CN104497385B - Aminated graphene oxide/high-density polyethylane nano composite membrane and preparation method thereof - Google Patents
Aminated graphene oxide/high-density polyethylane nano composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an aminated graphene oxide/high-density polyethylane nano composite membrane and a preparation method thereof, which belong to the technical field of high-molecular composite material. A technical scheme is characterized in that graphene oxide and lauryl amine are reacted to prepare the aminated graphene oxide, the aminated graphene oxide and high density polyethylane powder are fully mixed in xylene to prepare a fluid suspension, pumping filtration under vacuum and drying processes are carried out on the fluid suspension, melting hot-pressing treatment is carried out, so that the aminated graphene oxide/high-density polyethylane nano composite membrane is prepared. According to the invention, technology is simple, cost is low, a polymer is not required for being dissolved, and interface compatibility of between the nano composite membrane and a polar polymer/a non-polar polymer can be effectively increased. Simultaneously, a shell-core isolation structure which is characterized in that the aminated graphene oxide is taken as a shell and high density polyethylane is taken as a core can be formed through high-temperature hot pressing, gas permeable area can be greatly reduced, gas diffusion path can be obviously complicated, and the gas barrier property of the material can be obviously increased.
Description
Technical field
The invention belongs to technical field of polymer composite materials, relate to a kind of nano composite membrane and preparation side thereof
Method, is specifically related to a kind of amination graphene oxide/high density ethylene nano composite membrane and preparation method thereof.
Background technology
In recent years, thin polymer film is used widely in industrial or agricultural with the combination property of its excellence.So
And, owing to the best security incident caused of commodity polymer polymeric material barrier and middle loss make it
Can not be widely popularized in certain fields, as oil-gas gathering and transportation polymeric material is easily caused oil because barrier is low
Gas leakage, causes serious accident, causes huge economic loss, casualties and environmental problem.Food,
Drug packing material is because intercepting loss up to 30～50% in the middle of the best product caused.Therefore, further
The barrier property improving thin polymer film has become a key issue urgently to be resolved hurrily.
In improving thin polymer film barrier technology, utilize between nanoscale twins filler and polymer good
Interface interaction and nanoscale twins filler in polymeric matrix, cause " the permeable area that gas permeates
Reduce effect " and " multipath effect " improve the method for barrier property of polymeric matrix, there is behaviour
Make the advantages such as easy, product cost is high and is easily recycled, become thin film fabrication industry the most both at home and abroad and carry
The focus and emphasis of high polymer barrier property research.The method need to break through two key problem in technology points: 1. receives
Rice sheet filler should have bigger flakiness ratio；2. nanometer sheet layered fillers should be formed good with matrix
Interface cohesion.Functionalization graphene, such as graphene oxide, carboxylated Graphene, sulfonated graphene etc.,
It is the product that replaced by oxygen-containing functional group, organic molecule or macromole etc. of the partial double bond on Graphene,
With its huge flakiness ratio (thickness is only about 1nm, and its width is maximum up to ten microns) and at water
With the easily disperse in other solvents so that it is become scientific circles in recent years and improve grinding of polymer barrier performance
Study carefully focus.
Patent " preparation method of a kind of oxidized graphene coated film " (Publication No. CN102173145A)
Adding graphene oxide in water, the stirring of supersound process limit, limit obtains the soliquid of graphene oxide
(adding 1mg graphene oxide in 1mL water), then by graphite oxide by the way of spraying or roll-in
The soliquid of alkene is coated in general purpose film surface, forms graphene oxide film after drying.If coating
Dried layer, after topmost one layer of graphite oxide ene coatings is dried formation thin film, Landfill covering one layer is general thin
Film, i.e. obtains oxidized graphene coated film.Oxidized graphene coated film prepared by the method is the most transparent
Well, safety is high, the feature of environmental protection is good, and has the barrier of excellence, especially to carbon dioxide
Barrier be greatly improved.But nano graphene oxide is passed through spraying or rolling techniques by said method
After coating film forming, be transformed into macroscopic view graphite oxide, after polymeric matrix and graphite oxide self assembly layer with
The adhesion of interlayer is more weak, is susceptible to stripping and comes off, is unfavorable for life-time service.
Patent " graphene oxide with high barrier and the preparation method of polymer nanocomposite membrane " (Publication No.
CN102115566A) add graphene oxide in solvent, supersound process stirring under the conditions of 20～45 DEG C
Mixing is for graphene oxide soliquid.Then in the soliquid of graphene oxide, add polymerization
Thing, stirs on 20～120 DEG C of following supersound process limits, makes polymer be completely dissolved, obtain graphene oxide
/ polymer solution.After removing the bubble in graphene oxide/polymer solution, employing is cast or is blow molded
Method obtains graphene oxide/polymer composite film.Graphene oxide/the polymerization prepared by the method
Thing nano compound film not Presence of an interface departs from or the risk that comes off, to the barrier of carbon dioxide significantly
Degree improves.But polymeric matrix must be dissolved in the middle of solvent by premise prepared by this laminated film uniformly.
And practical situation is, dissolve polymer need take a significant amount of time, and partial polymer such as polyethylene, surpass
High molecular weight polyethylenes etc. also are difficult to be dissolved by a solvent, and therefore the method operating procedure is relative complex, no
There is practicality and versatility.Filler and matrix in laminated film prepared by the method being simultaneously cast or be blow molded
Between the most inevitably there are some residual channel, gas barrier property improves limited.
The barrier property preparing composite raising matrix it is combined, not only by graphene oxide and polymer
Require that graphene oxide can be evenly dispersed in matrix, it is often more important that need graphene oxide with high
Good interface compatibility is had between polymers.The graphene oxide hydroxyl abundant because its surface and edge contain,
The oxygen-containing functional group such as carboxyl and epoxy radicals and there is good hydrophilic, but cause and non-polar polymer
As poor in the interface compatibility between the matrix such as polyethylene, polypropylene, and the resistance of above matrix can not be effectively improved
Separating performance, can reduce its barrier on the contrary.Additionally, graphene oxide organic solvent such as acetone, methanol,
Bad dispersibility in ethanol and dichloromethane, it is impossible to preserve for a long time, also can limit graphene oxide/polymer
The preparation of composite.
Summary of the invention
For the defect overcoming above-mentioned prior art to exist, it is an object of the invention to provide a kind of amination
Graphene oxide/high density polyethylene (HDPE) nano composite membrane and preparation method thereof, the method can overcome existing side
In method, solvent indissoluble non-polar polymer and conventional oxidation Graphene cannot improve non-polar polymer barrier
Can defect, simultaneously can reduce gas infiltration lane, the amination graphene oxide prepared through the method/
Polyethylene nano composite membrane has uniform shell core isolation structure, and barrier property is high.
The present invention is to be achieved through the following technical solutions:
The preparation method of a kind of amination graphene oxide/high density polyethylene (HDPE) nano composite membrane, will aoxidize stone
Ink alkene reacts with lauryl amine after making amination graphene oxide, by amination graphene oxide with high
Density polyethylene powder is sufficiently mixed in dimethylbenzene and prepares suspension, will be dried after suspension vacuum filtration,
Again by melted hot-pressing processing, prepare amination graphene oxide/polyethylene nano composite membrane.
The preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane, comprises the following steps:
1) amination graphene oxide is prepared
Graphene oxide is scattered in deionized water, prepares graphene oxide soliquid；According to
The ratio of (3～5) g:100mL, is dissolved in lauryl amine in dehydrated alcohol, and stirring is to dodecyl
Amine fully dissolves, and obtains lysate, is added by lysate in graphene oxide soliquid, and stirring is all
Even, obtain amination graphene oxide dispersion soln, by this amination graphene oxide dispersion soln through true
Empty sucking filtration, washing and dried, obtain amination graphene oxide；
2) amination graphene oxide/high density polyethylene (HDPE) suspension is prepared
According to the ratio of 1g:100mL, amination graphene oxide is added in dimethylbenzene, ultrasonic dissociate
And stir, prepare amination graphene oxide dispersion, add in amination graphene oxide dispersion
High-density polyethylene powder, stirs, and obtains amination graphene oxide/high density polyethylene (HDPE) suspension；
Wherein, the quality of amination graphene oxide accounts for amination graphene oxide/high density polyethylene (HDPE) suspension
The 7～10% of liquid gross mass；
3) the standby amination graphene oxide/high density polyethylene (HDPE) nano composite membrane of melting heat compacting
By being dried after amination graphene oxide/high density polyethylene (HDPE) suspension vacuum filtration, obtain amination
Graphene oxide/high density polyethylene (HDPE) mixture, then by this amination graphene oxide/high-density polyethylene
Alkene mixture is under conditions of 260～270 DEG C, 15～20MPa, and melting and making thickness is 10～12 μm,
A diameter of 120～the circular membrane of 130mm, i.e. obtain amination graphene oxide/high density polyethylene (HDPE) and receive
Rice composite membrane.
Step 1) described in stir, be lysate to be added in graphene oxide soliquid,
At 50～60 DEG C, mechanical agitation 24～48h；Described washing be by vacuum filtration after amination oxidation stone
Ink alkene dispersion soln washes of absolute alcohol 4～6 times；Described dry be at 50～60 DEG C, vacuum is done
Dry 24～30h.
Step 2) described in ultrasonic to dissociate and stir be ultrasonic under conditions of 25～40 DEG C to dissociate and stir
1～2h；Described stirring is addition high density polyethylene (HDPE) powder in amination graphene oxide dispersion
Last, mechanical agitation 5～10min.
Described ultrasonic dissociating is to dissociate under conditions of ultrasonic power is 100W.
Step 3) described in dry be at 50～60 DEG C be dried 24～48h.
The preparation of graphene oxide, specifically includes following steps:
(1) according to the ratio of (2～4) g:100mL, it is 98% that expansible graphite adds to mass fraction
Concentrated sulphuric acid in, add KMnO under ice bath while stirring4, stirring reaction 2～2.5h at 10～15 DEG C,
Then in the water bath with thermostatic control of 33～37 DEG C, continue reaction 1～1.5h；
(2) according to concentrated sulphuric acid: deionized water: hydrogen peroxide=100:(400～800): the body of (5～10)
Long-pending ratio, in the reaction system of step (1), successively add deionized water and mass concentration be 30% double
Oxygen water, after stirring, filtered while hot, prepare pasty mixture；
(3) by pasty mixture washing to filter liquor without SO4 2-, then it is scattered under ultrasound condition
In deionized water, prepare graphene oxide soliquid, then drying prepares graphene oxide.
The KMnO that step (1) adds4Quality is expansible graphite quality 3～5 times.
Washing described in step (3) is first with the washing of HCl solution that mass concentration is 5%, then spend from
Sub-water cyclic washing does not contains SO to filter liquor4 2-；Wherein, mass concentration used is the HCl solution of 5%
Volume is 1～2 times of pasty mixture volume.
A kind of amination graphene oxide/polyethylene nano composite membrane, this amination graphene oxide/poly-second
The saturating Oxygen Coefficients of alkene nano composite membrane is 1.12 × 10-15～2.52 × 10-15cm3·cm/(cm2S Pa), thickness
It is 10～12 μm, a diameter of 120～130mm.
Compared with prior art, the present invention has a following useful technique effect:
First graphene oxide and lauryl amine effect is made amination graphene oxide by the present invention, and ten
Amino on the long hydrocarbon chain molecule of dialkylamine has higher with carboxyl and the epoxy radicals of surface of graphene oxide
Reactivity, thus utilize the long hydrocarbon chain on its surface can be effectively improved between filler and non-polar polymer
Interface compatibility, and then improve the barrier property of composite membrane of polymer；Then by prepared amination oxidation
Graphene and high-density polyethylene powder are sufficiently mixed in solvent xylene, form mixed uniformly suspension
Liquid.A large amount of lamella amination graphene oxides have wrapped up high-density polyethylene powder, through high-temperature fusion hot pressing
Rear formation is with amination graphene oxide as shell, and high density polyethylene (HDPE) is the shell core isolation structure of core, amino
Change surface of graphene oxide, with alkyl chain, in hot pressing, can be formed with high density polyethylene (HDPE) molecule
Good interface interaction.
The preparation method technique of the laminated film that the present invention provides is simple, with low cost, it is not necessary to dissolve polymerization
Thing, can solve preparation such as indissoluble depolymerization compound such as polyethylene, ultra-high molecular weight polyethylene, polypropylene etc. multiple
Close the difficult point of thin film.The amination graphene oxide related in the inventive method has good in solvent xylene
Good dispersibility, can guarantee that and do not precipitate by least three moon, can be effectively improved and polar polymer and non-
Interface compatibility between polar polymer.Meanwhile, define after high temperature hot pressing with amination oxidation stone
Ink alkene be shell, high density polyethylene (HDPE) be the shell core isolation structure of core, considerably reduce the permeable of gas
Area, makes gas diffusion path the most meandering, hence it is evident that improve the gas barrier property of material.
Amination graphene oxide/high density polyethylene (HDPE) nano composite membrane that the present invention prepares has uniformly
Shell core isolation structure, barrier property is high.When gas molecules is by this laminated film internal penetration, meeting
Run into substantial amounts of amination graphene oxide sealing coat, owing to amination graphene oxide skeleton is by densification
Carbon atom is combined closely and is formed, and gas molecules can not be directed through, can only be along amination graphene oxide
Sheet surfaces is walked around, and this makes the permeable area of gas be greatly reduced.And the amination oxidation stone added
Spacing between ink alkene lamella is the least, makes gas diffusion path the most meandering, causes gas to permeate road
Footpath increases.Therefore, the effect of amination stannic oxide/graphene nano obstruct wall significantly improves high-density polyethylene
The barrier property of alkene thin film, the nano compound film making the present invention prepare is thin with existing high density polyethylene (HDPE)
The saturating Oxygen Coefficients of film is compared and be have dropped about 98%.
Accompanying drawing explanation
Fig. 1 is the FTIR curve chart of graphene oxide and amination graphene oxide；
Fig. 2 is amination graphene oxide/high density polyethylene (HDPE) laminated film that the embodiment of the present invention 1 prepares
Polarizing microscope figure；
Fig. 3 is that amination graphene oxide/high density polyethylene (HDPE) that the embodiment of the present invention 1 prepares is nano combined
The permeable model figure of gas in thin film.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, described in be to the present invention
Explanation rather than restriction.
Embodiment 1
A kind of amination graphene oxide/high density polyethylene (HDPE) nano composite membrane and preparation method thereof, including with
Lower step:
1) graphene oxide is prepared
First, the Hummers method improved is utilized to prepare graphene oxide: to weigh 2g expansible graphite and add
Enter to the dense H that 100mL mass concentration is 98%2SO4In, after stirring in ice-water bath, gradually
Add 10gKMnO4, at 10 DEG C, react 2.5h.Reaction is continued subsequently in the water bath with thermostatic control of 35 DEG C
1.25h, more successively addition 400mL deionized water and 5mL mass concentration are 30% in mixture system
H2O2, by mixture filtered while hot after stirring, molten with the HCl that 30mL mass concentration is 5%
After liquid washing again with a large amount of deionized water cyclic washings until without SO in filtrate4 2-(use BaCl2Solution is examined
Test), then utilize ultrasonication to be scattered in 200mL deionized water, obtain graphene oxide glue
Liquid suspension.
2) amination graphene oxide is prepared
Weighing 3g lauryl amine to be dissolved in 100mL dehydrated alcohol, stirring makes it fully dissolve, by molten
Solve liquid and join in graphene oxide soliquid, 50 DEG C of mechanical agitation 48h, obtain amination oxidation
Graphene dispersion solution；Finally, amination graphene oxide dispersion soln vacuum is filtered, uses anhydrous second
Alcohol cleans 6 times, keeps 24h, obtain the amination graphene oxide that 3.8g is dried in 60 DEG C of vacuum drying ovens.
3) nano composite membrane is prepared
Take in the amination graphene oxide addition 100mL dimethylbenzene that 1g is dried, ultrasonic (merit at 30 DEG C
Rate is 100W) and stir 2h and obtain amination graphene oxide dispersion；Then stone is aoxidized to amination
Ink alkene colloidal dispersion adds 10g high-density polyethylene powder, mechanical agitation 10min, makes high density
Polyethylene powders is sufficiently mixed, and obtains amination graphene oxide/high density polyethylene (HDPE) suspension；Again should
Amination graphene oxide/high density polyethylene (HDPE) suspension carries out vacuum and filters, at 60 DEG C of dry 24h；?
After at 260 DEG C, melted under the pressure of 20MPa make thickness 12 μm, the circular membrane of diameter 120mm.
The FTIR curve chart of graphene oxide shown in Figure 1 and amination graphene oxide, from figure
In it can be seen that containing substantial amounts of oxygen-containing functional group in graphene oxide, wherein 3421～3438cm-1,
1728cm-1, 1624～1650cm-1With 1030～1160cm-1Place is respectively hydroxyl (O-H), carboxyl (-O-C
=O), carbonyl (C=O) and the stretching vibration peak of epoxy radicals (C-O-C), 2921cm-1And 2852cm-1
For CH2C-H stretching vibration peak with CH group.Compared with the infrared spectrogram of graphene oxide, ammonia
Base graphene oxide is at 2921/2852cm-1The peak intensity at place is significantly raised, shows to pass through lauryl amine
The carbonyl condensation reaction of amino and surface of graphene oxide, a large amount of alkyl chains are grafted to graphene oxide table
Face, graphene oxide is by successful modification.Thus make the O-H vibration peak of amination graphene oxide to Gao Bo
Number skew 17cm-1, show the interaction relatively graphene oxide fall between amination graphene oxide lamella
Low.Additionally, amination graphene oxide is at 1560cm-1(the bending amide of N-H), 1460/1462cm-1
(C-N stretches amide) and 720cm-1The vibration peak at (C-H bending vibration) place shows graphite oxide
Amido link is there is between alkene lamella and dodecyl amine molecule.
The polarisation of amination graphene oxide/high density polyethylene (HDPE) nano composite material shown in Figure 2
Microscope figure, as seen from the figure, the amination graphene oxide/high density polyethylene (HDPE) prepared is nano combined
Film presents the isolation structure that good interface combines, and wherein black region is substantial amounts of amination graphene oxide,
White-bright zone territory is high density polyethylene (HDPE).
The saturating Oxygen Coefficients of existing density polyethylene film with high is 5.70 × 10-14cm3·cm/(cm2S Pa), and
The saturating Oxygen Coefficients of amination graphene oxide/high density polyethylene (HDPE) laminated film prepared by the present embodiment is
1.12×10-15cm3·cm/(cm2S Pa), have dropped about 98%.
Embodiment 2
A kind of amination graphene oxide/high density polyethylene (HDPE) nano composite membrane and preparation method thereof, including with
Lower step:
1) graphene oxide is prepared
First, the Hummers method improved is utilized to prepare graphene oxide: to weigh 3g expansible graphite and add
Enter to the dense H that 110mL mass concentration is 98%2SO4In, after stirring in ice-water bath, gradually add
Enter 12g KMnO4, at 15 DEG C, react 2h.Reaction 1.5h is continued subsequently in the water bath with thermostatic control of 33 DEG C,
In mixture system, successively add 450mL deionized water again and 20mL mass concentration is 30%
H2O2, by mixture filtered while hot after stirring, it is the HCl solution of 5% by 35mL mass concentration
After washing again with a large amount of deionized water cyclic washings until without SO in filtrate4 2-(use BaCl2Solution is checked),
Then utilize ultrasonication to be scattered in 300mL deionized water, obtain graphene oxide colloidal suspension
Liquid.
2) amination graphene oxide is prepared
Weighing 4.5g lauryl amine to be dissolved in 110mL dehydrated alcohol, stirring makes it fully dissolve, will
Lysate joins in graphene oxide soliquid, 60 DEG C of mechanical agitation 20h, obtains amination oxygen
Functionalized graphene dispersion soln；Finally, amination graphene oxide dispersion soln vacuum is filtered, with anhydrous
Ethanol purge 5 times, keeps 36h, obtains the amination graphite oxide that 8.4g is dried in 55 DEG C of vacuum drying ovens
Alkene.
3) nano composite membrane is prepared
Take in the amination graphene oxide addition 125mL dimethylbenzene that 1.25g is dried, ultrasonic at 30 DEG C
(power is 100W) is also stirred 1.5h and is obtained amination graphene oxide dispersion；Then to amination
Addition 13.75g high-density polyethylene powder in graphene oxide colloidal dispersion, mechanical agitation 8min,
Make high-density polyethylene powder be sufficiently mixed, obtain amination graphene oxide/high density polyethylene (HDPE) and suspend
Liquid；Again this amination graphene oxide/high density polyethylene (HDPE) suspension is carried out vacuum to filter, at 55 DEG C
It is dried 36h；Last at 265 DEG C, melt under the pressure of 18MPa and make thickness 11 μm, diameter 125mm
Circular membrane.
The saturating Oxygen Coefficients of existing density polyethylene film with high is 5.70 × 10-14cm3·cm/(cm2S Pa), and
The saturating Oxygen Coefficients of amination graphene oxide/high density polyethylene (HDPE) laminated film prepared by the present embodiment is
1.43×10-15cm3·cm/(cm2S Pa), have dropped about 97.5 times.
Embodiment 3
A kind of amination graphene oxide/high density polyethylene (HDPE) nano composite membrane and preparation method thereof, including with
Lower step:
1) graphene oxide is prepared
First, the Hummers method improved is utilized to prepare graphene oxide: to weigh 4g expansible graphite and add
Enter to the dense H that 120mL mass concentration is 98%2SO4In, after stirring in ice-water bath, gradually
Add 20g KMnO4, at 15 DEG C, react 2h.Reaction is continued subsequently in the water bath with thermostatic control of 37 DEG C
1h, more successively addition 600mL deionized water and 25mL mass concentration are 30% in mixture system
H2O2, by mixture filtered while hot after stirring, it is the HCl solution of 5% by 40mL mass concentration
After washing again with a large amount of deionized water cyclic washings until without SO in filtrate4 2-(use BaCl2Solution is checked),
Then utilize ultrasonication to be scattered in 400mL deionized water, obtain graphene oxide colloidal suspension
Liquid.
2) amination graphene oxide is prepared
Weighing 5g lauryl amine to be dissolved in 120mL dehydrated alcohol, stirring makes it fully dissolve, by molten
Solve liquid and join in graphene oxide soliquid, 55 DEG C of mechanical agitation 36h, obtain amination oxidation
Graphene dispersion solution；Finally, amination graphene oxide dispersion soln vacuum is filtered, uses anhydrous second
Alcohol cleans 4 times, keeps 48h, obtain the amination graphene oxide that 10.0g is dried in 50 DEG C of vacuum drying ovens.
3) nano composite membrane is prepared
Take in the amination graphene oxide addition 250mL dimethylbenzene that 2.5g is dried, ultrasonic at 35 DEG C
(power is 100W) is also stirred 1.5h and is obtained amination graphene oxide dispersion；Then to amination
Addition 32.75g high-density polyethylene powder in graphene oxide colloidal dispersion, mechanical agitation 6min,
Make high-density polyethylene powder be sufficiently mixed, obtain amination graphene oxide/high density polyethylene (HDPE) and suspend
Liquid；Again this amination graphene oxide/high density polyethylene (HDPE) suspension is carried out vacuum to filter, at 50 DEG C
It is dried 48h；Last at 270 DEG C, melt under the pressure of 15MPa and make thickness 10 μm, diameter 130mm
Circular membrane.
The saturating Oxygen Coefficients of existing density polyethylene film with high is 5.70 × 10-14cm3·cm/(cm2S Pa), and
The saturating Oxygen Coefficients of amination graphene oxide/high density polyethylene (HDPE) laminated film prepared by the present embodiment is
2.52×10-15cm3·cm/(cm2S Pa), have dropped about 95.6 times.
The mechanism of action of the present invention is described below:
Gas molecule penetrating through absorption, dissolve, spread and separate out Four processes in the film.Its base
This permeability mechanism is: gas molecule first with film contacts, be enriched with at film surface subsequently and dissolve, making
Both sides, film surface produce concentration difference.Under the effect of concentration difference, gas molecule is with polymer macromolecule segment
" the moment hole " that strenuous exercise occurs progressively at film internal diffusion, finally arrives the another of thin film as passage
Side and separate out.
Use amination graphene oxide prepared by the inventive method, under ultrasonic dissociation, it is possible to all
Even it is scattered in xylene solvent, after stirring, forms mixed uniformly suspension with high-density polyethylene powder.
A large amount of lamella amination graphene oxides have wrapped up high-density polyethylene powder, formed after high temperature hot pressing with
Amination graphene oxide is shell, and high density polyethylene (HDPE) is the shell core isolation structure (Fig. 2) of core.Additionally,
Owing to amination surface of graphene oxide is with alkyl chain, in hot pressing, energy and high density polyethylene (HDPE)
Molecule forms good interface interaction.
Gas is by the amination graphene oxide/high density polyethylene (HDPE) nano compound film of isolation structure
Process of osmosis is as it is shown on figure 3, high density polyethylene (HDPE) is by the parcel isolation of a large amount of lamella amination graphene oxides.
When gas molecules is by thin film internal penetration, substantial amounts of amination graphene oxide sealing coat can be run into.
Forming owing to amination graphene oxide skeleton is combined closely by fine and close carbon atom, gas molecules can not
Being directed through, can only walk around along amination graphene oxide lamella surface, this makes permeable of gas
Amass and be greatly reduced.Additionally, the spacing between the amination graphene oxide lamella added is the least, make gas
The evolving path is the most meandering, causes gas leak path to increase.Therefore, amination graphene oxide
The effect of nanometer barrier wall significantly improves the barrier property of density polyethylene film with high, makes the nanometer of preparation
The saturating Oxygen Coefficients of laminated film have dropped about 98%.
In sum, melted press mold technique one step of the present invention i.e. can get high-barrier composite film, is suitable for
In extensive preparation.The amination graphite oxide that the present invention is prepared by heat pressing process at a lower temperature
Alkene/high density polyethylene (HDPE) laminated film has regular uniform shell core isolation structure, and gas can be greatly lowered
Infiltrating area, improves gas leak path, hence it is evident that improve the barrier to all kinds of gases.Used
Polymeric matrix can also include other alkanes polymer such as ultra-high molecular weight polyethylene, polypropylene or be total to
Polymers.
Claims (9)
1. the preparation method of amination graphene oxide/polyethylene nano composite membrane, it is characterised in that
Comprise the following steps:
1) amination graphene oxide is prepared
Graphene oxide is scattered in deionized water, prepares graphene oxide soliquid；According to
The ratio of (3～5) g:100mL, is dissolved in lauryl amine in dehydrated alcohol, and stirring is to dodecyl
Amine fully dissolves, and obtains lysate, is added by lysate in graphene oxide soliquid, and stirring is all
Even, obtain amination graphene oxide dispersion soln, by this amination graphene oxide dispersion soln through true
Empty sucking filtration, washing and dried, obtain amination graphene oxide；
2) amination graphene oxide/high density polyethylene (HDPE) suspension is prepared
According to the ratio of 1g:100mL, amination graphene oxide is added in dimethylbenzene, ultrasonic dissociate
And stir, prepare amination graphene oxide dispersion, add in amination graphene oxide dispersion
High-density polyethylene powder, stirs, and obtains amination graphene oxide/high density polyethylene (HDPE) suspension；
Wherein, the quality of amination graphene oxide accounts for amination graphene oxide/high density polyethylene (HDPE) suspension
The 7～10% of liquid gross mass；
3) the standby amination graphene oxide/high density polyethylene (HDPE) nano composite membrane of melting heat compacting
By being dried after amination graphene oxide/high density polyethylene (HDPE) suspension vacuum filtration, obtain amination
Graphene oxide/high density polyethylene (HDPE) mixture, then by this amination graphene oxide/high-density polyethylene
Alkene mixture is under conditions of 260～270 DEG C, 15～20MPa, and melting and making thickness is 10～12 μm,
A diameter of 120～the circular membrane of 130mm, i.e. obtain amination graphene oxide/high density polyethylene (HDPE) and receive
Rice composite membrane, the saturating Oxygen Coefficients of this amination graphene oxide/polyethylene nano composite membrane is
1.12×10-15～2.52 × 10-15cm3·cm/(cm2S Pa), thickness is 10～12 μm, a diameter of
120～130mm.
A kind of amination graphene oxide/polyethylene nano composite membrane the most according to claim 1
Preparation method, it is characterised in that step 1) described in stir, be by lysate add oxidation stone
In ink alkene soliquid, at 50～60 DEG C, mechanical agitation 24～48h；Described washing is vacuum to be taken out
Amination graphene oxide dispersion soln after filter washes of absolute alcohol 4～6 times；Described dry be
At 50～60 DEG C, it is vacuum dried 24～30h.
A kind of amination graphene oxide/polyethylene nano composite membrane the most according to claim 1
Preparation method, it is characterised in that step 2) described in ultrasonic to dissociate and stir be the bar at 25～40 DEG C
Ultrasonic under part dissociate and stir 1～2h；Described stirring is in amination graphene oxide dispersion
After adding high-density polyethylene powder, mechanical agitation 5～10min.
A kind of amination graphene oxide/polyethylene nano composite membrane the most according to claim 3
Preparation method, it is characterised in that described ultrasonic dissociating is to enter under conditions of ultrasonic power is 100W
Row dissociates.
A kind of amination graphene oxide/polyethylene nano composite membrane the most according to claim 1
Preparation method, it is characterised in that step 3) described in dry be at 50～60 DEG C be dried 24～48h.
A kind of amination graphene oxide/polyethylene nano composite membrane the most according to claim 1
Preparation method, it is characterised in that the preparation of described graphene oxide, specifically includes following steps:
(1) according to the ratio of (2～4) g:100mL, it is 98% that expansible graphite adds to mass fraction
Concentrated sulphuric acid in, add KMnO under ice bath while stirring4, stirring reaction 2～2.5h at 10～15 DEG C,
Then in the water bath with thermostatic control of 33～37 DEG C, continue reaction 1～1.5h；
(2) according to concentrated sulphuric acid: deionized water: hydrogen peroxide=100:(400～800): the body of (5～10)
Long-pending ratio, in the reaction system of step (1), successively add deionized water and mass concentration be 30% double
Oxygen water, after stirring, filtered while hot, prepare pasty mixture；
(3) by pasty mixture washing to filter liquor without SO4 2-, then it is scattered under ultrasound condition
In deionized water, prepare graphene oxide soliquid, then drying prepares graphene oxide.
A kind of amination graphene oxide/polyethylene nano composite membrane the most according to claim 6
Preparation method, it is characterised in that the KMnO that step (1) adds4Quality be expansible graphite quality
3～5 times.
A kind of amination graphene oxide/polyethylene nano composite membrane the most according to claim 6
Preparation method, it is characterised in that the washing described in step (3) is to be first the HCl of 5% by mass concentration
Solution washs, then with deionized water cyclic washing to filter liquor without SO4 2-；Wherein, mass concentration used
It it is volume is pasty mixture volume 1～2 times of HCl solution of 5%.
9. amination graphene oxide/poly-second that in claim 1～8, method described in any one prepares
Alkene nano composite membrane, it is characterised in that the oxygen flow of this amination graphene oxide/polyethylene nano composite membrane
Gas coefficient is 1.12 × 10-15～2.52 × 10-15cm3·cm/(cm2S Pa), thickness is 10～12 μm, a diameter of
120～130mm.
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| US10800907B2 (en) | 2016-01-15 | 2020-10-13 | Qenos Pty Ltd | Process for preparation of polyethylene nanocomposite |
| CN107383518B (en) * | 2016-05-16 | 2020-01-07 | 中国石油天然气股份有限公司 | Preparation method of polyethylene-graphene compound |
| CN106317578A (en) * | 2016-09-12 | 2017-01-11 | 福州大学 | High-ultraviolet-shielding high-barrier nanomaterial film and preparation method thereof |
| CN109250710A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of amination graphene oxide |
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| CN108586813A (en) * | 2018-04-28 | 2018-09-28 | 西安理工大学 | A kind of preparation method of the cellulose nano-fibrous laminated film of graphene oxide with high barrier- |
| CN110240763B (en) * | 2019-05-23 | 2022-03-15 | 大连工业大学 | Method for preparing bromobutyl rubber/polyethylene barrier function composite membrane by wet method |
| CN110183844A (en) * | 2019-05-30 | 2019-08-30 | 陕西科技大学 | A kind of amination graphene enhancing aqueous polyurethane and preparation method thereof |
| CN111171449B (en) * | 2020-02-05 | 2022-10-28 | 上海大学 | High-thermal-conductivity polypropylene/graphene composite material and preparation method thereof |
| CN111544795A (en) * | 2020-04-08 | 2020-08-18 | 常州美洛医疗科技有限公司 | Preparation method of graphene filtering particulate respirator antibacterial filter element and prepared filter element |
| CN114456470A (en) * | 2022-03-09 | 2022-05-10 | 中海石油(中国)有限公司 | Polymer composite material with gas high-barrier property |
| CN116589777A (en) * | 2023-06-16 | 2023-08-15 | 高尚蓉 | Halogen-free flame-retardant crosslinked polyethylene cable material and preparation method thereof |
| CN117819864B (en) * | 2024-03-04 | 2024-05-14 | 四川蜀道建筑科技有限公司 | Polycarboxylic acid high-performance water reducer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103897244A (en) * | 2014-03-10 | 2014-07-02 | 西安理工大学 | Method for preparing high-barrier graphene oxide-polyethylene nano composite film |
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