CN106335235A - Graphene gas barrier laminated film and preparation method thereof - Google Patents
Graphene gas barrier laminated film and preparation method thereof Download PDFInfo
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- CN106335235A CN106335235A CN201610698156.0A CN201610698156A CN106335235A CN 106335235 A CN106335235 A CN 106335235A CN 201610698156 A CN201610698156 A CN 201610698156A CN 106335235 A CN106335235 A CN 106335235A
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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
The invention discloses a graphene gas barrier laminated film and a preparation method thereof, and belongs to the field of polymer composite materials, the graphene gas barrier laminated film includes at least one stacked unit which is stacked up, each stacked unit includes a hydrogen bond acceptor organic layer, a graphene layer and a hydrogen bond donor organic layer which are sequentially adjacently arranged, hydrogen bonds are formed between the hydrogen bond acceptor organic layer and the hydrogen bond donor organic layer, and the hydrogen bond acceptor organic layers and the hydrogen bond donor organic layers of adjacent stacked units are adjacent. The preparation method is as follows: the hydrogen bond acceptor organic layer and the hydrogen bond donor organic layer are respectively arranged on the surface of opposite two sides of the graphene layer to form the stacked unit, the at least one stacked unit is stacked up, and the hydrogen bond acceptor organic layers and the hydrogen bond donor organic layers of adjacent stacked units are adjacent. The graphene gas barrier laminated film has good barrier property and is simple to prepare.
Description
Technical field
The present invention relates to field of polymer composite material, and it is laminated film and its system particularly to a kind of Graphene gas barrier
Preparation Method.
Background technology
Separating polymer has become more and more important in polymeric food packaging, Key works Drug packing, commercial Application, very
Extremely also it is widely used in terms of electronic equipment, the such as application of OLED (oled) encapsulating material aspect.
Graphene is to be constituted with the periodically closelypacked carbon atom of benzene ring structure (i.e. hexagonal honeycomb structure) by one layer
A kind of two dimension material with carbon element, its thickness be 0.335nm, the thickness of only one individual layer carbon atom.Due to the special structure of Graphene
Make it have excellent barrier property, including the helium that molecular diameter is minimum, therefore, Graphene is in oled, flexible solar electricity
The fields such as pond, military project have potentially extensively applies.But the restriction due to current graphene growth and transfer techniques, graphene growth
During can there are a lot of crystal boundaries, defect, fold or breakage occur in substrate transfer process, therefore, in the crystalline substance of Graphene
Boundary, defect and breakage, are that passing freely through of gas provides path, greatly reduce the barrier property of Graphene, existing skill
In art, the Graphene Obstruct membrane of preparation, in order to obtain higher barrier property, needs transfer Graphene more than ten times, shifts every time
Graphene in 1-5 layer, its production process is complicated, relatively costly.
Content of the invention
It is an object of the invention to provide a kind of Graphene gas barrier is laminated film, the barrier property of this Graphene Obstruct membrane
It is greatly improved.
Another object of the present invention is to providing a kind of Graphene gas barrier to be laminated the preparation method of film, this preparation method
Simply, shorten Obstruct membrane production process simultaneously.
The present invention solves its technical problem and employs the following technical solutions to realize.
The present invention proposes a kind of Graphene gas barrier and is laminated film, including at least one lamination unit being stacked, often
Individual lamination unit includes hydrogen bond receptor organic layer, graphene layer and the hydrogen bond donor organic layer being disposed adjacent successively, hydrogen bond receptor
It is formed with hydrogen bond, hydrogen bond receptor organic layer and the hydrogen bond donor of adjacent lamination unit have between organic layer and hydrogen bond donor organic layer
Machine layer is adjacent.
The present invention proposes the preparation method that a kind of Graphene gas barrier is laminated film, comprising: graphene layer is relative
Both side surface be respectively provided with hydrogen bond receptor organic layer and hydrogen bond donor organic layer and form lamination unit, will be single at least one stacking
Unit 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, by hydrogen bond receptor organic layer and hydrogen
Be formed between key donor organic layer hydrogen bond can to Graphene in growth and transfer process the breakage occurring and defect carry out
Effectively repair, effectively shorten the microcosmic distance between Graphene and Graphene, reduce the probability that gas transverse is revealed, improve
The barrier property of Graphene, while shortening Obstruct membrane production process, reduces the cost of Graphene Obstruct membrane.
Brief description
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below will be attached to use required in embodiment
Figure is briefly described it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, and it is right to be therefore not construed as
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the structural representation of the Graphene gas barrier stacking film of the embodiment of the present invention 1；
Fig. 2 is the structural representation of the Graphene gas barrier stacking film of the embodiment of the present invention 3；
Fig. 3 is the structural representation of the Graphene gas barrier stacking film of the embodiment of the present invention 4；
Fig. 4 is the structural representation of the Graphene gas barrier stacking film of the embodiment of the present invention 5；
Fig. 5 is the structural representation of the Graphene gas barrier stacking film of the embodiment of the present invention 6；
Fig. 6 is the structural representation of the Graphene gas barrier stacking film of the embodiment of the present invention 7.
Reference is summarized as follows: 100- Graphene gas barrier stacking film, 110- basalis, 200- hierarchical element,
201- hydrogen bond receptor organic layer, 202- graphene layer, 203- hydrogen bond donor organic layer, 210- first hierarchical element, 220- second
Hierarchical element, 300- diaphragm.
Specific embodiment
Purpose, technical scheme and advantage for making the embodiment of the present invention are clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.In embodiment, unreceipted actual conditions person, builds according to normal condition or manufacturer
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, being can be by the commercially available conventional product bought and obtain
Product.
It is laminated film and preparation method thereof to the Graphene gas barrier of the embodiment of the present invention below to be specifically described.
The present invention provides a kind of Graphene gas barrier to be laminated film, including at least one lamination unit being stacked, example
If product structure can be lamination unit, can also be lamination unit-lamination unit from top to bottom successively, each lamination unit
Including the hydrogen bond receptor organic layer being disposed adjacent successively, graphene layer and hydrogen bond donor organic layer, hydrogen bond receptor organic layer and hydrogen
It is formed with hydrogen bond, the hydrogen bond receptor organic layer of adjacent lamination unit is adjacent with hydrogen bond donor organic layer between key donor organic layer,
Such as product structure can be hydrogen bond donor organic layer-graphene layer-hydrogen bond receptor organic layer-hydrogen bond from top to bottom successively
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 hydrogen bond receptor organic layer is made up of one kind in urethane acrylate and modification acrylate,
Such as hydrogen bond receptor organic layer is made up of epoxy resin it is also possible to be made up of polyurethane, can also be by acrylate and methyl
The mixture of acrylate is made.Epoxy resin has good physical and chemical performance, to metal and non-metal material surface tool
There is excellent adhesion strength；Polyurethane is that main chain contains the one of nhcoo constitutional repeating unit and birdss of the same feather flock together compound, has good viscous
Conjunction property；Acrylate is that the general name of the esters of acrylic acid and its homologue has good caking property, resistance to water；Methacrylic acid
Ester, modification acrylate and urethane acrylate all have good cohesive.
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 be made up of polyvinyl alcohol it is also possible to by
Ethylene-vinyl alcohol copolymer is made, and can also be made up of the mixture of modified polyvinylalcohol and ethylene-vinyl alcohol copolymer,
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, have vapour lock function and also have preferably bonding simultaneously
Property.
Hydrogen bond donor organic layer can also be by polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer and modification
The mixture of at least one of ethylene-vinyl alcohol copolymer and polyvinylidene chloride is made, and polyvinylidene chloride barrier property is relatively
Good, polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer and modified ethylene vinyl alcohol copolymer any one with
Hydrogen bond receptor organic layer all can produce the interaction of hydrogen bond, be therefore mixed to form hydrogen bond donor organic layer with polyvinylidene chloride
Enhance its barrier property, such as hydrogen bond donor organic layer is made up of the mixture of polyvinyl alcohol and polyvinylidene chloride, also may be used
Made with the mixture by modified ethylene vinyl alcohol copolymer and polyvinylidene chloride, can also be by ethylene vinyl alcohol copolymer
The mixture of thing, 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 and hydrogen bond donor have
Machine layer is very big by the proton on highly polar key and electronegativity, atom formation hydrogen bond containing lone electron pair, and hydrogen bond is between change
Learn a kind of intermolecular force between key and Van der Waals force, because Graphene can be defective in growth course, in Graphene
Fold and damaged appearance is had, these all can affect the barrier property of Graphene, hydrogen bond donor organic layer repairing in transfer process
While mending Graphene defect, by the defect on Graphene and the interaction by hydrogen bond for the hydrogen bond receptor organic layer, effectively
Reduce Graphene interfloor distance, reduce gas transverse leakage probability, enhance its barrier property.
Graphene can be obtained by chemical vapour deposition technique (cvd) growth, and cvd method is by one or more gaseous material
Import to a reaction chamber and chemical reaction occurs, generate a kind of new material the method being deposited on substrate surface, but not only
It is limited to this to obtain it is also possible to be grown by additive method, such as oxidation-reduction method.Graphene is with benzene ring structure (i.e. six by one layer
Angular honeycomb structure) a kind of two dimension material with carbon element that periodically closelypacked carbon atom is constituted, due to the special structure of Graphene
Make it have excellent barrier property.Every layer graphene layer can include one or more layers Graphene sample layer, that is to say every layer
Graphene layer can be formed by the Graphene sample layer stacking repeatedly shifting, and preferred Graphene sample layer is 1～5 layer, adjacent
Graphene sample layer pass through heat release adhesive tape transfer.
Graphene gas barrier stacking film can also include basalis, and at least side of basalis is provided with least one layer
Folded unit, such as product structure are followed successively by least one lamination unit-basalis from top to bottom, can also be at least one layer
Folded unit-basalis-at least one lamination unit, basalis is bonded with the hydrogen bond receptor organic layer of adjacent lamination unit,
Which adds the adhesion of graphene layer and basalis, reduce the micro interface distance between graphene layer and basalis,
Reduce the probability that gas transverse is revealed.Preferably, basalis 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 light weight, pliable and tough, easy processing, air-tightness be good, can effectively stop oxygen, vapor etc..Such as substrate
Layer can be polyethylene film or polyester film, can also be polypropylene film.
Graphene gas barrier stacking film can also include diaphragm, and the outermost hydrogen bond of at least one lamination unit supplies
The surface away from the graphene layer being adjacent of body is bonded with diaphragm, and for example product structure is followed successively by protection from top to bottom
Film-at least one lamination unit or diaphragm-at least one lamination unit-basalis, can also be protection
Film-at least one lamination unit-basalis-at least one lamination unit-diaphragm.Preferably, diaphragm can be poly-
Ethene diaphragm, polypropylene diaphragm, polyester diaphragm, polystyrene diaphragm, polyamide diaphragm, polycarbonate diaphragm
With polyvinyl acetal resin diaphragm etc..
The Graphene gas barrier that the present invention provides is laminated what film can occur in growth and transfer process to Graphene
Damaged and defect is effectively repaired, and effectively shortens the microcosmic distance between Graphene and Graphene, reduces gas transverse
The probability revealed, improves the barrier property of Graphene.
The present invention also provides above-mentioned Graphene gas barrier to be laminated the preparation method of film, by the relative both sides of graphene layer
Surface is respectively provided with hydrogen bond receptor organic layer and hydrogen bond donor organic layer forms lamination unit, and 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.
For example can be prepared in the following ways, smear hydrogen bond receptor on Graphene sample layer side first organic
Layer is it is preferable that the mode smeared can be during spin coating, spraying, blade coating, cup painting, curtain coating, dip-coating, flow coat, cutter painting or bar apply one
Kind.Wherein smear condition at normal temperatures, smearing pressure is 0.1-10kg, preferably 1-5kg, and coating layer thickness is 15-300 μm, preferably
25-188μm.Then erode the copper on Graphene it is preferable that adopting fecl3、hno3、(nh4)2s2o8Solution is corroded.So
Smear hydrogen bond donor organic layer in graphene-structured layer other side afterwards, define a lamination unit it is preferable that the side smeared
Formula can be a kind of in spin coating, spraying, cup painting, curtain coating, dip-coating or flow coat, and its coating thickness is 15-300 μm, preferably 25-
188μm.At least one lamination unit can also be stacked, the hydrogen bond receptor organic layer of adjacent lamination unit and hydrogen bond donor
Organic layer is adjacent.The side of the hydrogen bond receptor organic layer side of at least one lamination unit above-mentioned and basalis can also be glued
Close；Can also basalis both sides arrange at least one lamination unit above-mentioned, the hydrogen bond receptor organic layer side of lamination unit with
Basalis bonds, and wherein when being provided with basalis, hydrogen bond receptor organic layer and the coating layer thickness of hydrogen bond donor organic layer are preferably
2-100 μm, more preferably 2-10 μm；Diaphragm can also be covered in the hydrogen bond donor organic layer side of at least one lamination unit,
It is more than 50g/25mm preferably under the viscosity normal temperature of diaphragm.
This preparation method, while shortening Obstruct membrane production process, reduces the cost of Graphene Obstruct membrane.
With reference to embodiments the feature and performance of the present invention is described in further detail.
Embodiment 1
Graphene sample is grown using cvd method, smears epoxy resin in Graphene sample side by the way of spraying,
The condition of spraying is to smear pressure 1kg, and coating layer thickness is 15 μm, then passes through fecl3Solution corrosion falls on Graphene sample
Copper, smears polyvinyl alcohol on Graphene sample opposite side by the way of spin coating, obtains Graphene gas barrier stacking film, its
The condition of middle spin coating is 15 μm for coating layer thickness.The Graphene gas barrier that the present embodiment obtains is laminated structure such as Fig. 1 of film 100
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 in Graphene sample side by the way of spraying
Ester, the condition of spraying is 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 Graphene sample opposite side,
Obtain Graphene gas barrier stacking film, the wherein condition of spin coating is 188 μm for coating layer thickness, the graphite obtaining with embodiment 1
The structure that alkene gas barrier is laminated film is identical.
Embodiment 3
Graphene sample is grown using cvd method, smears polyurethane in Graphene sample side by the way of blade coating, scrape
The condition applying is to smear pressure 5kg, and coating layer thickness is 100 μm, then passes through (nh4)2s2o8Solution corrosion falls on Graphene
Copper, is being transferred on polyethylene film by polyurethane, is being smeared second on Graphene sample opposite side by the way of dip-coating
Alkene-ethenol copolymer, obtains Graphene gas barrier stacking film, and the wherein condition of dip-coating is 100 μm for coating layer thickness.This
Embodiment obtains Graphene gas barrier and is laminated the structure of film 100 as shown in Fig. 2 being followed successively by hydrogen bond donor organic layer from top to bottom
203rd, graphene layer 202, hydrogen bond receptor organic layer 201 and basalis 110.
Embodiment 4
Graphene sample is grown using cvd method, smears acrylate in Graphene sample side by the way of cup painting,
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, smear modified ethylene vinyl alcohol copolymer by the way of flow coat in Graphene sample opposite side, the condition of flow coat is
Coating layer thickness is 300 μm, is finally covered with the polystyrene that viscosity is 80g/25mm on modified ethylene vinyl alcohol copolymer and protects
Cuticula diaphragm obtains Graphene gas barrier stacking film, and the present embodiment obtains the structure that Graphene gas barrier is laminated film 100
As shown in figure 3, it is organic to be followed successively by diaphragm 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 the first layer graphene sample side
Base acrylate, the condition of curtain coating is 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-ethene on the first layer graphene sample opposite side by the way of spin coating
The mixture of alcohol copolymer, the condition of spin coating is 25 μm for coating layer thickness, then in the 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 fecl3Molten
Corrosion falls the copper on the second layer graphene sample, by methacrylic acid transesterify second layer Graphene sample to polyvinyl alcohol
On the mixture of modified ethylene vinyl alcohol copolymer, on the opposite side of the second layer graphene sample by the way of spin coating
The mixture smearing polyvinyl alcohol with modified ethylene vinyl alcohol copolymer obtains Graphene gas barrier stacking film, the bar of spin coating
Part is 25 μm for coating layer thickness.Graphene gas barrier that the present embodiment obtains is laminated the structure of film 100 as shown in figure 4, from upper
To under be followed successively by the first hierarchical element 210 and the second hierarchical element 220.
Embodiment 6
Graphene sample is grown using cvd method, smears modified propylene in Graphene sample side by the way of bar painting
Acid esters, the condition that bar applies is to smear pressure 0.1kg, and coating layer thickness is 2 μm, then passes through hno3Solution corrosion falls Graphene sample
On copper, by modified acroleic acid transesterify Graphene sample to polyester film both sides, in the Graphene of polyester film both sides
Modified polyvinylalcohol is smeared by the way of curtain coating on the opposite side of sample, the condition of curtain coating is 2 μm for coating layer thickness.This enforcement
The Graphene gas barrier that example obtains is laminated the structure of film as shown in figure 5, being 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 is to smear pressure 0.1kg, and coating layer thickness is 10 μm, then passes through hno3Solution corrosion falls on Graphene
Copper, by modified acroleic acid transesterify Graphene sample to polypropylene film side, Graphene sample opposite side is adopted
Smear the mixture of modified polyvinylalcohol and polyvinylidene chloride with the mode of spraying, the condition of spraying is 10 μ for coating layer thickness
M, is finally covered with the polyvinyl alcohol contracting second that viscosity is 60g/25mm on the mixture with polyvinylidene chloride for the modified polyvinylalcohol
Urea formaldehyde diaphragm obtains Graphene gas barrier stacking film, and the Graphene gas barrier that the present embodiment obtains is laminated the structure of film
As shown in fig. 6, being hydrogen bond receptor organic layer 201, graphene layer 202, hydrogen bond donor organic layer successively on basalis 110
203 and diaphragm 300, form Graphene Obstruct membrane 100, 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
Olefin(e) acid ester and the mixture of modification acrylate, the condition of flow coat is to smear pressure 0.1kg, and coating layer thickness is 5 μm, then passes through
hno3Solution corrosion falls the copper on Graphene, shifts Graphene by the mixture of urethane acrylate and modification acrylate
Sample, to polystyrene film side, smears modified polyvinylalcohol on the opposite side of Graphene sample by the way of curtain coating
With the mixture of polyvinylidene chloride, the condition of curtain coating is 5 μm for coating layer thickness, finally in modified polyvinylalcohol and poly- inclined dichloro
The polypropylene diaphragm that viscosity is 80g/25mm is covered with the mixture of ethene and obtains Graphene Obstruct membrane, obtain with embodiment 7
Graphene gas barrier be laminated film structure 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 is 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, in graphite
The mixture of ethylene-vinyl alcohol copolymer and polyvinylidene chloride, the bar of curtain coating are smeared by the way of curtain coating on alkene opposite side
Part is 100 μm for coating layer thickness, is finally covered with viscosity on the mixture of ethylene-vinyl alcohol copolymer and polyvinylidene chloride
Polyamide diaphragm for 80g/25mm obtains Graphene gas barrier stacking film, the Graphene gas resistance obtaining with embodiment 7
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 is 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, in Graphene sample opposite side
On 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
The polycarbonate diaphragm that viscosity is 60g/25mm is covered with alcohol and obtains Graphene gas barrier stacking film, obtain with embodiment 7
Graphene gas barrier be laminated film structure identical.
Embodiment 11
Graphene sample is grown using cvd method, smears polyurethane third by the way of spin coating in Graphene sample side
Olefin(e) acid ester and the mixture of modification acrylate, the condition of spin coating is to smear pressure 0.1kg, and coating layer thickness is 50 μm, Ran Houtong
Cross hno3Solution corrosion falls the copper on Graphene, shifts graphite by the mixture of urethane acrylate and modification acrylate
Alkene sample, to polyamide film side, smears ethene improved-ethene on Graphene sample opposite side by the way of spraying
Alcohol copolymer and the mixture of polyvinylidene chloride, the condition of spraying is 50 μm for coating layer thickness, finally in ethene improved-second
The polycarbonate diaphragm that viscosity is 60g/25mm is covered with the mixture of enol copolymer and polyvinylidene chloride and obtains graphite
Alkene gas barrier is laminated film, identical with the structure that the Graphene gas barrier that embodiment 7 obtains is laminated film.
Embodiment 12
Graphene is grown using cvd method, smears modified acroleic acid by the way of dip-coating in the first layer graphene side
Ester, the condition of dip-coating is to smear pressure 0.1kg, and coating layer thickness is 10 μm, then passes through hno3Solution corrosion falls ground floor graphite
Copper on alkene, by modified acroleic acid transesterify ground floor Graphene to polycarbonate membrane side, by heat release glue
On band transfer the second layer graphene to the first layer graphene sample, the second layer graphene sample is smeared by the way of spraying
Modified polyvinylalcohol, the condition of spraying is 10 μm for coating layer thickness, and being finally covered with viscosity on smearing modification is 60g/25mm's
Polyester diaphragm obtains Graphene gas barrier stacking film, and the Graphene gas barrier obtaining with embodiment 7 is laminated the structure of film
Identical.
Embodiment 13
Graphene is grown using cvd method, smears modified acroleic acid by the way of spin coating in the first layer graphene side
Ester, the condition of spin coating is to smear pressure 0.1kg, and coating layer thickness is 2 μm, then passes through hno3Solution corrosion falls the first layer graphene
On copper, by modified acroleic acid transesterify ground floor Graphene to polyamide film side, by heat release adhesive tape turning
Move the second layer graphene to the first layer graphene, heat release adhesive tape transfer the 3rd is then passed through on the second layer graphene sample
Layer graphene, passes through heat release adhesive tape on third layer Graphene and shifts the 4th layer graphene, pass through on the 4th layer graphene
Heat release adhesive tape transfer layer 5 Graphene, smears modified polyvinylalcohol, spray on layer 5 Graphene by the way of spraying
The condition applying is 2 μm for coating layer thickness, is finally covered with the polyethylene protective film that viscosity is 60g/25mm on modified polyvinylalcohol
Obtain Graphene Obstruct membrane, identical with the structure that the Graphene gas barrier that embodiment 7 obtains is laminated film.
The product of the present embodiment 1-13 and control sample are carried out hindering the test of helium, resistance oxygen, test is according to the principle of pressure differential method
Tested, sample is cut into the disk of a diameter of 97mm, with fluid sealant, print is pasted onto after instrument cavity of resorption, tightens
Chamber, after vacuumizing more than 12h, starts to be passed through test gas and starts to test, it is ensured that the pressure of epicoele is in test process
0.1mpa.Control group a product sequentially consists of polystyrene film, a layer graphene sample, polyvinyl alcohol and polyethylene
Diaphragm, the product contrast no hydrogen bond receptor organic layer with the present embodiment 1-13, control group b product sequentially consists of polyphenyl
Vinyl film, modification acrylate, a layer graphene sample and polyethylene protective film, are contrasted no with the product of the present embodiment 1-13
Hydrogen bond donor organic layer, control group c product sequentially consists of polystyrene film, modification acrylate, a layer graphene
Sample, polyvinylidene chloride and polyethylene protective film, wherein do not form hydrogen bond 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 is obtained for larger improvement.
In sum, Graphene gas barrier stacking film of the embodiment of the present invention and preparation method thereof is had by hydrogen bond receptor
Be formed between machine layer and hydrogen bond donor organic layer the breakage that hydrogen bond can occur in growth and transfer process to Graphene and
Defect is effectively repaired, and effectively shortens the microcosmic distance between Graphene and Graphene, reduces gas transverse and reveals
Probability, improve the barrier property of Graphene, while shortening Obstruct membrane production process, reduce the one-tenth of Graphene Obstruct membrane
This.
Embodiments described above is a part of embodiment of the present invention, rather than whole embodiments.The reality of the present invention
The detailed description applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected enforcement of the present invention
Example.Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under the premise of not making creative work
Every other embodiment, broadly falls into the scope of protection of the invention.
Claims (10)
1. a kind of Graphene gas barrier is laminated film it is characterised in that including at least one lamination unit being stacked, each
Described lamination unit includes hydrogen bond receptor organic layer, graphene layer and the hydrogen bond donor organic layer being disposed adjacent successively, described hydrogen
It is formed with hydrogen bond, the described hydrogen bond receptor of adjacent described lamination unit between key acceptor organic layer and described hydrogen bond donor organic layer
Organic layer is adjacent with described hydrogen bond donor organic layer.
2. Graphene gas barrier according to claim 1 stacking film is it is characterised in that described Graphene gas-barrier layer
Folded film also includes basalis, the outermost described hydrogen bond receptor organic layer of at least one lamination unit described away from its phase
The adjacent surface of described graphene layer and described basalis bonding.
3. the Graphene gas barrier stacking film according to any one of claim 1-2 is it is characterised in that described Graphene gas
Body intercepts stacked film and also includes diaphragm, the outermost described hydrogen bond donor organic layer of at least one lamination unit described remote
From the surface of the described graphene layer being adjacent and described diaphragm bonding.
4. Graphene gas barrier according to claim 3 stacking film it is characterised in that described hydrogen bond receptor organic layer by
Epoxy resin, vinylacetate, polyvinylidene fluoride resin, polyurethane, acrylate, methacrylate, modification acrylate
Make with one or more of urethane acrylate.
5. Graphene gas barrier according to claim 3 stacking film it is characterised in that described hydrogen bond donor organic layer by
One or more of polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer, modified ethylene vinyl alcohol copolymer
Make.
6. Graphene gas barrier according to claim 3 stacking film it is characterised in that described hydrogen bond donor organic layer by
At least one in polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer and modified ethylene vinyl alcohol copolymer
Make with the mixture of polyvinylidene chloride.
7. Graphene gas barrier stacking film according to claim 2 is it is characterised in that described basalis is organic thin
Film, described organic film includes polyethylene film, polypropylene film, polyester film, polystyrene film, polyamide film, gathers
One of carbonic acid membrane of lipoprotein and polyvinyl acetal resin film.
8. Graphene gas barrier stacking film according to claim 3 is it is characterised in that described diaphragm includes polyethylene
Diaphragm, polypropylene diaphragm, polyester diaphragm, polystyrene diaphragm, polyamide diaphragm, polycarbonate diaphragm and poly-
One of vinyl acetal resin diaphragm.
9. a kind of Graphene gas barrier is laminated the preparation method of film it is characterised in that comprising: relative in graphene layer
Both side surface is respectively provided with hydrogen bond receptor organic layer and hydrogen bond donor organic layer forms lamination unit, by least one described stacking
Unit is stacked, and the described hydrogen bond receptor organic layer of adjacent described lamination unit is adjacent with described hydrogen bond donor organic layer.
10. Graphene gas barrier according to claim 9 is laminated the preparation method of film it is characterised in that described in each
Graphene layer all includes 1～5 layer graphene sample layer.
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Cited By (1)
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| WO2021212582A1 (en) * | 2020-04-23 | 2021-10-28 | 深圳市华星光电半导体显示技术有限公司 | Thin film transistor and display device |
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