CN106674989B - A kind of poly- p-phenylenediamine of redox graphene -/TPU laminated film - Google Patents
A kind of poly- p-phenylenediamine of redox graphene -/TPU laminated film Download PDFInfo
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Abstract
The invention discloses a kind of poly- p-phenylenediamine of redox graphene -/TPU laminated films, it is under the initiation of ammonium persulfate, the poly- p-phenylenediamine of in-situ polymerization on sheet graphene oxide, obtain GO-PPDA nanometer powder, RGO-PPDA nanometer powder is made through hydrazine hydrate reduction again, RGO-PPDA/TPU laminated film finally is made using solution coating film-forming process.Serious reunion can occur in the polymer to avoid graphene for layered laminate structure；Graphene oxide and DMF poor compatibility, and on graphene oxide after the poly- p-phenylenediamine of in-situ polymerization, it can be made to be uniformly distributed in DMF, and then realize the fine dispersion in TPU matrix in solution coating film forming procedure；And graphene and poly- p-phenylenediamine have excellent conduction, thermal conductivity, and can greatly extend channel when small-molecule substance passes through laminated film, to achieve the purpose that improve TPU film barrier, electricity and heating conduction.
Description
Technical field
The invention belongs to technical field of high-molecule composite preparation, and in particular to a kind of poly- pair of redox graphene-
Phenylenediamine/TPU laminated film.
Background technique
Graphene is by single layer Sp2Hydbridized carbon atoms are tightly packed at bi-dimensional cellular shape lattice structure carbon material.Graphene
Special monoatomic layer structure determines its unique physical property, and such as high intensity, high-modulus, high thermal conductivity, high electronics move
Shifting rate, high-specific surface area and high obstructing performance etc..Graphene is to have now known one of highest material of thermal conductivity in material, heat
Conductance is up to 5300W/ (mK).The unique electronic and physical characteristic that graphene shows, keep it compound in polymer
It is with important application prospects in material.
P-phenylenediamine is the aromatic amine with reproducibility, oxidizable in air.Poly- p-phenylenediamine has phenyl ring and quinoid
Alternate hierarchic structure, electric conductivity were similar to nigrosine, and conductivity is lower, and about 6 × 10-6S/cm, using graphene
Doped polymer composite material is remarkably improved the conductivity of polymer.
Thermoplastic polyurethane elastomer (TPU) is one kind as composed by diisocyanate, polyalcohol and short chain glycol
Heating can be plasticized, (AB) that solvent can dissolvenType block linear polymer.Polyurethane is a kind of height with extensive use
Molecular material is mainly used for automobile, building, pavement material, mine, exploitation, electronics and space flight etc..In recent years, as weight
The polyurethane injecting paste material development of one of the chemical consolidation material wanted is also very rapid, and people have also turned one's attention to TPU
The military oil storage bag of water storage bag, TPU, TPU paddle class product etc..As other high molecular materials, polyurethane material thermal conductivity itself
Rate is low, has very high sheet resistance, is easy to produce static charge accumulation in use, is to cause the safety such as fire, explosion
The important hidden danger of accident.
Graphene oxide (GO) although surface has an oxygen-containing functional groups such as carboxyl, hydroxyl, epoxy group, it is sonicated after energy
It is enough to realize removing and evenly dispersed in water and in DMF, but dispersibility is general, stands a moment, GO will be deposited on the bottom of DMF
Portion.In current domestic and foreign literature, antistatic treatment is carried out to TPU and mainly passes through a large amount of carbon blacks of addition and metal oxide etc.
Based on, and in-situ polymerization grows also being rarely reported for nanometer conductive polymer on graphene.The present invention be successfully prepare it is novel
Comprehensive TPU nanocomposite provides new approach, while also compound for Future Development novel high-performance polymer nanocomposite
Material provides new thinking and exploration, so that the present invention academicly has innovation research value, has in practical applications
Extensive economic results in society and strategic value.
Summary of the invention
The present invention aiming at the shortcomings in the prior art with defect, by graphene oxide in-situ polymerization it is poly- to benzene two
The GO-PPDA powder of energy stable and uniform being dispersed in DMF solution is prepared in amine, compound with TPU after then being restored,
Obtain a kind of poly- p-phenylenediamine of redox graphene -/TPU laminated film, the thin-film material have good barrier, it is thermally conductive,
Antistatic property has extensive economic results in society and strategic value.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of poly- p-phenylenediamine of redox graphene -/TPU laminated film uses and improves the preparation oxidation of Hummers method
Graphene on it after the poly- p-phenylenediamine of in-situ polymerization, through hydrazine hydrate reduction, then is scattered in DMF then in ice-water bath
In, after ultrasonic treatment, the TPU swollen in DMF is poured into, the reduction-oxidation graphite is made using solution coating film-forming process
The poly- p-phenylenediamine of alkene -/TPU laminated film.
The preparation method of the poly- p-phenylenediamine of the redox graphene -/TPU laminated film, the specific steps are as follows:
1) it after graphite being carried out cold treatment, is placed in low-temp reaction bath, is slowly added to the concentrated sulfuric acid while stirring, and in 3h
It is added portionwise potassium permanganate, after low-temp reaction 0.5h, is again heated to 50 DEG C, then the reaction was continued 12h is added deionized water, stirs
15min is mixed, and hydrogen peroxide is added dropwise, through pickling, is washed to neutrality, is lyophilized, obtains the graphene oxide of sheet；
2) by graphene oxide ultrasonic disperse in deionized water, p-phenylenediamine monomer and mistake is added in low-temp reaction bath
Ammonium persulfate initiator, 4 DEG C or less low temperature polymerization reactions for 24 hours, are then allowed to stand 2h, are washed with deionized water and dehydrated alcohol to nothing
Color, freeze-drying, obtains GO-PPDA powder；
3) it disperses gained GO-PPDA powder ultrasonic in deionized water, hydrazine hydrate is then added, be heated to 90 DEG C, instead
It answers 3h, stands 2h, then washed with deionized water and dehydrated alcohol to colourless, freeze-drying obtains RGO-PPDA nanometer powder；
4) it by RGO-PPDA nanometer powder obtained in step 3), is added in DMF solution, 100W 1 ~ 2h of ultrasonic disperse,
The TPU swollen in DMF is poured into, stirs 2 ~ 5h, then 100W 1 ~ 2h of ultrasonic disperse under room temperature, 1 ~ 2h is stood and excludes air；
5) film, control film thickness are 0.06 ~ 0.08mm, obtain RGO-PPDA/TPU THIN COMPOSITE after solvent sufficiently volatilizees
Film.
The mass ratio of graphene oxide and p-phenylenediamine monomer is 1:2.7-1:10.8 in step 2；P-phenylenediamine monomer with
The molar ratio of ammonium persulfate is 1:0.67.
The mass volume ratio of GO-PPDA powder and hydrazine hydrate is 1:1 ~ 1:3 g/mL in step 3).
In RGO-PPDA/TPU laminated film obtained by step 5), the content of RGO-PPDA is 0.1 ~ 1.5wt%.
The poly- p-phenylenediamine of gained redox graphene -/TPU laminated film can be used for preparing water storage bag, oil storage bag or instrument
Device packaging bag.
The beneficial effects of the present invention are:
(1) the present invention poly- p-phenylenediamine of in-situ polymerization, GO-PPDA of formation on sheet graphene oxide is nano combined
Material uniform and stable can be dispersed in DMF solvent, solve the problems, such as that GO is easy to reunite in DMF；Meanwhile poly- p-phenylenediamine
Belong to organic amine with DMF, a large amount of hydrogen bonds can be formed, greatly improve GO-PPDA dispersibility in DMF, be more advantageous to its
It is evenly dispersed in polymeric matrix, and divide the RGO-PPDA nanocomposite obtained by hydrazine hydrate reduction in DMF
Scattered performance is equally fine, and then can coat in solution and realize the fine dispersion in TPU matrix in film forming procedure, significantly improves
Compatibility between inorganic filler and polymeric matrix.
(2) so far, hydrazine hydrate reduction graphene oxide is a kind of fairly simple, efficient restoring method, can be preferably
Redox graphene, and give full play to the excellent mechanical property of graphene, barrier property and electric property etc..Therefore,
The redox graphene of preparation/poly- p-phenylenediamine can be consolidated and is evenly distributed in TPU matrix, and closely be tied with it
It closes, forms three-dimensional conductive network in TPU matrix, the antistatic property and heating conduction of material can be improved.
(3) TPU laminated film safety and environmental protection prepared by the present invention, it is dust-proof, prevent that quiet, barrier property is excellent and conductance is hot fast,
It is applicable not only to prepare water storage, oil storage bag thin-film material, is also applied for the packaging of precision instrument；Meanwhile present invention adaptation is worked as
The demand in modern market, preparation method is scientific and reasonable, strong operability, greatly improves TPU value-added content of product, and extend it
Application range, have extensive market prospects and significant social benefit.
Detailed description of the invention
Fig. 1 is GO(A) and SEM GO-PPDA(B) scheme.
Fig. 2 is GO(A), GO-PPDA(B) and RGO-PPDA(C) XPS figure.
Fig. 3 is GO(A), GO-PPDA(B) and RGO-PPDA(C) the dispersion figure in DMF.
Fig. 4 is saturating for the GO-PPDA/TPU laminated film of different quality containing and the oxygen of RGO-PPDA/TPU laminated film
Cross rate figure of changing.
Fig. 5 is the GO-PPDA/TPU laminated film of different quality containing and the volume electricity of RGO-PPDA/TPU laminated film
Resistance rate figure of changing.
Fig. 6 is the GO-PPDA/TPU laminated film of different quality containing and the thermal conductivity of RGO-PPDA/TPU laminated film
Figure of changing.
Specific embodiment
A kind of preparation method of the poly- p-phenylenediamine of redox graphene -/TPU laminated film, the specific steps are as follows:
1) it after graphite being carried out cold treatment, is placed in low-temp reaction bath, is slowly added to the concentrated sulfuric acid while stirring, and in 3h
Potassium permanganate is added portionwise, at 4 DEG C after low-temp reaction 0.5h, is again heated to 50 DEG C, then deionization is added in the reaction was continued 12h
Water stirs 15min, and 30% hydrogen peroxide is added dropwise, and through pickling, is washed to neutrality, is lyophilized, obtains the graphene oxide of sheet；
2) by graphene oxide ultrasonic disperse in deionized water, p-phenylenediamine monomer and mistake is added in low-temp reaction bath
Ammonium persulfate initiator, 4 DEG C or less low temperature polymerization reactions for 24 hours, are then allowed to stand 2h, are washed with deionized water and dehydrated alcohol to nothing
Color, freeze-drying, obtains GO-PPDA powder；Wherein, the mass ratio of graphene oxide and p-phenylenediamine monomer is 1:2.7-1:10.8；
The molar ratio of p-phenylenediamine monomer and ammonium persulfate is 1:0.67；
3) disperse gained GO-PPDA powder ultrasonic in deionized water, be then added hydrazine hydrate, GO-PPDA powder with
The mass volume ratio of hydrazine hydrate is 1:1 ~ 1:3 g/mL, is heated to 90 DEG C, reacts 3h, stands 2h, then with deionized water and anhydrous
For ethanol washing to colourless, freeze-drying obtains RGO-PPDA nanometer powder；
4) it by RGO-PPDA nanometer powder obtained in step 3), is added in DMF solution, 100W 1 ~ 2h of ultrasonic disperse,
The TPU swollen in DMF is poured into, stirs 2 ~ 5h, then 100W 1 ~ 2h of ultrasonic disperse under room temperature, 1 ~ 2h is stood and excludes air；
5) film, control film thickness are 0.06 ~ 0.08mm, obtained after solvent sufficiently volatilize RGO-PPDA content for 0.1 ~
1.5% RGO-PPDA/TPU laminated film.
SEM of the Fig. 1 for graphene oxide GO(A) and GO-PPDA(B) schemes.From the figure, it can be seen that poly- p-phenylenediamine attachment
On graphene oxide, show poly- p-phenylenediamine monomer in-situ polymerization on graphene oxide.
Fig. 2 is GO(A), GO-PPDA(B) and RGO-PPDA(C) XPS figure.It can be seen from the figure that graphene oxide
The C/O that C/O is 0.556, GO-PPDA, which is that the relative amount of carbon in 1.197, GO-PPDA is opposite, to be improved, and is because graphite oxide is dilute
Contain carbon in the poly- p-phenylenediamine of surface in situ growth, without oxygen-containing, therefore increases C/O than significant；And the C/O of RGO-PPDA
The value for reaching 1.398, C/O further increases, and is the hydroxyl of surface of graphene oxide because under the strong reducing action of hydrazine hydrate
The oxygen-containing groups such as base, carboxyl, epoxy group are reduced, and revert to the dilute carbon-carbon double bond structure of graphite.
Fig. 3 is GO(A), GO-PPDA(B) and RGO-PPDA(C) be dispersed in 10mL DMF solution respectively, concentration obtained
Situation figure of the dispersion liquid of 1mg/mL through ultrasonic 1h and after standing 30d.In Fig. 3 A, GO is substantially completely deposited in bottom, illustrates GO
Dispersibility in DMF is poor；And GO-PPDA and RGO-PPDA uniform and stable for a long time can be dispersed in Fig. 3 B and Fig. 3 C
In DMF solution, this is because having amido in poly- p-phenylenediamine and DMF, is mixed due to similar, enhance GO-PPDA and RGO-
Dispersibility of the PPDA in DMF, for later period GO-PPDA and RGO-PPDA, uniform and stable dispersion provides guarantee in TPU.
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
1) it improves Hummers method and prepares graphene oxide: after 1g graphite is first carried out cold treatment, delaying in low-temp reaction bath
It is slow that 98% concentrated sulfuric acid of 45mL and 5mL concentrated phosphoric acid is added, it stirs and evenly mixs, and 7g potassium permanganate is added portionwise in nitration mixture in 3h,
Reaction system is moved in water-bath after low-temp reaction half an hour again and is heated to 50 DEG C, 1000mL is added after the reaction was continued 12h and goes
Ionized water obtains rufous graphite suspension, continues that 30% hydrogen peroxide is added dropwise after stirring 15min, obtains the dilution of glassy yellow graphite
Liquid finally carries out pickling with 3% hydrochloric acid solution, then is washed to neutrality, obtains graphene oxide gel, graphene oxide is coagulated
Glue carries out frozen dried, and fluffy graphene oxide (GO) solid is made；
2) synthesis of GO-PPDA composite material: being added 1.53 g ammonium persulfates in 25mL HCl, stirs to completely molten
Solution is put into ice bath cooling 5 min, pours into separatory funnel；100mg GO solid is added to the HCl's of 75mL 1mol/L
In beaker, and the ultrasonic disperse 1h at 100W, pour into flask, add 1.08g p-phenylenediamine monomer, be put into togerther 4 DEG C with
Magnetic stirring 0.5h in lower ice bath pot, then controls rate of addition, and ammonium persulfate solution is dripped in 0.5-1.0h, continues
Reaction for 24 hours, stands 2h, and repeatedly wash filtering with deionized water and dehydrated alcohol, until filtrate clear, colorless is in neutrality, then puts
Enter in freeze dryer, freeze-drying obtains the nanometer GO-PPDA powder of black；
3) synthesis of RGO-PPDA composite material: nanometer GO-PPDA powder 100mg made from step 2 is taken to burn in round bottom
Bottle, is added 100mL deionized water, then ultrasonic disperse 1h is added 0.2 mL hydrazine hydrate, is heated to 90 DEG C, heating reflux reaction
3h stands 2h, and repeatedly washs filtering with deionized water and dehydrated alcohol, until filtrate clear, colorless is in neutrality, is then placed in jelly
In dry machine, freeze-drying obtains the RGO-PPDA nanometer powder of black；
4) preparation of mixing liquid: weighing 0.015g RGO-PPDA nano powder dispersion in 40mL DMF solution,
7.5g TPU is then added thereto, above-mentioned mixed system is put into 70 DEG C by ultrasonic disperse 1h in the ultrasonic cleaner of 100W
Vacuum oven in be swollen 20h, and then the mixed system is stirred on machine mixer 5h until TPU be completely dissolved
Afterwards, it is placed in ultrasonic disperse 1h in the ultrasonic cleaner of 100W, and stands 1h to ensure sufficiently to remove the bubble in mixing liquid；
5) film: sheet glass is placed on film applicator, and then on the glass sheet by the coating of gained mixing liquid, control applies
Film thickness is 0.08mm；After the completion of coating, sheet glass is dried for 24 hours in 90 DEG C of baking oven, it is multiple to obtain 0.2% RGO-PPDA/TPU
Close film.
Embodiment 2
0.038g RGO-PPDA nanometer powder is added in step 4), other conditions parameter is same as Example 1, final
To 0.5% RGO-PPDA/TPU laminated film.
Embodiment 3
0.060g RGO-PPDA nanometer powder is added in step 4), other conditions parameter is same as Example 1, final
To 0.8% RGO-PPDA/TPU laminated film.
Embodiment 4
0.076g RGO-PPDA nanometer powder is added in step 4), other conditions parameter is same as Example 1, final
To 1%RGO-PPDA/TPU laminated film.
Embodiment 5
0.015g nanometers of GO-PPDA powder are added in step 4), other conditions parameter is same as Example 1, finally obtains
0.2% GO-PPDA/TPU laminated film.
Embodiment 6
0.038g nanometers of GO-PPDA powder are added in step 4), other conditions parameter is same as Example 1, finally obtains
0.5% GO-PPDA/TPU laminated film.
Embodiment 7
0.060g nanometers of GO-PPDA powder are added in step 4), other conditions parameter is same as Example 1, finally obtains
0.8% GO-PPDA/TPU laminated film.
Embodiment 8
0.076g nanometers of GO-PPDA powder are added in step 4), other conditions parameter is same as Example 1, finally obtains
1% GO-PPDA/TPU laminated film.
Fig. 4 is saturating for the GO-PPDA/TPU laminated film of different quality containing and the oxygen of RGO-PPDA/TPU laminated film
Cross rate figure of changing.As seen in Figure 4, under the experiment condition that the present invention is controlled, as GO-PPDA and RGO-PPDA
When mass fraction is 0.8%, the OTR oxygen transmission rate of laminated film respectively reaches 137.692 cm of minimum3•(m2•d•Pa)-1With
113.492 cm3•(m2•d•Pa)-1, compare pure TPU film [462.238 cm3•(m2•d•Pa)-1] have dropped 68.04% He
73.28%, barrier property is significantly improved.Meanwhile can be also clearly seen that from Fig. 4, when mass fraction is identical, RGO-
The OTR oxygen transmission rate of PPDA/TPU film ratio GO-PPDA/TPU film is lower, and barrier property is more preferable.When addition mass fraction is more than
When 0.8%, the OTR oxygen transmission rate of laminated film is begun to ramp up.
Fig. 5 is the GO-PPDA/TPU laminated film of different quality containing and the volume electricity of RGO-PPDA/TPU laminated film
Resistance rate (ρv) figure of changing.It can be obtained by Fig. 5, with the increase of GO-PPDA and RGO-PPDA mass fraction, laminated film ρvOccur
Apparent decline, when their mass fractions reach 0.8%, the Log (ρ of composite material filmv) it is respectively 5.987 and 4.825,
7 orders of magnitude and 8 orders of magnitude are had dropped respectively compared to pure TPU film (12.543), continue growing GO-PPDA and RGO-PPDA
Mass fraction, laminated film ρvThere is no significant change occurs, its conduction of deducibility changes infiltration value about between 0.5% ~ 0.8%,
Continuous conductive path or network are basically formed in compound system at this time, the laminated film of formation has good conduction
Property.Meanwhile can be also clearly seen that from Fig. 5, when mass fraction is identical, RGO-PPDA/TPU film ratio GO-PPDA/TPU is thin
The ρ of filmvAbout low an order of magnitude illustrates that RGO-PPDA/TPU film has more excellent antistatic property, quiet resisting
The application in conductive film field has bigger potentiality.
Fig. 6 is the GO-PPDA/TPU laminated film of different quality containing and the thermal conductivity of RGO-PPDA/TPU laminated film
Figure of changing.As seen in Figure 6, the thermal conductivity of laminated film with GO-PPDA and RGO-PPDA mass fraction increasing
Add and increase, when GO-PPDA and RGO-PPDA mass fraction reaches 1%, the thermal conductivity of laminated film is respectively 1.384 W/
(mK) and 1.512 W/ (mK), 5.550 times and 6.10 times are improved than pure TPU [0.213 W/ (mK)], are illustrated compound
The thermal conductivity of film greatly improves, and greatly extends TPU film in the application of thermally conductive aspect.Meanwhile it being also easy from Fig. 6
Out, when mass fraction is identical, the thermal conductivity of RGO-PPDA/TPU film ratio GO-PPDA/TPU film is high, and heating conduction is more preferable,
Illustrate that RGO-PPDA/TPU film also more has prospect at thermally conductive aspect.
Laminated film safety and environmental protection provided by the present invention, particularly useful for making TPU medical mattress, TPU biogas storage
Bag, TPU paddle the field that the packaging etc. of class product, precision instrument has higher requirements to the barrier of material and antistatic property.Together
When, the present invention adapts to the demand in current market, and preparation method is scientific and reasonable, strong operability, greatly improves the attached of TPU product
It is value added, and its application range is extended, there is extremely vast potential for future development and economic results in society.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (7)
1. a kind of poly- p-phenylenediamine of redox graphene -/TPU laminated film, it is characterised in that: in ice-water bath, aoxidizing
The poly- p-phenylenediamine of in-situ polymerization on graphene, then through hydrazine hydrate reduction, then is scattered in DMF, after ultrasonic treatment, is poured into
The TPU in DMF is swollen in, it is multiple that the poly- p-phenylenediamine/TPU of the redox graphene-is made using solution coating film-forming process
Close film.
2. the poly- p-phenylenediamine of redox graphene -/TPU laminated film according to claim 1, it is characterised in that: it is made
Specific step is as follows for Preparation Method:
1) using the graphene oxide for improving Hummers method preparation sheet；
2) by gained graphene oxide ultrasonic disperse in deionized water, p-phenylenediamine monomer and mistake is added in low-temp reaction bath
Ammonium persulfate initiator, 4 DEG C or less low temperature polymerization reactions for 24 hours, are then allowed to stand 2h, are washed with deionized water and dehydrated alcohol to nothing
Color, freeze-drying, obtains GO-PPDA powder；
3) it disperses gained GO-PPDA powder ultrasonic in deionized water, hydrazine hydrate is then added, be heated to 90 DEG C, react 3h,
2h is stood, then is washed with deionized water and dehydrated alcohol to colourless, freeze-drying obtains RGO-PPDA nanometer powder；
4) RGO-PPDA nanometer powder obtained in step 3) is added in DMF solution, 100W 1 ~ 2h of ultrasonic disperse is poured into molten
The swollen TPU in DMF stirs 2 ~ 5h under room temperature, then at 100W 1 ~ 2h of ultrasonic disperse, stands 1 ~ 2h and excludes air；
5) film, control film thickness are 0.06 ~ 0.08mm, obtain RGO-PPDA/TPU laminated film after solvent sufficiently volatilizees.
3. the poly- p-phenylenediamine of redox graphene -/TPU laminated film according to claim 2, it is characterised in that: step
2) mass ratio of graphene oxide and p-phenylenediamine monomer is 1:2.7-1:10.8 in.
4. the poly- p-phenylenediamine of redox graphene -/TPU laminated film according to claim 2, it is characterised in that: step
2) molar ratio of p-phenylenediamine monomer and ammonium persulfate is 1:0.67 in.
5. the poly- p-phenylenediamine of redox graphene -/TPU laminated film according to claim 2, it is characterised in that: step
3) mass volume ratio of GO-PPDA powder and hydrazine hydrate is 1:1 ~ 1:3 g/mL in.
6. the poly- p-phenylenediamine of redox graphene -/TPU laminated film according to claim 2, it is characterised in that: step
5) in gained RGO-PPDA/TPU laminated film, the content of RGO-PPDA is 0.1 ~ 1.5wt%.
7. a kind of poly- p-phenylenediamine of redox graphene-as described in claim 1/TPU laminated film is in water storage bag, oil storage bag
Or the application on instrumentation package bag.
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| CN101709147A (en) * | 2009-11-25 | 2010-05-19 | 中国科学院电工研究所 | Method for preparing composite material of graphene and graphene poly-p-phenylenediamine |
| CN104804204A (en) * | 2015-04-23 | 2015-07-29 | 福州大学 | Graphene/thermoplastic polyurethane composite and preparation method thereof |
| CN106147204A (en) * | 2016-08-30 | 2016-11-23 | 苏州佰锐生物科技有限公司 | A kind of preparation method of graphene/polyaniline/conductive polyurethane laminated film |
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| CN101709147A (en) * | 2009-11-25 | 2010-05-19 | 中国科学院电工研究所 | Method for preparing composite material of graphene and graphene poly-p-phenylenediamine |
| CN104804204A (en) * | 2015-04-23 | 2015-07-29 | 福州大学 | Graphene/thermoplastic polyurethane composite and preparation method thereof |
| CN106147204A (en) * | 2016-08-30 | 2016-11-23 | 苏州佰锐生物科技有限公司 | A kind of preparation method of graphene/polyaniline/conductive polyurethane laminated film |
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