CN104119595B - Polymer of magnetic oxygenated graphene film containing orientations and preparation method thereof - Google Patents
Polymer of magnetic oxygenated graphene film containing orientations and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polymer of magnetic oxygenated graphene film containing orientations and preparation method thereof, the polymer of the described magnetic oxygenated graphene film containing orientations, it is characterized in that, the graphene oxide sheet magnetic/functionalized by polymer and orientations graft type in the polymer forms.Present invention can apply to various fields, as prepared by packing film, various container bottle, record standby etc..The present invention substantially increases the barrier property of gas, liquid etc., solve thin polymer film or the problem of container barrier difference present in prior art, not only there is the high intensity of graphene oxide, and big wide thick ratio can be obtained, high specific surface area and closely surface texture, also have nanometer Fe3O4The magnetic of particle, it is achieved thereby that its functionalization.
Description
Technical field
The present invention relates to polymer of magnetic oxygenated graphene film containing orientations and preparation method thereof.
Background technology
Polymer composite is with the combination property of its excellence, as glass, the succedaneum of pottery even metal material
Productive life obtains increasingly be widely applied.Particularly the plastic various packaging applications in life are (such as: food
Product packaging, drug packaging) and liquid, gas storage container application aspect etc..But general packaging material and storage are held
The sealing property of equipment material and mechanical performance are still difficult to meet actual operation requirements, replace because package encapsulation is bad and used
The wasting of resources caused for the factor such as expensive of material is up to 1,000,000,000 yuan/year.Therefore improve packaging material and store appearance
The sealing property of equipment material and mechanical performance are always emphasis and the focus of the high industry research of domestic and international sealing requirements.
At present in the Barrier Technology of polymer composite, multiplex nanoscale twins material, as the system of filling, utilizes polymerization
Gas infiltration " multipath effect " that interface interaction between thing matrix and inserts and inserts cause in the polymer or " receive
Rice obstruct wall ", the effective barrier property improving polymeric material.
The most existing main method preparing barrier material has following several:
Filing date: 2011.01.06, Application No.: 201110001525.3, Publication No.: CN102173145A, public
Opening the date is: 2011.09.07, patent name is: " preparation method of a kind of oxidized graphene coated film ", with graphene oxide
For being coated with dressing, coated with multiple layer graphene oxide on general purpose polystyrene thin film, in order to improve the barrier properties for gases of thin-film material.
Filing date: 2002.09.19, Application No.: 02137053.2, Authorization Notice No. is: CN1169880C, authorizes
Date of declaration is: 2004.10.06, and patent name is " preparation method of high barrier nylon composite materials ", with high barrier gold
Genus scale, as filler, utilizes twin screw extrusion process to realize the compound of nylon 6/ metal scale, and prepares high barrier and be combined
Material.
Filing date 2005.05.20, Application No.: 200510031564.2, Publication No.: CN1754908A, publication date
Phase is: 2006.04.05, patent name is " HDPE/PA-6 high-barrier polymer laminated blending material ", uses high-density polyethylene
Alkene and nylon 6, add compatilizer, then utilize twin screw extrusion process to prepare the material of high barrier.
Filing date: 2009.08.27, Application No.: 200910065952.0, Authorization Notice No. is:
CN101633761B, authorized announcement date is: 2012.08.08, patent name be " a kind of isolating polypropylene composite material and
Preparation method ", with polypropylene, ethylene-vinyl alcohol copolymer, compatilizer as raw material, it is blended and prepares barrier composite.
Filing date: 2005.08.15, Application No.: 200580035390.5, Authorization Notice No. is:
CN101039801B, authorized announcement date is: 2010.05.30, and PCT application announces data: W02006/
019083JA2006.02.23, the request for data of PCT application: PCT/JP2005/0149262005.08.15, PCT application enters
Thenational phase day: 2007.04.16. patent name is " barrier properties for gases laminate film and manufacture method thereof ", is first at thin film
Plate one layer of inorganic oxide evaporation film on layer, then coat one layer of gas barrier film changing on evaporation film, the most just become
Isolation laminated thin film.
Filing date: 2006.05.30, Application No.: 200610051697.0, Authorization Notice No. is:
CN100415508C, authorized announcement date is 2008.09.03, and patent name is " a kind of high obstruction self assembling multilayer composite film
Preparation method ", be first substrate was once carried out electrification process, then utilize electrostatic precipitation principle to realize the group of negative and positive electrolyte
Dress deposition, obtains self-assembled film, and finally compound upper hot sealing layer, has just obtained the multi-layer compound film that high resistant oxygen blocks water.
Filing date: 2011.10.24, Application No.: 201110325321.5, application publication number is:
CN102382429A, Shen Qing Publication day is: 2012.03.21, and patent name is that " a kind of polyethylene terephthalate intercepts
Property composite and preparation technology thereof ", with PET, barrier nylon, nano imvite, interfacial compatibilizer as raw material, prepare
Barrier composite.
More than study some be by different materials be blended preparation to composite, thus improve its barrier property；Have
It is to improve its barrier by interpolation barrier filler and multiple process means.
Graphene is the two-dimension plane structure material that Recent study is burning the hotest, not only in electricity, calorifics, mechanical property
Aspect performance excellence, because its planar structure also gains great popularity in terms of barrier property.Graphene is applied in polymer strengthen it
The existing less report of barrier property, wherein graphene nanometer sheet dispersion direction in the polymer is the pass of its barrier property
Key.
But, current technology, graphene nanometer sheet random dispersion in the polymer, lack good planar orientation knot
Structure, still cannot realize good barriering effect.The present invention is by introducing magnetic nano-particle at graphenic surface, the most outside
Realize its planar orientation dispersion in the polymer under the action of a magnetic field, finally realize the barrier property of its excellence.
Summary of the invention
It is an object of the invention to provide polymer and the preparation thereof of a kind of magnetic oxygenated graphene film containing orientations
Method, with the defect overcoming limit prior art to exist.
The polymer of the described magnetic oxygenated graphene film containing orientations, by polymer and orientations described
The graphene oxide sheet composition that graft type in polymer is magnetic/functionalized, the graphene oxide sheet that described graft type is magnetic/functionalized
Sheet footpath is 20nm-100um, with described total polymer gauge, the weight of the graphene oxide sheet that described graft type is magnetic/functionalized
Amount degree is 0.05～5%；
The magnetic/functionalized graphene oxide of described graft type is graphene oxide and magnetic nano-particle, at catalyst action
The product of lower formation；
Preferably, for graphene oxide and the Fe of surface carboxyl groups of surface amination3O4Magnetic nano-particle, in catalysis
Combine the product formed with covalent bond under the effect of agent；
Preferably, described catalyst is dibutyl tin laurate or pyridine or EDAC (Ethyldimethylaminopropyl carbonization
Diimine)；
The spacing of the magnetic particle of described magnetic/functionalized graphene oxide sheet surface grafting is at least 8nm.
Described orientations, refers to the magnetic/functionalized graphene oxide sheet of described graft type in described polymer,
Arrange with two dimensional surface orientation texture；
Described orientation, refers to graphene oxide sheet and has certain aligning, form certain orientation angles.
Described polymer is selected from the polyolefin polymers such as polyethylene, polypropylene, polystyrene, polyvinylidene chloride, gathers
The rubber polymers such as the polyester polymer such as ethylene glycol terephthalate, Merlon, silicone rubber or polyformaldehyde, polysulfones,
Polylactic acid etc..
The preparation method of the polymer of the described magnetic oxygenated graphene film containing orientations, comprises the steps:
(1) amination graphene oxide suspension is prepared:
P-phenylenediamine is dissolved in nitrogen-nitrogen dimethylformamide (DMF), add through hot soarfing from montmorillonite-based nano
The suspension of sheet, graphene oxide and water, 80～100 DEG C of reactions 10～14h, amination graphene oxide suspension；
In DMF solution:
The weight percent content of p-phenylenediamine is 0.08%～8%, preferably 0.12～0.18%；
The weight percent content of graphene oxide is 0.1%～1%, preferably 0.3～0.7%；
Described hot soarfing from montmorillonite-based nano sheet weight consumption is graphene oxide 1%～50%, described illiteracy take off
Soil nanometer blade footpath is 1～20nm；
The weight consumption of water is 800～1200 times of graphene oxide, and the consumption of water is not crucial, as long as can shape
Become suspension；
Described graphene oxide can use commercially produced product, if the Nanjing Ji Cang nanosecond science and technology company limited trade mark is JCGO-
The product of 98-1-5, or use J.Am.Chem.Soc., 1958,80 (6), pp1339 1339, Preparation of
Prepared by the Hummers method of Graphitic Oxide document report；
Described hot soarfing from montmorillonite-based nano sheet, polymer material science and engineering, 2008,24 (7) document reports can be used
Prepared by the method in road；
(2) magnetic nano-particle is prepared
By Fe3O4Magnetic nanoparticle adds in hexamethylene, oleic acid and oleyl amine, and then ultrasonic disperse is collected oil-soluble
Fe3O4Nanoparticle；
The parts by weight of component are:
Preferably, the parts by weight of component are:
Fe3O4The particle diameter of magnetic nanoparticle is 8-20nm；
Described Fe3O4Magnetic nanoparticle can use the method for routine to prepare, as used Hubei University's journal, Huang Qing
The mountain valley with clumps of trees and bamboos etc., chemical coprecipitation prepares nano ferriferrous oxide particle, prepared by method disclosed in document；
The oil-soluble Fe that will be obtained3O4Nanoparticle dissolution is in toluene, then with DMSA's (dimercaptosuccinic acid)
DMSO (dimethyl sulfoxide) solution mixes, 10～30 DEG C of reactions 8～14h, is subsequently adding ethyl acetate, collects precipitation with Magnet,
Washing, is subsequently adding water, and the weight of water is with for sedimentary 90～110 times, then with alkaline matter, as sodium hydroxide regulates it
PH to 7-8, obtains the Fe containing surface carboxyl groups3O4The solution of magnetic nano-particle；
The parts by weight of component are:
Preferably, the parts by weight of component are:
(3) preparation of the graphene oxide that graft type is magnetic/functionalized
By amination graphene oxide suspension, Fe containing surface carboxyl groups3O4The solution of magnetic nano-particle and EDAC
(Ethyldimethylaminopropyl carbodiimides) or pyridine or dibutyl tin laurate mixing, 10～25 DEG C reaction 10～
28h, then collects the product obtained, washing, 50～70 DEG C of vacuum drying, can obtain described graft type magnetic merit with Magnet
The graphene oxide of energyization；
The parts by weight of component are:
Amination graphene oxide suspension 100 parts
Fe containing surface carboxyl groups3O4The solution 30 of magnetic nano-particle～50 parts
EDAC (Ethyldimethylaminopropyl carbodiimides) or pyridine etc. 0.1～0.5 part
Preferably, the parts by weight of component are:
Amination graphene oxide suspension 100 parts
Fe containing surface carboxyl groups3O4The solution 35 of magnetic nano-particle～45 parts
EDAC (Ethyldimethylaminopropyl carbodiimides) or pyridine etc. 0.15～0.3 part
(4) the preparation magnetic/functionalized graphite oxide alkene polymer containing orientations.
Graphene oxide that the graft type that step (3) obtained is magnetic/functionalized and polymer mixed, then at the action of a magnetic field
Lower melted mold pressing, can obtain the polymer of the described magnetic oxygenated graphene film containing orientations；
Or:
Graphene oxide that the graft type that step (3) obtained is magnetic/functionalized and polymer mixed, then at the action of a magnetic field
Lower melt-blown, can obtain the thin polymer film of the described magnetic oxygenated graphene film containing orientations；
Or:
Graphene oxide that the graft type that step (3) obtained is magnetic/functionalized and polymer mixed, then at the action of a magnetic field
Lower solution coating (including spin-coating, knifing etc.), can obtain the described magnetic oxygenated graphene film containing orientations
Thin polymer film；
The present invention contains the polymer of the magnetic oxygenated graphene film of graft type of orientations, can be applicable to various fields,
As prepared by packing film, various container bottle, record standby etc..
The invention has the beneficial effects as follows:
Variable uniform magnetic field is used to guide technique to realize controlled in base polymer material of magnetic oxygenated graphene film
Align, thus substantially increase the barrier property of gas, liquid etc., solve thin polymer film present in prior art
Or the problem of container barrier difference.Utilize prepared by the inventive method containing the controlled magnetic oxygenated graphite of the graft type aligned
The polymer of alkene sheet, not only has the high intensity of graphene oxide, and can obtain big wide thick ratio, high specific surface area and
Surface texture, also has nanometer Fe closely3O4The magnetic of particle, it is achieved thereby that its functionalization.Next to that uniform magnetic field guides
The technique preparing magnetic oxygenated graphene sheet composite material, it is achieved that graphene oxide sheet controlled orientation row in the polymer
Row, thus substantially increase polymer composites to gaseous state or the barrier property of liquid and the machine of composite
Tool intensity.
Accompanying drawing explanation
Fig. 1 embodiment 2 contains the structural representation of the polymer of the magnetic oxygenated graphene film aligned.
The magnetic oxygenated graphene film floor map that in Fig. 2 embodiment 1, surface portion is covered by montmorillonite.
Fe in Fig. 3 embodiment 13O4The XRD figure of magnetic particle.
The SEM figure of magnetic oxygenated graphene film in Fig. 4 embodiment 1.
In Fig. 5 embodiment 1, magnetic oxygenated graphene film is applied in polymer (non-magnetic field guiding) SEM figure.
In Fig. 6 embodiment 1, magnetic oxygenated graphene film is applied in polymer (introduction by magnetic field) SEM figure.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
Embodiment 1
Weigh 10gP2O5、10gK2S2O8Being mixed in 250ml beaker, put into magneton, ice bath stirring is lower adds 150g weight
Concentration is the H of 98%2SO4React and clarify to system, add 400mg expanded graphite, at 90 DEG C, stir 4.5h.With ice bath by body
System cools down, and the lower 2000g deionized water that adds of stirring, sand core funnel sucking filtration, deionized water wash solid is to neutrality, vacuum drying oven
Drying at 50 DEG C, the amount of above-mentioned product is about 500mg, adds in there-necked flask, and adding 184g weight concentration is the H of 98%2SO4
Reaction, the lower 10g potassium permanganate that adds of ice bath stirring, 50 DEG C of reaction 2h, add 1000g deionized water under ice bath, go in large beaker,
H is dripped under stirring2O2Being yellow to system, centrifugation, regulating final pH value is 7, is dried, obtains graphene oxide；
Then 0.15g graphene oxide and the montmorillonite that 0.05g sheet footpath is 1-20nm are scattered in 150g deionized water,
Ultrasonic disperse 60min, obtains the graphene oxide sheet suspension that surface portion is covered by montmorillonite, and surface portion is covered by montmorillonite
The structure of the graphene oxide sheet of lid is shown in Fig. 2, and wherein, 3 represent magnetic nano-particle, and 4 represent montmorillonite sheet, and 5 represent oxidation stone
Ink alkene sheet；
Then weigh 1.35g p-phenylenediamine to be dissolved in 142gDMF, then by two homogeneous dispersion mixing, under stirring in
Reacting 12h in 70 DEG C of water-baths, reaction terminates rear centrifugation, it is thus achieved that amination graphene oxide suspension A；
By the Fe that 0.6g mean diameter is 10 nanometers3O4Nanoparticle, with 8g hexamethylene, 0.015g oleic acid and 0.015g oil
Amine mixes, ultrasonic disperse, centrifugal (8000r min-1) 30min, collect precipitation, add 8g hexamethylene, 0.015g oleic acid wherein
With 0.015g oleyl amine, ultrasonic disperse. centrifugal (6000r min again-1) 30min, collect precipitation, it is thus achieved that oil-soluble Fe3O4Nanometer
Particle；
By the oil-soluble Fe of 20mg3O4Nanoparticle, is dissolved in 1.5g toluene；
20mgDMSA (dimercaptosuccinic acid) is dissolved in 2gDMSO (dimethyl sulfoxide), is then added to Fe3O4Nanometer
In the toluene solution of particle, stirring reaction 12h at 25 DEG C；After reaction terminates, add 1g ethyl acetate precipitation in the solution, use
Magnet collects precipitation, is repeated 3 times, then cleans 3 times with ultra-pure water, is dissolved in the water of 2g, regulates its pH with sodium hydroxide
To 7, i.e. obtain water solublity and well contained the magnetic nano-particle (Fe of surface carboxyl groups3O4-DMSA) solution B；
Fig. 3 is Fe3O4The XRD figure spectrum of magnetic nanoparticle, has obvious Fe in collection of illustrative plates3O4Nanoparticle characteristic peak；
In the round-bottomed flask of amination graphene oxide suspension A containing 3g, add 1.2g containing surface carboxyl groups
Magnetic nano-particle (the Fe changed3O4-DMSA) solution B, (Ethyldimethylaminopropyl carbodiimides, 20 DEG C are stirred 0.2gEDAC
Mix lower reaction 24h, after reaction terminates, be enriched with the product obtained with Magnet, clean three times with ultra-pure water, remove in solution the most anti-
The EDAC answered, 60 DEG C of vacuum drying, i.e. obtain the graphene oxide composite material C that graft type is magnetic/functionalized, magnetic Fe3O4Particle
Spacing in surface of graphene oxide is 8-30nm.Fig. 4 is magnetic/functionalized graphene oxide composite material SEM picture；
By graphene oxide composite material C magnetic/functionalized for 0.1 above-mentioned weight portion graft type and the poly-second of 100 weight portions
Alkene is blended, and then under the action of a magnetic field, melted molds, and can obtain described containing the controlled graft type magnetic oxygen aligned
The polyethylene of functionalized graphene sheet；
The melted device molded includes mould and is arranged on the Magnet of described mould upper and lower side, Magnet magnetic size according to
Required degree of orientation scalable；
Under the action of a magnetic field, the magnetic/functionalized graphene oxide composite material C of graft type aligns along magnetic direction
In polyethylene, the scanning electron microscope (SEM) of material is shown in Fig. 6.
By graphene oxide composite material C magnetic/functionalized for 0.1 above-mentioned weight portion graft type and the poly-second of 100 weight portions
Alkene is blended, and directly melted molds (being not added with magnetic field), it is thus achieved that the polymer of the magnetic oxygenated graphene film of graft type, sweeping of its material
Retouch Electronic Speculum (SEM) and see Fig. 5.
Can be seen that when being not added with magnetic field, magnetic oxygenated graphene film is distributed at random in polyethylene, unordered say.
By graphene oxide composite material C magnetic/functionalized for 0.5 above-mentioned weight portion graft type and the poly-second of 100 weight portions
Alkene is blended, then under the action of a magnetic field, melt-blown, it is thus achieved that the graft type containing orientations magnetic oxygenated graphene film
The thin film of polyethylene.
Blowing device includes mould and is arranged on the Magnet of the upper and lower both sides of described blow mold, and Magnet magnetic size is according to institute
Need degree of orientation scalable.
Polyethylene is selected to prepare film forming as polymeric matrix.
The saturating CO of polyethylene film2Coefficient is 3.379 × 10-15cm3.cm(cm2.s.Pa)-1, rate of perviousness is 5.65g/
(m2.24h)；In the present embodiment, being not added with adding under magnetic field condition, magnetic oxygenated graphene film content is the saturating CO of 0.1%2Coefficient is
0.0356×10-15cm3.cm(cm2.s.Pa)-1, have dropped 94.9 times, rate of perviousness also drops to 2.032g/ (m2.24h)；Magnetic
Graphene oxide sheet content is the saturating CO of 0.5%2Coefficient is 0.0082 × 10-15cm3.cm(cm2.s.Pa)-1, have dropped 412.1
Times, rate of perviousness also drops to 1.637g/ (m2.24h)。
Add under magnetic field condition, it is achieved that it is 0 degree that the angle of orientation is perpendicular to the direction in magnetic field, the i.e. angle of orientation, obtained complex
At the saturating CO that magnetic oxygenated graphene film content is 0.1%2Coefficient is: 0.0052 × 10-15cm3.cm(cm2.s.Pa)-1, decline
649.8 times, rate of perviousness also drops to 1.085g/ (m2.24h)；Magnetic oxygenated graphene film content is the saturating CO of 0.5%2Coefficient
It is 0.0025 × 10-15cm3.cm(cm2.s.Pa)-1, have dropped 1351.6 times, rate of perviousness also drops to 1.178g/ (m2.24h)。
Embodiment 2
Weigh 10gP2O5、10gK2S2O8Being mixed in 250ml beaker, put into magneton, ice bath stirring is lower adds 150g weight
Concentration is the H of 98%2SO4React to system clarification (if do not clarified, can heat).Add 400mg graphite (expanded graphite) in 90
4.5h is stirred at DEG C.System being cooled down with ice bath, stirring is lower adds 2000g deionized water, is diluted to a certain degree, sand core funnel
Sucking filtration, deionized water wash solid to filtrate, close to neutral, is dried at 50 DEG C of vacuum drying oven.The amount of above-mentioned product about 500mg,
Adding in there-necked flask, adding 184g weight concentration is the H of 98%2SO4Reaction, is slowly added to 10g potassium permanganate under ice bath stirring
(K2MnO4), 50 DEG C of reaction 2h.Enter 1000g deionized water under ice bath, go in large beaker, under stirring, drip H2O2To system in
Yellow, centrifugation, regulating final pH value is 7, is drying to obtain graphene oxide.
Then 0.3g graphene oxide is scattered in the montmorillonite that 0.1g sheet footpath is 1-20nm divide with in 300g deionized water,
Ultrasonic disperse 30min, obtains the graphene oxide sheet suspension that surface portion is covered by montmorillonite；
Then weigh 2.7g this diamidogen is dissolved in 284gDMF, then by two homogeneous dispersion mixing, in 80 under stirring
Reacting 16h in DEG C water-bath, reaction terminates rear centrifugation, both amination graphene oxide sheet suspending liquid A.
By the Fe that 1.2g mean diameter is 15 nanometers3O4Nanoparticle, with 16g hexamethylene, 0.03g oleic acid and 0.03g oleyl amine
Mixing, ultrasonic disperse, centrifugal (8000r min-1) 30min, collect precipitation, wherein add 16g hexamethylene, 0.03g oleic acid and
0.03g oleyl amine, ultrasonic disperse. centrifugal (6000r min again-1) 30min, collect precipitation, it is thus achieved that oil-soluble Fe3O4Nanoparticle
Son；
By the oil-soluble Fe of 40mg3O4Nanoparticle, is dissolved in 3g toluene；
40mgDMSA (dimercaptosuccinic acid) is dissolved in 4gDMSO (dimethyl sulfoxide), is then added to Fe3O4Nanometer
In the toluene solution of particle, stirring reaction 14h at 28 DEG C；After reaction terminates, add 2g ethyl acetate precipitation in the solution, use
Magnet collects precipitation, is repeated 3 times, then cleans 3 times with ultra-pure water, is dissolved in the water of 4g. regulate its pH with sodium hydroxide
To 7, i.e. obtain water solublity and well contained the magnetic nano-particle (Fe of surface carboxyl groups3O4-DMSA) solution B；
In the round-bottomed flask of amination graphene oxide suspension A containing 4g, add 2.4g containing surface carboxyl groups
Magnetic nano-particle (the Fe changed3O4-DMSA) solution B, (Ethyldimethylaminopropyl carbodiimides, 22 DEG C are stirred 0.4gEDAC
Mix lower reaction 28h, after reaction terminates, be enriched with the product obtained with Magnet, clean three times with ultra-pure water, remove in solution the most anti-
The EDAC answered, 60 DEG C of vacuum drying, i.e. obtain the graphene oxide composite material C that graft type is magnetic/functionalized；
Poly-to benzene by graphene oxide composite material C magnetic/functionalized for 1 above-mentioned weight portion graft type and 100 weight portions
Naphthalate (PET) is blended, then under the action of a magnetic field, and melted mold pressing, described containing can be obtained and align
The polyethylene terephthalate (PET) of the magnetic oxygenated graphene film of graft type；
The melted device molded includes mould and is arranged on the Magnet of described mould upper and lower side, Magnet magnetic size according to
Required degree of orientation scalable.
Under the action of a magnetic field, the magnetic/functionalized graphene oxide composite material C of graft type aligns along magnetic direction
In polyethylene terephthalate (PET), such as Fig. 1, wherein: 1 represents polyethylene terephthalate, 2 represent magnetic merit
The graphene oxide composite material of energyization；B represents magnetic field, and the arrow below B represents magnetic direction；
Poly-to benzene by graphene oxide composite material C magnetic/functionalized for 1 above-mentioned weight portion graft type and 100 weight portions
Naphthalate (PET) is blended, directly melted mold (being not added with magnetic field), it is thus achieved that the magnetic oxygenated graphene film of graft type
Polymer；
Can be seen that when being not added with magnetic field, the magnetic oxygenated graphene film of graft type is at polyethylene terephthalate (PET)
Middle distribution is at random, unordered says.
Poly-to benzene by graphene oxide composite material C magnetic/functionalized for 2 above-mentioned weight portion graft types and 100 weight portions
Naphthalate (PET) be blended, then under the action of a magnetic field, melt-blown, it is thus achieved that the graft type magnetic containing orientations
The thin film of the polyethylene of property graphene oxide sheet.
Blowing device includes mould and is arranged on the Magnet of the upper and lower both sides of described blow mold, and Magnet magnetic size is according to institute
Need degree of orientation scalable.
Polyethylene terephthalate (PET) is selected to prepare film forming as polymeric matrix.
The saturating O of pet film2Coefficient is 1.872 × 10-15cm3.cm(cm2.s.Pa)-1, moisture-inhibiting
Rate is 4.35g/ (m2.24h)；In the present embodiment, being not added with adding under magnetic field condition, magnetic oxygenated graphene film content is the saturating O of 1%2
Coefficient is 0.0342 × 10-15cm3.cm(cm2.s.Pa)-1, have dropped 54.7 times, rate of perviousness also drops to 2.030g/
(m2.24h)；Magnetic oxygenated graphene film content is the saturating O of 2%2Coefficient is 0.0080 × 10-15cm3.cm(cm2.s.Pa)-1Under,
Having dropped 234 times, rate of perviousness also drops to 1.626g/ (m2.24h).Add under magnetic field condition, it is achieved that the angle of orientation is perpendicular to magnetic field
Direction, the i.e. angle of orientation are 0 degree, and obtained complex is at the saturating O that magnetic oxygenated graphene film content is 1%2Coefficient is 0.0050
×10-15cm3.cm(cm2.s.Pa)-1, have dropped 374.4 times, rate of perviousness also drops to 1.798g/ (m2.24h)；Magnetic oxygenated stone
Ink alkene sheet content is the saturating O of 2%2Coefficient is 0.0024 × 10-15cm3.cm(cm2.s.Pa)-1, have dropped 780 times, rate of perviousness is also
Drop to 1.182g/ (m2.24h)。
Embodiment 3
Weigh 10gP2O5、10gK2S2O8Being mixed in 250ml beaker, put into magneton, ice bath stirring is lower adds 150g weight
Concentration is the H of 98%2SO4React and clarify to system, add 400mg expanded graphite, at 90 DEG C, stir 4.5h.With ice bath by body
System cools down, and the lower 2000g deionized water that adds of stirring, sand core funnel sucking filtration, deionized water wash solid is to neutrality, vacuum drying oven
Drying at 50 DEG C, the amount of above-mentioned product is about 500mg, adds in there-necked flask, and adding 184g weight concentration is the H of 98%2SO4
Reaction, the lower 10g potassium permanganate that adds of ice bath stirring, 50 DEG C of reaction 2h, add 1000g deionized water under ice bath, go in large beaker,
H is dripped under stirring2O2Being yellow to system, centrifugation, regulating final pH value is 7, is dried, obtains graphene oxide；
Then 0.45g graphene oxide and the montmorillonite that 0.2g sheet footpath is 1-20nm are scattered in 450g deionized water,
Ultrasonic disperse 30-60min, obtains the graphene oxide sheet suspension that surface portion is covered by montmorillonite；
Then weigh 3.2g p-phenylenediamine to be dissolved in 336gDMF, then by two homogeneous dispersion mixing, in 90 under stirring
Reacting 24h in DEG C water-bath, reaction terminates rear centrifugation, it is thus achieved that amination graphene oxide suspension A；
By the Fe that 1.5g mean diameter is 20 nanometers3O4Nanoparticle, with 20g hexamethylene, 0.0375g oleic acid and 0.0375g
Oleyl amine mixes, ultrasonic disperse, centrifugal (8000r min-1) 30min, collect precipitation, add 20g hexamethylene, 0.0375g wherein
Oleic acid and 0.0375g oleyl amine, ultrasonic disperse. centrifugal (6000r min again-1) 30min, collect precipitation, it is thus achieved that oil-soluble
Fe3O4Nanoparticle；
By the oil-soluble Fe of 60mg3O4Nanoparticle, is dissolved in 4.5g toluene；
60mgDMSA (dimercaptosuccinic acid) is dissolved in 3gDMSO (dimethyl sulfoxide), is then added to Fe3O4Nanometer
In the toluene solution of particle, stirring reaction 16h at 30 DEG C；After reaction terminates, add 3g ethyl acetate precipitation in the solution, use
Magnet collects precipitation, is repeated 3 times, then cleans 3 times with ultra-pure water, is dissolved in the water of 5g.Its pH is regulated with sodium hydroxide
To 7, i.e. obtain water solublity and well contained the magnetic nano-particle (Fe of surface carboxyl groups3O4-DMSA) solution B；
In the round-bottomed flask of amination graphene oxide suspension A containing 5g, add 3.6g containing surface carboxyl groups
Magnetic nano-particle (the Fe changed3O4-DMSA) solution B, 0.25gEDAC (Ethyldimethylaminopropyl carbodiimides, 24 DEG C
React 32h under stirring, after reaction terminates, be enriched with the product obtained with Magnet, clean three times with ultra-pure water, in removing solution not
The EDAC of reaction, 60 DEG C of vacuum drying, i.e. obtain the graphene oxide composite material C that graft type is magnetic/functionalized；
By graphene oxide composite material C magnetic/functionalized for 2 above-mentioned weight portion graft types and the poly-breast of 100 weight portions
Acid, then under the action of a magnetic field, melted mold pressing, the described magnetic oxygenated Graphene of the graft type containing orientations can be obtained
The polylactic acid of sheet；
The melted device molded includes mould and is arranged on the Magnet of described mould upper and lower side, Magnet magnetic size according to
Required degree of orientation scalable.
Under the action of a magnetic field, the magnetic/functionalized graphene oxide composite material C of graft type aligns along magnetic direction
In polylactic acid.
By graphene oxide composite material C magnetic/functionalized for 2 above-mentioned weight portion graft types and the polylactic acid of 100 weight portions
Be blended, directly melted mold (being not added with magnetic field), it is thus achieved that the polymer of the magnetic oxygenated graphene film of graft type.
Can be seen that when being not added with magnetic field, the magnetic oxygenated graphene film of graft type is distributed at random in polylactic acid, unordered say.
By graphene oxide composite material C magnetic/functionalized for 3 above-mentioned weight portion graft types and the polylactic acid of 100 weight portions
Be blended, then under the action of a magnetic field, room temperature compression molding, it is thus achieved that containing the magnetic oxygenated graphene film of graft type that aligns
The thin film of polylactic acid.
Molding device includes mould and is arranged on the Magnet Magnet magnetic size of the upper and lower both sides of described molding die according to institute
Need degree of orientation scalable.
Polylactic acid is selected to prepare film forming as polymeric matrix.
The saturating N of polylactic acid film2Coefficient is 3.552 × 10-12cm3.cm(cm2.s.Pa)-1, rate of perviousness is 7.54g/
(m2.24h)；In the present embodiment, being not added with adding under magnetic field condition, magnetic oxygenated graphene film content is the saturating N of 2%2Coefficient is
0.0248×10-12cm3.cm(cm2.s.Pa)-1, have dropped 143.2 times, rate of perviousness also drops to 3.245g/ (m2.24h)；Magnetic
Graphene oxide sheet content is the saturating N of 3%2Coefficient is 0.0064 × 10-12cm3.cm(cm2.s.Pa)-1, have dropped 555 times, thoroughly
Wet rate also drops to 1.836g/ (m2.24h).Add under magnetic field condition, it is achieved that the angle of orientation is perpendicular to the direction in magnetic field, is i.e. orientated
Angle is 0 degree, and obtained complex is at the saturating N that magnetic oxygenated graphene film content is 2%2Coefficient is 0.00382 × 10-12cm3.cm
(cm2.s.Pa)-1, have dropped 929.8 times, rate of perviousness also drops to 1.220g/ (m2.24h)；Magnetic oxygenated graphene film content
It is the saturating N of 3%2Coefficient is 0.00214 × 10-12cm3.cm(cm2.s.Pa)-1Have dropped 1659.8 times, rate of perviousness also drops to
1.026g/(m2.24h)。
Claims (4)
1. contain the preparation method of the polymer of the magnetic oxygenated graphene film of orientations, it is characterised in that include walking as follows
Rapid:
(1) amination graphene oxide suspension is prepared:
P-phenylenediamine is dissolved in DMF (DMF), add through hot soarfing from montmorillonite-based nano sheet, oxidation
Graphene and the suspension of water, 80～100 DEG C of reactions 10～14h, it is thus achieved that amination graphene oxide suspension；
(2) magnetic nano-particle is prepared:
By Fe3O4Magnetic nanoparticle adds in hexamethylene, oleic acid and oleyl amine, and then ultrasonic disperse collects oil-soluble Fe3O4Receive
Rice corpuscles；
The oil-soluble Fe that will be obtained3O4Nanoparticle dissolution is in toluene, then with the dimethyl sulfoxide of dimercaptosuccinic acid
Solution mixes, 10～30 DEG C of reactions 8～14h, is subsequently adding ethyl acetate, collects precipitation, washing with Magnet, is subsequently adding water,
Regulate its pH to 7-8, obtain the Fe containing surface carboxyl groups3O4The solution of magnetic nano-particle；
(3) preparation of the graphene oxide that graft type is magnetic/functionalized
By amination graphene oxide suspension, Fe containing surface carboxyl groups3O4The solution of magnetic nano-particle and ethyl diformazan
Base amine carbodiimide or pyridine mixing, 10～25 DEG C of reactions 10～28h, the product obtained then is collected with Magnet
Thing, washing, vacuum drying, the graphene oxide that described graft type is magnetic/functionalized can be obtained；
(4) the preparation magnetic/functionalized graphite oxide alkene polymer containing orientations:
Graphene oxide that the graft type that step (3) obtained is magnetic/functionalized and polymer mixed, then molten under the action of a magnetic field
Melt mold pressing, the polymer of the described magnetic oxygenated graphene film containing orientations can be obtained；
Or:
Graphene oxide that the graft type that step (3) obtained is magnetic/functionalized and polymer mixed, then molten under the action of a magnetic field
Melt blowing, the thin polymer film of the magnetic oxygenated graphene film containing orientations can be obtained；
Or:
Graphene oxide that the graft type that step (3) obtained is magnetic/functionalized and polymer mixed, then molten under the action of a magnetic field
Liquid is coated with, and can obtain the thin polymer film of the magnetic oxygenated graphene film containing orientations；
In step (1), in DMF solution:
The weight percent content of p-phenylenediamine is 0.08%～8%；
The weight percent content of graphene oxide is 0.1%～1%；
Described hot soarfing from montmorillonite-based nano sheet weight consumption is graphene oxide 1%～50%, in step (2), group
The parts by weight divided are:
In step (3), the parts by weight of component are:
Amination graphene oxide suspension 100 parts
Fe containing surface carboxyl groups3O4The solution 30 of magnetic nano-particle～50 parts
Ethyldimethyl amine carbodiimide or pyridine 0.1～0.5 part.
Method the most according to claim 1, it is characterised in that described polymer is selected from polyolefin, polyester, rubber, poly-first
Aldehyde or polysulfones.
Method the most according to claim 1, it is characterised in that with described total polymer gauge, described graft type magnetic
The weight percent content of the graphene oxide sheet of functionalization is 0.05～5%.
Method the most according to claim 1, it is characterised in that the magnetic of magnetic/functionalized graphene oxide sheet surface grafting
The spacing of particle is at least 8nm.
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