness is 10 μm, then passes through HNO3Solution corrosion falls on graphene
Copper, by being adopted on the graphene sample other side in modified acroleic acid transesterify graphene sample to polypropylene film side
The mixture of modified polyvinylalcohol and polyvinylidene chloride is smeared with the mode of spraying, the condition of spraying is that coating layer thickness is 10 μ
M is finally covered with the polyvinyl alcohol contracting second that viscosity is 60g/25mm on the mixture of modified polyvinylalcohol and polyvinylidene chloride
Urea formaldehyde protective film obtains graphene gas barrier stacking film, the structure for the graphene gas barrier stacking film that the present embodiment obtains
As shown in fig. 6, being successively hydrogen bond receptor organic layer 201, graphene layer 202, hydrogen bond donor organic layer on basal layer 110
203 and protective film 300, graphene barrier film 100 is formed, hydrogen bond receptor organic layer 201, graphene layer 202 and hydrogen bond donor have
Machine layer 203 forms hierarchical element 200.
Embodiment 8
Graphene sample is grown using CVD method, smears polyurethane third by the way of flow coat in graphene sample side
The mixture of olefin(e) acid ester and modification acrylate, the condition of flow coat are to smear pressure 0.1kg, and coating layer thickness is 5 μm, is then passed through
HNO3Solution corrosion falls the copper on graphene, shifts graphene by the mixture of urethane acrylate and modification acrylate
On sample to polystyrene film side, modified polyvinylalcohol is smeared by the way of curtain coating on the other side of graphene sample
With the mixture of polyvinylidene chloride, the condition of curtain coating is that coating layer thickness is 5 μm, finally modified polyvinylalcohol and is gathering inclined dichloro
It is covered with the polypropylene protective film that viscosity is 80g/25mm on the mixture of ethylene and obtains graphene barrier film, is obtained with embodiment 7
Graphene gas barrier stacking film structure it is identical.
Embodiment 9
Graphene sample is grown using CVD method, smears polyvinylidene fluoride by the way of cutter painting in graphene sample side
Olefine resin, the condition of cutter painting are to smear pressure 0.1kg, and coating layer thickness is 100 μm, then passes through HNO3Solution corrosion falls graphene
On copper, by polyvinylidene fluoride resin shift graphene sample to polyvinyl acetal resin film side on, in graphite
The mixture of ethylene-vinyl alcohol copolymer and polyvinylidene chloride, the item of curtain coating are smeared on the alkene other side by the way of curtain coating
Part is that coating layer thickness is 100 μm, is finally covered with viscosity on the mixture of ethylene-vinyl alcohol copolymer and polyvinylidene chloride
Graphene gas barrier stacking film is obtained for the polyamide protective film of 80g/25mm, the graphene gas resistance obtained with embodiment 7
It is identical every the structure of stacked film.
Embodiment 10
Graphene sample is grown using CVD method, smears polyurethane third by the way of spin coating in graphene sample side
Olefin(e) acid ester, the condition of spin coating are to smear pressure 0.1kg, and coating layer thickness is 10 μm, then passes through HNO3Solution corrosion falls graphene
On copper, by urethane acrylate shift graphene sample to polyamide film side on, in the graphene sample other side
Upper to smear modified polyvinylalcohol by the way of spraying, the condition of spraying is that coating layer thickness is 10 μm, finally in modified poly ethylene
It is covered with the polycarbonate protective film that viscosity is 60g/25mm on alcohol and obtains graphene gas barrier stacking film, is obtained with embodiment 7
Graphene gas barrier stacking film structure it is identical.
Embodiment 11
Graphene sample is grown using CVD method, smears polyurethane third by the way of spin coating in graphene sample side
The mixture of olefin(e) acid ester and modification acrylate, the condition of spin coating are to smear pressure 0.1kg, and coating layer thickness is 50 μm, is then led to
Cross HNO3Solution corrosion falls the copper on graphene, shifts graphite by the mixture of urethane acrylate and modification acrylate
On alkene sample to polyamide film side, ethene improved-ethylene is smeared by the way of spraying on the graphene sample other side
The mixture of alcohol copolymer and polyvinylidene chloride, the condition of spraying is that coating layer thickness is 50 μm, finally in ethene improved-second
It is covered with the polycarbonate protective film that viscosity is 60g/25mm on the mixture of enol copolymer and polyvinylidene chloride and obtains graphite
Film is laminated in alkene gas barrier, identical as the graphene gas barrier stacking structure of film that embodiment 7 obtains.
Embodiment 12
Graphene is grown using CVD method, smears modified acroleic acid by the way of dip-coating in first layer graphene side
Ester, the condition of dip-coating are to smear pressure 0.1kg, and coating layer thickness is 10 μm, then passes through HNO3Solution corrosion falls first layer graphite
Copper on alkene, by discharging glue by heat on modified acroleic acid transesterify first layer graphene to polycarbonate membrane side
On band transfer second layer graphene to first layer graphene sample, smeared by the way of spraying in second layer graphene sample
Modified polyvinylalcohol, the condition of spraying are that coating layer thickness is 10 μm, and it is 60g/25mm's that viscosity is finally covered on smearing is modified
Polyester protective film obtains graphene gas barrier stacking film, the structure of the graphene gas barrier stacking film obtained with embodiment 7
It is identical.
Embodiment 13
Graphene is grown using CVD method, smears modified acroleic acid by the way of spin coating in first layer graphene side
Ester, the condition of spin coating are to smear pressure 0.1kg, and coating layer thickness is 2 μm, then passes through HNO3Solution corrosion falls first layer graphene
On copper turn discharging adhesive tape by heat by modified acroleic acid transesterify first layer graphene to polyamide film side
It moves on second layer graphene to first layer graphene, adhesive tape is then discharged by heat in second layer graphene sample and shifts third
Layer graphene discharges adhesive tape by heat on third layer graphene and shifts the 4th layer of graphene, pass through on the 4th layer of graphene
Heat release adhesive tape shifts layer 5 graphene, smears modified polyvinylalcohol by the way of spraying on layer 5 graphene, sprays
The condition of painting is that coating layer thickness is 2 μm, and the polyethylene protective film that viscosity is 60g/25mm is finally covered on modified polyvinylalcohol
Graphene barrier film is obtained, it is identical as the graphene gas barrier stacking structure of film that embodiment 7 obtains.
The test that the product of the present embodiment 1-13 and control sample are carried out resistance helium, hinder oxygen, tests the principle according to pressure differential method
It is tested, sample is cut into the disk that diameter is 97mm and is tightened after print is pasted onto instrument cavity of resorption with sealant
Chamber vacuumizes and starts to test greater than after 12h, starting to be passed through test gas, in test process, guarantees that the pressure of epicoele is
0.1MPa.Control group A product sequentially consists of polystyrene film, one layer of graphene sample, polyvinyl alcohol and polyethylene
Protective film is compared with the product of the present embodiment 1-13 without hydrogen bond receptor organic layer, and control group B product sequentially consists of polyphenyl
Vinyl film, modification acrylate, one layer of graphene sample and polyethylene protective film compare nothing with the product of the present embodiment 1-13
Hydrogen bond donor organic layer, control group C product sequentially consist of polystyrene film, modification acrylate, one layer of graphene
Sample, polyvinylidene chloride and polyethylene protective film, do not form hydrogen bond wherein between modification acrylate and polyvinylidene chloride,
Test data is as follows:
From experimental data as can be seen that the barrier property of the product of embodiment 1-13 has all obtained biggish improvement.
In conclusion the graphene gas barrier stacking film and preparation method thereof of the embodiment of the present invention has by hydrogen bond receptor
Be formed between machine layer and hydrogen bond donor organic layer hydrogen bond can to the breakage that graphene occurs in growth and transfer process and
Defect is effectively repaired, and the microcosmic distance between graphene and graphene is effectively shortened, and reduces gas transverse leakage
Probability, improve the barrier property of graphene, while shortening barrier film production process, reduce graphene barrier film at
This.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (7)
1. film is laminated in a kind of graphene gas barrier, which is characterized in that including at least one lamination unit being stacked, each
The lamination unit includes the hydrogen bond receptor organic layer, graphene layer and hydrogen bond donor organic layer being successively disposed adjacent, the hydrogen
Hydrogen bond, the hydrogen bond receptor of the adjacent lamination unit are formed between key receptor organic layer and the hydrogen bond donor organic layer
Organic layer is adjacent with the hydrogen bond donor organic layer, the hydrogen bond receptor organic layer by epoxy resin, vinylacetate, gather inclined fluorine
One of vinyl, polyurethane, acrylate, methacrylate, modification acrylate and urethane acrylate or
It is several to be made；The hydrogen bond donor organic layer is by polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer, modified second
One or more of alkene-ethenol copolymer is made or the hydrogen bond donor organic layer is by polyvinyl alcohol, modified poly ethylene
The mixing of at least one of alcohol, ethylene-vinyl alcohol copolymer and modified ethylene vinyl alcohol copolymer and polyvinylidene chloride
Object is made.
2. film is laminated in graphene gas barrier according to claim 1, which is characterized in that the graphene gas-barrier layer
Folded film further includes basal layer, separate and its phase of the outermost hydrogen bond receptor organic layer of at least one lamination unit
The surface of the adjacent graphene layer and the basal layer bond.
3. film is laminated in -2 described in any item graphene gas barriers according to claim 1, which is characterized in that the graphene gas
Body obstruct stacked film further include protective film, the outermost hydrogen bond donor organic layer of at least one lamination unit it is remote
Surface and the protective film from the graphene layer adjacent thereto bond.
4. film is laminated in graphene gas barrier according to claim 2, which is characterized in that the basal layer is organic thin
Film, the organic film include polyethylene film, polypropylene film, polyester film, polystyrene film, polyamide film, gather
One of carbonic ester film and polyvinyl acetal resin film.
5. film is laminated in graphene gas barrier according to claim 3, which is characterized in that the protective film includes polyethylene
Protective film, polypropylene protective film, polyester protective film, polystyrene protective film, polyamide protective film, polycarbonate protective film and poly-
One of vinyl acetal resin protective film.
6. the preparation method of graphene gas barrier stacking film according to claim 1, characterized in that it comprises: in
Hydrogen bond receptor organic layer is respectively set in the opposite both side surface of graphene layer and hydrogen bond donor organic layer forms lamination unit, will
At least one described lamination unit is stacked, and the hydrogen bond receptor organic layer of the adjacent lamination unit and the hydrogen bond
Donor organic layer is adjacent.
7. the preparation method of graphene gas barrier stacking film according to claim 6, which is characterized in that each stone
Black alkene layer includes 1~5 layer of graphene sample layer.
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| TWI515102B (en) * | 2014-08-18 | 2016-01-01 | 中原大學 | Transparent gas barrier composite film and its preparation method |
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