CN104497385A - 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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- 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
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- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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 method thereof, be specifically related to a kind of amination graphene oxide/high density ethylene nano composite membrane and preparation method thereof.
Background technology
In recent years, polymeric film is used widely in industrial or agricultural with the over-all properties of its excellence.But, because the not good security incident caused of commodity polymer polymer materials barrier and middle loss make it can not extensively be promoted in certain fields, as oil-gas gathering and transportation polymer materials easily causes oil and gas leakage because barrier is low, cause serious accident, cause huge financial loss, loss of life and personal injury and environmental problem.Food, drug packing material lose up to 30 ~ 50% because intercepting in the middle of the not good product caused.Therefore, the barrier property improving further polymeric film has become a key issue urgently to be resolved hurrily.
In raising polymeric film barrier technology, utilize interface interaction good between nanoscale twins filler and polymkeric substance and nanoscale twins filler in polymeric matrix, cause " the permeable area reduction effect " and " multipath effect " of gas-permeable to improve the method for the barrier property of polymeric matrix, have easy and simple to handle, product cost is high and be easy to the advantages such as recovery, become at present both at home and abroad thin film fabrication industry and improve the focus and emphasis of polymer barrier performance study.The method need break through two key problem in technology points: 1. nanometer sheet layered fillers should have larger flakiness ratio; 2. nanometer sheet layered fillers should form good interface cohesion with matrix.Functionalization graphene, as graphene oxide, carboxylated Graphene, sulfonated graphene etc., partial double bond on Graphene by oxygen-containing functional group, organic molecule or macromole etc. the product that replaces, (thickness is only about 1nm to the flakiness ratio huge with it, its width is maximum reaches ten microns) and easily disperse in water and other solvents, become scientific circles in recent years and improve the study hotspot of polymer barrier performance.
Graphene oxide is added to the water by patent " a kind of preparation method of oxidized graphene coated film " (publication number is CN102173145A), the soliquid (adding 1mg graphene oxide in 1mL water) obtaining graphene oxide is stirred on supersound process limit, limit, then by the mode of spraying or roll-in, the soliquid of graphene oxide is coated in general purpose film surface, after drying, forms graphene oxide film.Apply some layers, after topmost the drying of one deck graphite oxide ene coatings forms film, Landfill covering one deck general purpose film, namely obtains oxidized graphene coated film.The oxidized graphene coated film prepared of the method not only transparent good, security is high, the feature of environmental protection good, and has excellent barrier, especially the barrier of carbon dioxide is greatly improved.But aforesaid method is by nano graphene oxide by after spraying or rolling techniques coating film forming, and be transformed into macroscopical graphite oxide, after polymeric matrix and graphite oxide self-assembly, layer is more weak with the bonding force of interlayer, and easy generation stripping comes off, and is unfavorable for life-time service.
Graphene oxide adds in solvent by patent " preparation method of graphene oxide with high barrier and polymer nanocomposite membrane " (publication number is CN102115566A), and under 20 ~ 45 DEG C of conditions, supersound process also stirs and prepares graphene oxide soliquid.Then in the soliquid of graphene oxide, add polymkeric substance, stir on 20 ~ 120 DEG C of following supersound process limits, polymkeric substance is dissolved completely, obtains graphene oxide/polymers soln.After removing the bubble in graphene oxide/polymers soln, the method for curtain coating or blowing is adopted to obtain graphene oxide/polymer composite film.Graphene oxide/the polymer nano composite film prepared by the method not Presence of an interface is departed from or the risk that comes off, and increases substantially the barrier of carbon dioxide.But polymeric matrix must be dissolved in the middle of solvent by prerequisite prepared by this laminated film uniformly.And practical situation are, dissolve polymer need spend the plenty of time, and partial polymer as polyethylene, ultrahigh molecular weight polyethylene(UHMWPE) etc. and not easily dissolve by solvent, therefore the method operation steps relative complex, does not have practicality and versatility.Also inevitably there are some residual channel between filler and matrix in the laminated film that simultaneously prepared by the method for curtain coating or blowing, gas barrier property improves limited.
Prepare by graphene oxide and polymkeric substance compound the barrier property that matrix material improves matrix, not only require that graphene oxide can be evenly dispersed in matrix, the more important thing is and need between graphene oxide and superpolymer, there is good interface compatibility.Graphene oxide is because containing the oxygen-containing functional groups such as abundant hydroxyl, carboxyl and epoxy group(ing) and have good wetting ability in its surface and edge, but cause and non-polar polymer as poor in the interface compatibility between the matrix such as polyethylene, polypropylene, and effectively can not improve the barrier property of above matrix, its barrier can be reduced on the contrary.In addition, graphene oxide is bad dispersibility in organic solvent is as acetone, methyl alcohol, ethanol and methylene dichloride, can not preserve for a long time, also can limit the preparation of graphene oxide/polymer composites.
Summary of the invention
In order to overcome the defect that above-mentioned prior art exists, the object of the present invention is to provide a kind of amination graphene oxide/high density polyethylene(HDPE) nano composite membrane and preparation method thereof, the method can overcome solvent indissoluble non-polar polymer and conventional oxidation Graphene in existing method cannot improve the defect of non-polar polymer barrier property, gas-permeable passage can be reduced simultaneously, amination graphene oxide/polyethylene the nano composite membrane obtained through the method has uniform shell core isolation structure, and barrier property is high.
The present invention is achieved through the following technical solutions:
A kind of preparation method of amination graphene oxide/high density polyethylene(HDPE) nano composite membrane, graphene oxide and lauryl amine are reacted after making amination graphene oxide, amination graphene oxide and high-density polyethylene powder are fully mixed in obtained suspension in dimethylbenzene, by dry after suspension vacuum filtration, again by melting hot-pressing processing, obtained amination graphene oxide/polyethylene nano composite membrane.
A preparation method for amination graphene oxide/polyethylene nano composite membrane, comprises the following steps:
1) amination graphene oxide is prepared
Graphene oxide is scattered in deionized water, obtained graphene oxide soliquid; According to the ratio of (3 ~ 5) g:100mL, lauryl amine is dissolved in dehydrated alcohol, be stirred to lauryl amine fully to dissolve, obtain lysate, lysate is added in graphene oxide soliquid, stir, obtain amination graphene oxide dispersion soln, by this amination graphene oxide dispersion soln through vacuum filtration, washing and drying treatment, 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, ultrasonicly dissociate and stir, obtained amination graphene oxide dispersion, high-density polyethylene powder is added in amination graphene oxide dispersion, stir, obtain amination graphene oxide/high density polyethylene(HDPE) suspension;
Wherein, the quality of amination graphene oxide accounts for 7 ~ 10% of amination graphene oxide/high density polyethylene(HDPE) suspension total mass;
3) melting hot pressing amination graphene oxide/high density polyethylene(HDPE) nano composite membrane
By dry 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(HDPE) mixture 260 ~ 270 DEG C, under the condition of 15 ~ 20MPa, it is 10 ~ 12 μm that thickness is made in melting, diameter is the circular membrane of 120 ~ 130mm, namely obtains amination graphene oxide/high density polyethylene(HDPE) nano composite membrane.
Step 1) described in stir, be lysate is added in graphene oxide soliquid, at 50 ~ 60 DEG C, mechanical stirring 24 ~ 48h; Described washing be by vacuum filtration after amination graphene oxide dispersion soln washes of absolute alcohol 4 ~ 6 times; Described drying is at 50 ~ 60 DEG C, vacuum-drying 24 ~ 30h.
Step 2) described in ultrasonic to dissociate and stir be ultrasonicly under the condition of 25 ~ 40 DEG C dissociate and stir 1 ~ 2h; Described stirring is add high-density polyethylene powder in amination graphene oxide dispersion after, mechanical stirring 5 ~ 10min.
Described ultrasonic dissociating is dissociated under ultrasonic power is the condition of 100W.
Step 3) described in drying be dry 24 ~ 48h at 50 ~ 60 DEG C.
The preparation of graphene oxide, specifically comprises the following steps:
(1) according to the ratio of (2 ~ 4) g:100mL, expansible black lead being added to massfraction is in the vitriol oil of 98%, adds KMnO while stirring under ice bath
4, stirring reaction 2 ~ 2.5h at 10 ~ 15 DEG C, then continues reaction 1 ~ 1.5h in the water bath with thermostatic control of 33 ~ 37 DEG C;
(2) according to the vitriol oil: deionized water: hydrogen peroxide=100:(400 ~ 800): the volume ratio of (5 ~ 10), successively deionized water is added and mass concentration is the hydrogen peroxide of 30% in the reaction system of step (1), after stirring, filtered while hot, obtained pasty mixture;
(3) pasty mixture washing is not contained SO to filtrate
4 2-, be then scattered in deionized water under ultrasound condition, obtained graphene oxide soliquid, then drying obtains graphene oxide.
The KMnO that step (1) adds
4quality be 3 ~ 5 times of expansible black lead quality.
Washing described in step (3) is first with the HCl solution washing that mass concentration is 5%, then does not contain SO with deionized water repetitive scrubbing to filtrate
4 2-; Wherein, 1 ~ 2 times of mass concentration used to be the volume of the HCl solution of 5% be pasty mixture volume.
A kind of amination graphene oxide/polyethylene nano composite membrane, the saturating Oxygen Coefficients of this amination graphene oxide/polyethylene nano composite membrane is 1.12 × 10
-15~ 2.52 × 10
-15cm
3cm/ (cm
2sPa), thickness is 10 ~ 12 μm, and diameter is 120 ~ 130mm.
Compared with prior art, the present invention has following useful technique effect:
First graphene oxide and lauryl amine effect are made amination graphene oxide by the present invention, amino on the long hydrocarbon chain molecule of lauryl amine and the carboxyl of surface of graphene oxide and epoxy group(ing) have higher reactive behavior, thus utilize the long hydrocarbon chain on its surface effectively can improve interface compatibility between filler and non-polar polymer, and then improve the barrier property of composite membrane of polymer; Then obtained amination graphene oxide and high-density polyethylene powder are fully mixed in solvent xylene, form mixed uniformly suspension.A large amount of lamella amination graphene oxide has wrapped up high-density polyethylene powder, formed with amination graphene oxide as shell after high-temperature fusion hot pressing, high density polyethylene(HDPE) is the shell core isolation structure of core, amination surface of graphene oxide is with alkyl chain, in hot pressing, good interface interaction can be formed with high density polyethylene(HDPE) molecule.
Preparation method's technique of laminated film provided by the invention is simple, with low cost, without the need to dissolve polymer, can solve difficult dissolve polymer such as polyethylene, ultrahigh molecular weight polyethylene(UHMWPE), polypropylene etc. and prepare the difficult point of laminated film.The amination graphene oxide related in the inventive method has good dispersiveness in solvent xylene, can ensure not precipitate at least three months, can effectively improve and interface compatibility between polar polymer and non-polar polymer.Simultaneously, define after high temperature hot pressing with amination graphene oxide be shell, the high density polyethylene(HDPE) shell core isolation structure that is core, considerably reduce the permeable area of gas, make gas diffusion path significantly meandering, significantly improve the gas barrier property of material.
Amination graphene oxide/high density polyethylene(HDPE) nano composite membrane that the present invention obtains has uniform shell core isolation structure, and barrier property is high.When gas molecules is by this laminated film internal penetration, a large amount of amination graphene oxide sealing coats can be run into, form because amination graphene oxide skeleton is combined closely by the carbon atom of densification, gas molecules can not directly through, can only walk around along amination graphene oxide lamella surface, this makes the permeable area of gas greatly reduce.And spacing between the amination graphene oxide lamella added is very little, makes gas diffusion path significantly meandering, cause gas leak path to increase.Therefore, the effect of amination stannic oxide/graphene nano obstruct wall significantly improves the barrier property of density polyethylene film with high, and the nano compound film that the present invention is obtained have dropped about 98% compared with the saturating Oxygen Coefficients of existing density polyethylene film with high.
Accompanying drawing explanation
Fig. 1 is the FTIR graphic representation of graphene oxide and amination graphene oxide;
Fig. 2 is the polarizing microscope figure of amination graphene oxide/high density polyethylene(HDPE) laminated film that the embodiment of the present invention 1 obtains;
Fig. 3 is the permeable model figure of gas in the obtained amination graphene oxide/high density polyethylene(HDPE) nano compound film of the embodiment of the present invention 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
Embodiment 1
A kind of amination graphene oxide/high density polyethylene(HDPE) nano composite membrane and preparation method thereof, comprises the following steps:
1) graphene oxide is prepared
First, utilize the Hummers legal system improved for graphene oxide: to take 2g expansible black lead and join the dense H that 100mL mass concentration is 98%
2sO
4in, after stirring in ice-water bath, add 10gKMnO gradually
4, at 10 DEG C, reaction 2.5h.In the water bath with thermostatic control of 35 DEG C, continue reaction 1.25h subsequently, then in mixture system, successively add 400mL deionized water and 5mL mass concentration is the H of 30%
2o
2, by mixture filtered while hot after stirring, be use a large amount of deionized water repetitive scrubbing until without SO in filtrate again after the HCl solution washing of 5% by 30mL mass concentration
4 2-(use BaCl
2solution is checked), then utilize ultrasonication to be scattered in 200mL deionized water, obtain graphene oxide soliquid.
2) amination graphene oxide is prepared
Taking 3g lauryl amine is dissolved in 100mL dehydrated alcohol, stirs and makes it fully dissolve, joined by lysate in graphene oxide soliquid, 50 DEG C of mechanical stirring 48h, obtain amination graphene oxide dispersion soln; Finally, amination graphene oxide dispersion soln vacuum is filtered, with washes of absolute alcohol 6 times, keep 24h in 60 DEG C of vacuum drying ovens, obtain the amination graphene oxide of 3.8g drying.
3) nano composite membrane is prepared
The amination graphene oxide getting 1g drying adds in 100mL dimethylbenzene, and ultrasonic at 30 DEG C (power is 100W) is also stirred 2h and obtained amination graphene oxide dispersion; Then in amination graphene oxide colloidal dispersion, add 10g high-density polyethylene powder, mechanical stirring 10min, high-density polyethylene powder is fully mixed, obtain amination graphene oxide/high density polyethylene(HDPE) suspension; Again this amination graphene oxide/high density polyethylene(HDPE) suspension is carried out vacuum to filter, at 60 DEG C of dry 24h; Last at 260 DEG C, under the pressure of 20MPa, the circular membrane of thickness 12 μm, diameter 120mm is made in melting.
The FTIR graphic representation of graphene oxide shown in Figure 1 and amination graphene oxide, as can be seen from the figure, containing a large amount of oxygen-containing functional groups in graphene oxide, wherein 3421 ~ 3438cm
-1, 1728cm
-1, 1624 ~ 1650cm
-1with 1030 ~ 1160cm
-1place is respectively the stretching vibration peak of hydroxyl (O-H), carboxyl (-O-C=O), carbonyl (C=O) and epoxy group(ing) (C-O-C), 2921cm
-1and 2852cm
-1for CH
2with the C-H stretching vibration peak of CH group.Compared with the infrared spectrogram of graphene oxide, amination graphene oxide is at 2921/2852cm
-1the peak intensity at place obviously raises, and show the carbonyl condensation reaction of amino by lauryl amine and surface of graphene oxide, a large amount of alkyl chain is grafted to surface of graphene oxide, and graphene oxide is by successful modification.Make the O-H vibration peak of amination graphene oxide to high wave-number migration 17cm thus
-1, show the interaction comparatively graphene oxide reduction between amination graphene oxide lamella.In addition, amination graphene oxide is at 1560cm
-1(the bending acid amides of N-H), 1460/1462cm
-1(C-N stretches acid amides) and 720cm
-1the vibration peak at (C-H flexural vibration) place shows to there is amido linkage between graphene oxide lamella and dodecyl amine molecule.
The polarizing microscope figure of amination graphene oxide/high density polyethylene(HDPE) nano composite material shown in Figure 2, as seen from the figure, obtained amination graphene oxide/high density polyethylene(HDPE) nano composite membrane presents the isolation structure that good interface combines, wherein black region is a large amount of amination graphene oxide, and white-bright zone territory is high density polyethylene(HDPE).
The saturating Oxygen Coefficients of existing density polyethylene film with high is 5.70 × 10
-14cm
3cm/ (cm
2and the saturating Oxygen Coefficients of amination graphene oxide/high density polyethylene(HDPE) laminated film prepared by the present embodiment is 1.12 × 10 sPa),
-15cm
3cm/ (cm
2sPa), have dropped about 98%.
Embodiment 2
A kind of amination graphene oxide/high density polyethylene(HDPE) nano composite membrane and preparation method thereof, comprises the following steps:
1) graphene oxide is prepared
First, utilize the Hummers legal system improved for graphene oxide: to take 3g expansible black lead and join the dense H that 110mL mass concentration is 98%
2sO
4in, after stirring in ice-water bath, add 12g KMnO gradually
4, at 15 DEG C, reaction 2h.In the water bath with thermostatic control of 33 DEG C, continue reaction 1.5h subsequently, then in mixture system, successively add 450mL deionized water and 20mL mass concentration is the H of 30%
2o
2, by mixture filtered while hot after stirring, be use a large amount of deionized water repetitive scrubbing until without SO in filtrate again after the HCl solution washing of 5% by 35mL mass concentration
4 2-(use BaCl
2solution is checked), then utilize ultrasonication to be scattered in 300mL deionized water, obtain graphene oxide soliquid.
2) amination graphene oxide is prepared
Taking 4.5g lauryl amine is dissolved in 110mL dehydrated alcohol, stirs and makes it fully dissolve, joined by lysate in graphene oxide soliquid, 60 DEG C of mechanical stirring 20h, obtain amination graphene oxide dispersion soln; Finally, amination graphene oxide dispersion soln vacuum is filtered, with washes of absolute alcohol 5 times, keep 36h in 55 DEG C of vacuum drying ovens, obtain the amination graphene oxide of 8.4g drying.
3) nano composite membrane is prepared
The amination graphene oxide getting 1.25g drying adds in 125mL dimethylbenzene, and ultrasonic at 30 DEG C (power is 100W) is also stirred 1.5h and obtained amination graphene oxide dispersion; Then in amination graphene oxide colloidal dispersion, add 13.75g high-density polyethylene powder, mechanical stirring 8min, high-density polyethylene powder is fully mixed, obtain amination graphene oxide/high density polyethylene(HDPE) suspension; Again this amination graphene oxide/high density polyethylene(HDPE) suspension is carried out vacuum to filter, at 55 DEG C of dry 36h; Last at 265 DEG C, under the pressure of 18MPa, the circular membrane of thickness 11 μm, diameter 125mm is made in melting.
The saturating Oxygen Coefficients of existing density polyethylene film with high is 5.70 × 10
-14cm
3cm/ (cm
2and the saturating Oxygen Coefficients of amination graphene oxide/high density polyethylene(HDPE) laminated film prepared by the present embodiment is 1.43 × 10 sPa),
-15cm
3cm/ (cm
2sPa), 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, comprises the following steps:
1) graphene oxide is prepared
First, utilize the Hummers legal system improved for graphene oxide: to take 4g expansible black lead and join the dense H that 120mL mass concentration is 98%
2sO
4in, after stirring in ice-water bath, add 20g KMnO gradually
4, at 15 DEG C, reaction 2h.In the water bath with thermostatic control of 37 DEG C, continue reaction 1h subsequently, then in mixture system, successively add 600mL deionized water and 25mL mass concentration is the H of 30%
2o
2, by mixture filtered while hot after stirring, be use a large amount of deionized water repetitive scrubbing until without SO in filtrate again after the HCl solution washing of 5% by 40mL mass concentration
4 2-(use BaCl
2solution is checked), then utilize ultrasonication to be scattered in 400mL deionized water, obtain graphene oxide soliquid.
2) amination graphene oxide is prepared
Taking 5g lauryl amine is dissolved in 120mL dehydrated alcohol, stirs and makes it fully dissolve, joined by lysate in graphene oxide soliquid, 55 DEG C of mechanical stirring 36h, obtain amination graphene oxide dispersion soln; Finally, amination graphene oxide dispersion soln vacuum is filtered, with washes of absolute alcohol 4 times, keep 48h in 50 DEG C of vacuum drying ovens, obtain the amination graphene oxide of 10.0g drying.
3) nano composite membrane is prepared
The amination graphene oxide getting 2.5g drying adds in 250mL dimethylbenzene, and ultrasonic at 35 DEG C (power is 100W) is also stirred 1.5h and obtained amination graphene oxide dispersion; Then in amination graphene oxide colloidal dispersion, add 32.75g high-density polyethylene powder, mechanical stirring 6min, high-density polyethylene powder is fully mixed, obtain amination graphene oxide/high density polyethylene(HDPE) suspension; Again this amination graphene oxide/high density polyethylene(HDPE) suspension is carried out vacuum to filter, at 50 DEG C of dry 48h; Last at 270 DEG C, under the pressure of 15MPa, the circular membrane of thickness 10 μm, diameter 130mm is made in melting.
The saturating Oxygen Coefficients of existing density polyethylene film with high is 5.70 × 10
-14cm
3cm/ (cm
2and the saturating Oxygen Coefficients of amination graphene oxide/high density polyethylene(HDPE) laminated film prepared by the present embodiment is 2.52 × 10 sPa),
-15cm
3cm/ (cm
2sPa), have dropped about 95.6 times.
The mechanism of action of the present invention is described below:
Gas molecule in the film penetrate through absorption, dissolving, diffusion and separate out Four processes.Its basic permeability mechanism is: gas molecule first with film contacts, dissolve in film surface enrichment subsequently, make both sides, film surface produce concentration difference.Under the effect of concentration difference, " moment hole " that gas molecule occurs using polymer macromolecule segment strenuous exercise progressively at film internal diffusion as passage, finally arrives the opposite side of film and separates out.
Adopt the amination graphene oxide prepared of the inventive method, under ultrasonic dissociation, can be dispersed in xylene solvent, after stirring and high-density polyethylene powder form mixed uniformly suspension.A large amount of lamella amination graphene oxide has wrapped up high-density polyethylene powder, is formed with amination graphene oxide for shell after high temperature hot pressing, and high density polyethylene(HDPE) is the shell core isolation structure (Fig. 2) of core.In addition, because amination surface of graphene oxide is with alkyl chain, in hot pressing, good interface interaction can be formed with high density polyethylene(HDPE) molecule.
Gas passes through the process of osmosis of the amination graphene oxide/high density polyethylene(HDPE) nano compound film of isolation structure as shown in Figure 3, and high density polyethylene(HDPE) is by the isolation of a large amount of lamella amination graphene oxide parcel.When gas molecules is by film internal penetration, a large amount of amination graphene oxide sealing coats can be run into.Form because amination graphene oxide skeleton is combined closely by the carbon atom of densification, gas molecules can not directly through, can only walk around along amination graphene oxide lamella surface, this makes the permeable area of gas greatly reduce.In addition, the spacing between the amination graphene oxide lamella added is very little, makes gas diffusion path significantly meandering, causes gas leak path to increase.Therefore, the effect of amination stannic oxide/graphene nano obstruct wall significantly improves the barrier property of density polyethylene film with high, makes the saturating Oxygen Coefficients of the nano compound film of preparation have dropped about 98%.
In sum, melting press mold technique one step of the present invention can obtain high-barrier composite film, is applicable to extensive preparation.Amination graphene oxide/high density polyethylene(HDPE) laminated film that the present invention is prepared by heat pressing process at a lower temperature has regular uniform shell core isolation structure, can significantly reduce gas-permeable area, improve gas leak path, significantly improve the barrier to all kinds of gas.Used polymeric matrix can also comprise other alkanes polymkeric substance or the multipolymers such as ultrahigh molecular weight polyethylene(UHMWPE), polypropylene.
Claims (10)
1. the preparation method of amination graphene oxide/high density polyethylene(HDPE) nano composite membrane, it is characterized in that, graphene oxide and lauryl amine are reacted after making amination graphene oxide, amination graphene oxide and high-density polyethylene powder are fully mixed in obtained suspension in dimethylbenzene, by dry after suspension vacuum filtration, again by melting hot-pressing processing, obtained amination graphene oxide/polyethylene nano composite membrane.
2. the preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane according to claim 1, is characterized in that, comprise the following steps:
1) amination graphene oxide is prepared
Graphene oxide is scattered in deionized water, obtained graphene oxide soliquid; According to the ratio of (3 ~ 5) g:100mL, lauryl amine is dissolved in dehydrated alcohol, be stirred to lauryl amine fully to dissolve, obtain lysate, lysate is added in graphene oxide soliquid, stir, obtain amination graphene oxide dispersion soln, by this amination graphene oxide dispersion soln through vacuum filtration, washing and drying treatment, 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, ultrasonicly dissociate and stir, obtained amination graphene oxide dispersion, high-density polyethylene powder is added in amination graphene oxide dispersion, stir, obtain amination graphene oxide/high density polyethylene(HDPE) suspension;
Wherein, the quality of amination graphene oxide accounts for 7 ~ 10% of amination graphene oxide/high density polyethylene(HDPE) suspension total mass;
3) melting hot pressing amination graphene oxide/high density polyethylene(HDPE) nano composite membrane
By dry 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(HDPE) mixture 260 ~ 270 DEG C, under the condition of 15 ~ 20MPa, it is 10 ~ 12 μm that thickness is made in melting, diameter is the circular membrane of 120 ~ 130mm, namely obtains amination graphene oxide/high density polyethylene(HDPE) nano composite membrane.
3. the preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane according to claim 2, it is characterized in that, step 1) described in stir, be lysate is added in graphene oxide soliquid, at 50 ~ 60 DEG C, mechanical stirring 24 ~ 48h; Described washing be by vacuum filtration after amination graphene oxide dispersion soln washes of absolute alcohol 4 ~ 6 times; Described drying is at 50 ~ 60 DEG C, vacuum-drying 24 ~ 30h.
4. the preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane according to claim 2, is characterized in that, step 2) described in ultrasonic to dissociate and stir be ultrasonicly under the condition of 25 ~ 40 DEG C dissociate and stir 1 ~ 2h; Described stirring is add high-density polyethylene powder in amination graphene oxide dispersion after, mechanical stirring 5 ~ 10min.
5. the preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane according to claim 4, is characterized in that, described ultrasonic dissociating is dissociated under ultrasonic power is the condition of 100W.
6. the preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane according to claim 2, is characterized in that, step 3) described in drying be dry 24 ~ 48h at 50 ~ 60 DEG C.
7. the preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane according to claim 1 and 2, it is characterized in that, the preparation of described graphene oxide, specifically comprises the following steps:
(1) according to the ratio of (2 ~ 4) g:100mL, expansible black lead being added to massfraction is in the vitriol oil of 98%, adds KMnO while stirring under ice bath
4, stirring reaction 2 ~ 2.5h at 10 ~ 15 DEG C, then continues reaction 1 ~ 1.5h in the water bath with thermostatic control of 33 ~ 37 DEG C;
(2) according to the vitriol oil: deionized water: hydrogen peroxide=100:(400 ~ 800): the volume ratio of (5 ~ 10), successively deionized water is added and mass concentration is the hydrogen peroxide of 30% in the reaction system of step (1), after stirring, filtered while hot, obtained pasty mixture;
(3) pasty mixture washing is not contained SO to filtrate
4 2-, be then scattered in deionized water under ultrasound condition, obtained graphene oxide soliquid, then drying obtains graphene oxide.
8. the preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane according to claim 7, is characterized in that, the KMnO that step (1) adds
4quality be 3 ~ 5 times of expansible black lead quality.
9. the preparation method of a kind of amination graphene oxide/polyethylene nano composite membrane according to claim 7, it is characterized in that, washing described in step (3) is first with the HCl solution washing that mass concentration is 5%, then does not contain SO with deionized water repetitive scrubbing to filtrate
4 2-; Wherein, 1 ~ 2 times of mass concentration used to be the volume of the HCl solution of 5% be pasty mixture volume.
10. amination graphene oxide/polyethylene nano composite membrane that the method in claim 1 ~ 9 described in any one is obtained, it is characterized in that, the saturating Oxygen Coefficients of this amination graphene oxide/polyethylene nano composite membrane is 1.12 × 10
-15~ 2.52 × 10
-15cm
3cm/ (cm
2sPa), thickness is 10 ~ 12 μm, and diameter is 120 ~ 130mm.
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