CN103897244A - Method for preparing high-barrier graphene oxide-polyethylene nano composite film - Google Patents

Method for preparing high-barrier graphene oxide-polyethylene nano composite film Download PDF

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CN103897244A
CN103897244A CN201410085275.XA CN201410085275A CN103897244A CN 103897244 A CN103897244 A CN 103897244A CN 201410085275 A CN201410085275 A CN 201410085275A CN 103897244 A CN103897244 A CN 103897244A
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graphene oxide
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polyethylene
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stir
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CN103897244B (en
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任鹏刚
张晓亮
任联振
张媛
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Shanghai Chaidai New Material Technology Co., Ltd.
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Xian University of Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
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    • C08L2201/14—Gas barrier composition
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    • C08L2203/16—Applications used for films
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene

Abstract

The invention discloses a method for preparing a high-barrier graphene oxide-polyethylene nano composite film. The method comprises the following steps: ultrasonically dispersing modified graphene oxide into xylene and heating; then adding high-density polyethylene and stirring so as to obtain an ODA-GO/HDP mixed solution; cleaning an ultra-high molecular weight polyethylene film by xylene; after xylene is evaporated, soaking a UHMWPE film into a hot ODA-GO/HDPE mixed solution in a dipping manner; drying; and repeating the above steps until the required layer quantity is reached. The high-barrier graphene oxide-polyethylene nano composite film prepared by the method is high in safety and good in environmental protection property; the oxygen permeating coefficient is reduced by about 49%; the nano composite film has ultra-high oxygen barrier property, can meet the packaging requirements of a plurality of foods and drugs and use of other products, is simple in process and low in cost, and has broad practicability and promotional value.

Description

The preparation method of graphene oxide with high barrier-polyethylene nano compound film
Technical field
The invention belongs to high molecule nano composite material preparing technical field, be specifically related to a kind of preparation method of graphene oxide with high barrier-polyethylene nano compound film.
Background technology
In recent years, olefin polymer is because of its excellent mechanical property, outstanding moulding processability, good chemical stability and cheap etc., in food, pharmaceuticals packing, obtain application more and more widely, but not good its key issue applied in packing of restriction that becomes of barrier properties for gases, for meeting the need of market, improving its gas barrier property has become the important directions of research.At present, the method that improves polymer barrier property mainly contains vacuum evaporation, multi-layer co-extruded compound and laminar nano filler is compound.Wherein, laminar nano filler is compound is the focus that people pay close attention in recent years, this system is to utilize polymkeric substance and the good interface interaction of filler and nanoscale twins filler in polymeric matrix, to cause " multipath effect " or " nanometer barrier wall effect " of gas-permeable, effectively improve the barrier property of polymeric matrix, the plurality of advantages such as that though the method has is easy to process, product cost performance height, but also exist Nano filling and polymer-based carbon body interface to be difficult for the problem of combination, its film forming thickness is also uncontrollable, has limited the range of application of this technology.
Layer-by-layer is the method for preparing order thin film that development in recent years is got up.It utilizes the electrostatic adhesion characteristic of organic or inorganic zwitterion, forms film by the alternately molecule deposition of gegenion system.This technology has film forming and is not subject to the restrictions such as substrate kind, shape, size, chemical constitution and the thickness of film are controlled, preparation process is simple, facilitates scale operation, and these advantages make self-assembled film layer by layer become scientific circles to improve the study hotspot of polymkeric substance barrier property.
Patent CN101474897A discloses a kind of grapheme-organic material layered assembling film and preparation method thereof.It is take grapheme material and organic materials as raw material, utilize the interactions such as static, hydrogen bond, coordinate bond or electric charge transfer between Graphene and organic materials, by the method for manufacturing thin film such as spin coating, spraying, dipping-the lift film forming that is layering, every tunic is thick can be controlled at 10nm-2mm as required.Feature is to utilize the electricity of Graphene uniqueness, magnetic, mechanics and chemical property, according to the difference of selected organic materials, prepare the multilayered film material with difference in functionality, can be used as the manufacture of biomaterial, electro-conductive material, electromagnetic shielding and absorbing material, Precision Instrument and Machinery device.
The present invention, by compound comprehensive stratiform Nano filling and layer-by-layer, provides a kind of preparation method of graphene oxide with high barrier-polyethylene nano compound film.
Summary of the invention
The object of this invention is to provide a kind of preparation method of graphene oxide with high barrier-polyethylene nano compound film, adopt layer-by-layer to make and there is the nano compound film of structure layer by layer, have superelevation oxygen-barrier property its, and safe, the feature of environmental protection is good.
The technical solution adopted in the present invention is, the preparation method of graphene oxide with high barrier-polyethylene nano compound film, and concrete steps are as follows:
Step 1, graphene oxide (GO) 0.1～0.3g prepared by the Hummer method of modification is dispersed in 80～120ml distilled water and ultrasonic agitation 1～2h, to join in GO suspension containing the alcohol mixeding liquid of 1～2g octadecylamine (ODA) and at room temperature stir 24～30h, the product obtaining is repeatedly cleaned in water-ethanol mixed solution to the then vacuum-drying under 55～65 ℃ of conditions of purifying, obtain ODA-GO;
Step 2, ODA-GO that step 1 is obtained is ultrasonic to be scattered in 150～200ml dimethylbenzene and to be heated to 135～145 ℃, then by the high density polyethylene(HDPE) of 15～25mg (HDPE) grain dissolution in above-mentioned solution and continuously stirring, finally obtain hot ODA-GO/HDPE mixing solutions;
Step 3, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film is cleaned with dimethylbenzene, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 2 being obtained by the mode of dipping in film, then dry 3～5min in baking oven, repeats this step, is layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
Feature of the present invention is also,
The detailed process that the Hummer method of modification in step 1 is prepared graphene oxide is:
The first step, takes first respectively 3～5g K 2s 2o 8, 3～5g P 2o 5with 5～7g powdered graphite, mix, then add 20～30ml vitriol oil and after constant temperature stirring 4～5h, be cooled to room temperature at 75～85 ℃, after adding 1～1.5L distilled water, stir 12～14 hours, to remove residual part acid, dry product 24～30h can be obtained to the graphite of preoxidation with the micropore filter paper filtering of 0.4～0.5 μ m;
Second step, the graphite of the preoxidation that the first step is obtained is added in 240～250ml vitriol oil, constantly stirs and in ice bath, adds 25～35g KMnO 4, add 450～550ml distilled water diluting stir 2～3h at 30～40 ℃ after, continue to stir 1～2h, then add 1～1.5L distilled water, continue to stir, finally add 40～50ml, 25～35% H 2o 2solution continues to be stirred to solution and is light yellow, filters washing, the in a vacuum dry graphite oxide that obtains at 50～60 ℃;
The 3rd step, the graphite oxide that second step is obtained is dissolved in the distilled water of 100～200ml, and ultrasonic dispersion 30～40min, obtains graphene oxide.
In step 1, in water-ethanol mixed solution, the volume ratio of water and ethanol is 1:1.
The invention has the beneficial effects as follows, the preparation method of graphene oxide with high barrier-polyethylene nano compound film of the present invention, the main layer-by-layer that adopts, polyethylene film is immersed in (135～145 ℃) mixing solutions of heat, repeatedly makes and there is the nano compound film of structure layer by layer; Graphene oxide with high barrier-polyethylene the nano compound film preparing is safe, the feature of environmental protection is good, Oxygen Coefficients has declined approximately 49% thoroughly, there is superelevation oxygen-barrier property, can meet the requirement of numerous food, drug packaging and the purposes of other products, and technique is simple, with low cost, there is practicality and promotional value widely.
Accompanying drawing explanation
Fig. 1 is the permeable model figure of gas in graphene oxide with high barrier-polyethylene nano compound film preparation method of the present invention;
Fig. 2 is the SEM figure of graphene oxide with high barrier-polyethylene nano compound film of preparing of embodiment 1;
Fig. 3 is the FTIR curve of graphene oxide and amino modified graphene oxide in embodiment 1;
Fig. 4 is the XRD curve of graphene oxide and amino modified graphene oxide in embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The preparation method of graphene oxide with high barrier-polyethylene nano compound film of the present invention, concrete steps are as follows:
Step 1, the Hummer method of modification is prepared graphene oxide
First take respectively 3～5g K 2s 2o 8, 3～5g P 2o 5with 5～7g powdered graphite, mix, then add 20～30ml vitriol oil and after constant temperature stirring 4～5h, be cooled to room temperature at 75～85 ℃, after adding 1～1.5L distilled water, stir 12～14 hours, to remove residual part acid, dry product 24～30h can be obtained to the graphite of preoxidation with the micropore filter paper filtering of 0.4～0.5 μ m;
The graphite of preoxidation is added in 240～250ml vitriol oil, constantly stirs and in ice bath, add 25～35g KMnO 4, add 450～550ml distilled water diluting stir 2～3h at 30～40 ℃ after, continue to stir 1～2h, then add 1～1.5L distilled water, continue to stir, finally add 40～50ml, 25～35% H 2o 2solution continues to be stirred to solution and is light yellow, filters washing, the in a vacuum dry graphite oxide that obtains at 50～60 ℃;
Graphite oxide is dissolved in the distilled water of 100～200ml, ultrasonic dispersion 30～40min, obtains graphene oxide;
Step 2, graphene oxide (GO) 0.1～0.3g prepared by step 1 is dispersed in 80～120ml distilled water and ultrasonic agitation 1～2h, to join in GO suspension containing the alcohol mixeding liquid of 1～2g octadecylamine (ODA) and at room temperature stir 24～30h, the product obtaining is repeatedly cleaned in water-ethanol mixed solution (volume ratio of water and ethanol is 1:1) to the then vacuum-drying under 55～65 ℃ of conditions of purifying, obtain ODA-GO;
Step 3, ODA-GO that step 2 is obtained is ultrasonic to be scattered in 150～200ml dimethylbenzene and to be heated to 135～145 ℃, then by the high density polyethylene(HDPE) of 15～25mg (HDPE) grain dissolution in above-mentioned solution and continuously stirring, finally obtain hot ODA-GO/HDPE mixing solutions;
Step 4, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film is cleaned with dimethylbenzene, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 2 being obtained by the mode of dipping in film, then dry 3～5min in baking oven, repeats this step, is layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
The mechanism of action of the present invention is: the infiltration of gas molecule in film is a microprocess that adsorbs, dissolves, spreads and separate out.First gas molecule contacts with film, dissolve subsequently, thereby both sides, film surface produces concentration ladder at film surface enrichment.Under the effect of concentration difference, " moment hole " that gas molecule occurs using macromolecular chain segment strenuous exercise, finally arrives the opposite side of film and separates out progressively at film internal diffusion as passage, the general mechanism of Here it is film breathable.
Amino modified graphene oxide, under Ultrasonic Heating effect, can be dispersed in xylene solution, and forms mixed uniformly suspension with high-density polyethylene powder, and hot steeping process makes to form between mixing solutions and film good interface effect.
As shown in Figure 1, because modified graphene oxide skeleton is to be combined closely and formed by carbon atom, in the time that gas molecule runs into graphene oxide lamella, can not directly penetrate, can only walk around along modified graphene oxide lamella direction, this reduces the permeable area of gas; And spacing between modified graphene oxide lamella is very little, the modified graphene oxide lamella adding makes gas diffusion path become from the direction of vertical film the direction that is parallel to film, and the permeation pathway of gas is increased.The effect of modified graphene oxide nanometer barrier wall has significantly improved the barrier property of ultrahigh molecular weight polyethylene(UHMWPE) film, makes the saturating Oxygen Coefficients of the nano compound film that contains modified graphene oxide decline 48.7 times.
The preparation method of graphene oxide with high barrier-polyethylene nano compound film of the present invention, the main layer-by-layer that adopts, polyethylene film is immersed in (135～145 ℃) mixing solutions of heat, repeatedly makes and there is the nano compound film of structure layer by layer; Graphene oxide with high barrier-polyethylene the nano compound film preparing is safe, the feature of environmental protection is good, Oxygen Coefficients has declined approximately 49% thoroughly, there is superelevation oxygen-barrier property, can meet the requirement of numerous food, drug packaging and the purposes of other products, and technique is simple, with low cost, there is practicality and promotional value widely.
Embodiment 1
Step 1, the preparation of graphene oxide
First take respectively 5g K 2s 2o 8, 5g P 2o 5with 6g powdered graphite, mix, then add the 25ml vitriol oil and at 80 ℃ constant temperature stir after 5 hours and be cooled to room temperature, stir 12 hours after adding 1L distilled water, to remove residual part acid, product is dried to the graphite that obtains preoxidation for 24 hours with the micropore filter paper filtering of 0.45 μ m;
The graphite of preoxidation is added in the 250ml vitriol oil, constantly stirs and in ice bath, add 30gKMnO 4, at 40 ℃, stir after 2 hours and add 500ml distilled water diluting, continue to stir 2 hours, then add 1.5L distilled water, continue to stir, finally add 40ml, 30% H 2o 2solution continues to be stirred to solution and is light yellow, filters washing, the in a vacuum dry graphite oxide that obtains at 60 ℃;
Graphite oxide is dissolved in the distilled water of 150ml, ultrasonic dispersion 30min, obtains graphene oxide;
Step 2, the modification of graphene oxide
Graphene oxide (GO) 0.2g prepared by step 1 is dispersed in 100ml distilled water and ultrasonic agitation 1.5h, to join in GO suspension containing the alcohol mixeding liquid of 1.5g octadecylamine (ODA) and at room temperature stir 24 hours, the product obtaining is repeatedly cleaned in water-ethanol mixed solution (volume ratio of water and ethanol is 1:1) to the then vacuum-drying at 60 ℃ of purifying, obtain ODA-GO;
Step 3, in the ultrasonic 200ml of the being scattered in dimethylbenzene of ODA-GO that step 2 is obtained and be heated to 140 ℃, then by the high density polyethylene(HDPE) of 20mg (HDPE) grain dissolution in above-mentioned solution and continuously stirring, finally obtain hot ODA-GO/HDPE mixing solutions;
Step 4, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film is cleaned with dimethylbenzene, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 3 being obtained by the mode of dipping in film, then in baking oven, be dried 3 minutes, repeat this step, be layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
Fig. 2 is the SEM figure of graphene oxide with high barrier-polyethylene nano compound film of preparing of embodiment 1, can find out, the graphene oxide (ODA-GO) after modification is evenly distributed on ultrahigh molecular weight polyethylene(UHMWPE) film and has structure layer by layer.
Fig. 3 is the FTIR curve of graphene oxide and amino modified graphene oxide in embodiment 1; As can be seen from Figure 3, in graphene oxide, contain a large amount of oxygen-containing functional groups, wherein 3421～3438cm -1, 1720cm -1, 1624～1650cm -1with 1030～1160cm -1place is respectively the stretching vibration peak of carboxyl (O-C=O), carbonyl (C=O) and epoxy group(ing) (C-O-C), 2920cm -1and 2851cm -1for CH 2c-H stretching vibration peak with CH group.Compared with the infrared spectrogram of graphene oxide, modified graphene oxide is at 2920/2851cm -1the peak intensity at place significantly raises, and shows by the amino of octadecylamine and the carbonyl condensation reaction on graphene oxide surface, and a large amount of alkyl chains are grafted to graphene oxide surface.In addition, modified graphene oxide is at 1560cm -1(the bending acid amides of N-H), 1460/1472cm -1(C-N stretches acid amides) and 721cm -1the vibration peak that (C-H flexural vibration) are located shows to have amido linkage between graphene oxide lamella and octadecyl amine molecule, and graphene oxide is by successful modification.
Fig. 4 is the XRD curve of graphene oxide and amino modified graphene oxide in embodiment 1.As can be seen from Figure 4, graphene oxide shows typical diffraction absorption peak in 2 θ=10.1 °.According to Bragg equation formula: 2dsin θ=n λ can obtain the interlamellar spacing d=0.88nm of graphene oxide, compares original graphite layers apart from d=0.34nm, illustrates that oxidising process makes graphite surface and edge introduce a large amount of oxy radicals.Octadecyl modified graphene oxide shows typical diffraction absorption peak in 2 θ=3.78 °, d=2.33nm, diffraction peak diminishes, it is large that sheet interlayer spacing becomes, i.e. successful grafting ODA molecular chain.
The saturating Oxygen Coefficients of pure ultra-high molecular mass polyethylene film is 7.50 × 10 -14cm 3cm/ (cm 2, and the saturating Oxygen Coefficients of graphene oxide with high barrier-polyethylene nano compound film prepared by embodiment 1 is 1.54 × 10 sPa) -15cm 3cm/ (cm 2sPa), approximately 48.7 times have been declined.
Embodiment 2
Step 1, the preparation of graphene oxide
First take respectively 4g K 2s 2o 8, 3g P 2o 5with 5g powdered graphite, mix, then add the 20ml vitriol oil and at 85 ℃ constant temperature stir after 4 hours and be cooled to room temperature, stir 14 hours after adding 1.2L distilled water, to remove residual part acid, product is dried to the graphite that obtains preoxidation for 28 hours with the micropore filter paper filtering of 0.40 μ m;
The graphite of preoxidation is added in the 240ml vitriol oil, constantly stirs and in ice bath, add 35gKMnO 4, at 35 ℃, stir after 3 hours and add 450ml distilled water diluting, continue to stir 1.5 hours, then add 1.0L distilled water, continue to stir, finally add 50ml, 25% H 2o 2solution continues to be stirred to solution and is light yellow, filters washing, the in a vacuum dry graphite oxide that obtains at 50 ℃;
Graphite oxide is dissolved in the distilled water of 100ml, ultrasonic dispersion 40min, obtains graphene oxide;
Step 2, the modification of graphene oxide
Graphene oxide (GO) 0.3g prepared by step 1 is dispersed in 120ml distilled water and ultrasonic agitation 2h, to join in GO suspension containing the alcohol mixeding liquid of 1.0g octadecylamine (ODA) and at room temperature stir 28 hours, the product obtaining is repeatedly cleaned in water-ethanol mixed solution (volume ratio of water and ethanol is 1:1) to the then vacuum-drying at 55 ℃ of purifying, obtain ODA-GO;
Step 3, in the ultrasonic 150ml of the being scattered in dimethylbenzene of ODA-GO that step 2 is obtained and be heated to 135 ℃, then by the high density polyethylene(HDPE) of 15mg (HDPE) grain dissolution in above-mentioned solution and continuously stirring, finally obtain hot ODA-GO/HDPE mixing solutions;
Step 4, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film is cleaned with dimethylbenzene, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 3 being obtained by the mode of dipping in film, then in baking oven, be dried 4 minutes, repeat this step, be layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
Embodiment 3
Step 1, the preparation of graphene oxide
First take respectively 3g K 2s 2o 8, 4g P 2o 5with 7g powdered graphite, mix, then add the 30ml vitriol oil and at 75 ℃ constant temperature stir after 4.5 hours and be cooled to room temperature, stir 13 hours after adding 1.5L distilled water, to remove residual part acid, product is dried to the graphite that obtains preoxidation for 30 hours with the micropore filter paper filtering of 0.5 μ m;
The graphite of preoxidation is added in the 245ml vitriol oil, constantly stirs and in ice bath, add 25gKMnO 4, at 30 ℃, stir after 2.5 hours and add 550ml distilled water diluting, continue to stir 1 hour, then add 1.2L distilled water, continue to stir, finally add 45ml, 35% H 2o 2solution continues to be stirred to solution and is light yellow, filters washing, the in a vacuum dry graphite oxide that obtains at 55 ℃;
Graphite oxide is dissolved in the distilled water of 200ml, ultrasonic dispersion 35min, obtains graphene oxide;
Step 2, the modification of graphene oxide
Graphene oxide (GO) 0.1g prepared by step 1 is dispersed in 80ml distilled water and ultrasonic agitation 1h, to join in GO suspension containing the alcohol mixeding liquid of 2g octadecylamine (ODA) and at room temperature stir 30 hours, the product obtaining is repeatedly cleaned in water-ethanol mixed solution (volume ratio of water and ethanol is 1:1) to the then vacuum-drying at 65 ℃ of purifying, obtain ODA-GO;
Step 3, in the ultrasonic 180ml of the being scattered in dimethylbenzene of ODA-GO that step 2 is obtained and be heated to 145 ℃, then by the high density polyethylene(HDPE) of 25mg (HDPE) grain dissolution in above-mentioned solution and continuously stirring, finally obtain hot ODA-GO/HDPE mixing solutions;
Step 4, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film is cleaned with dimethylbenzene, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 3 being obtained by the mode of dipping in film, then in baking oven, be dried 5 minutes, repeat this step, be layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.

Claims (3)

1. the preparation method of graphene oxide with high barrier-polyethylene nano compound film, is characterized in that, concrete steps are as follows:
Step 1, graphene oxide 0.1～0.3g prepared by the Hummer method of modification is dispersed in 80～120ml distilled water and ultrasonic agitation 1～2h, to join in GO suspension containing the alcohol mixeding liquid of 1～2g octadecylamine and at room temperature stir 24～30h, the product obtaining is repeatedly cleaned in water-ethanol mixed solution to the then vacuum-drying under 55～65 ℃ of conditions of purifying, obtain ODA-GO;
Step 2, ODA-GO that step 1 is obtained is ultrasonic to be scattered in 150～200ml dimethylbenzene and to be heated to 135～145 ℃, then by the high density polyethylene(HDPE) grain dissolution of 15～25mg in above-mentioned solution and continuously stirring, finally obtain hot ODA-GO/HDPE mixing solutions;
Step 3, ultrahigh molecular weight polyethylene(UHMWPE) film is cleaned with dimethylbenzene, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 2 being obtained by the mode of dipping in film, then dry 3～5min in baking oven, repeats this step, is layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
2. the preparation method of graphene oxide with high barrier-polyethylene nano compound film according to claim 1, is characterized in that, the detailed process that the Hummer method of modification in step 1 is prepared graphene oxide is:
The first step, takes first respectively 3～5g K 2s 2o 8, 3～5g P 2o 5with 5～7g powdered graphite, mix, then add 20～30ml vitriol oil and after constant temperature stirring 4～5h, be cooled to room temperature at 75～85 ℃, after adding 1～1.5L distilled water, stir 12～14 hours, to remove residual part acid, dry product 24～30h can be obtained to the graphite of preoxidation with the micropore filter paper filtering of 0.4～0.5 μ m;
Second step, the graphite of the preoxidation that the first step is obtained is added in 240～250ml vitriol oil, constantly stirs and in ice bath, adds 25～35g KMnO 4, add 450～550ml distilled water diluting stir 2～3h at 30～40 ℃ after, continue to stir 1～2h, then add 1～1.5L distilled water, continue to stir, finally add 40～50ml, 25～35% H 2o 2solution continues to be stirred to solution and is light yellow, filters washing, the in a vacuum dry graphite oxide that obtains at 50～60 ℃;
The 3rd step, the graphite oxide that second step is obtained is dissolved in the distilled water of 100～200ml, and ultrasonic dispersion 30～40min, obtains graphene oxide.
3. the preparation method of graphene oxide with high barrier-polyethylene nano compound film according to claim 1 and 2, is characterized in that, in step 1, in water-ethanol mixed solution, the volume ratio of water and ethanol is 1:1.
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