CN106674989A - RGO-PPDA (reduction graphene oxide-polyp phenylenediamine)/TPU (thermoplastic polyurethane) composite thin film - Google Patents
RGO-PPDA (reduction graphene oxide-polyp phenylenediamine)/TPU (thermoplastic polyurethane) composite thin film Download PDFInfo
- Publication number
- CN106674989A CN106674989A CN201710016213.7A CN201710016213A CN106674989A CN 106674989 A CN106674989 A CN 106674989A CN 201710016213 A CN201710016213 A CN 201710016213A CN 106674989 A CN106674989 A CN 106674989A
- Authority
- CN
- China
- Prior art keywords
- ppda
- tpu
- phenylenediamine
- rgo
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an RGO-PPDA (reduction graphene oxide-polyp phenylenediamine)/TPU (thermoplastic polyurethane) composite thin film. The RGO-PPDA/TPU composite thin film is prepared by the following steps: under the initiation action of ammonium persulfate, reducing and polymerizing PPDA on laminar GO (graphene oxide), so as to obtain GO-PPDA nanometer powder; reducing by hydrazine hydrate, so as to obtain RGO-PPDA nanometer powder; finally, utilizing a solution coating and film forming technology to prepare the RGO-PPDA/TPU composite thin film. The RGO-PPDA/TPU composite thin film has the advantages that by adopting a laminar structure, the serious agglomeration of graphene on a polymer is avoided; the compatibility of the GO and DMF (dimethyl formamide) is poor, and after the PPDA is reduced and polymerized on the GO in situ, the PPDA can be uniformly dispersed into the DMF, and the good dispersing in a TPU matrix in a solution coating and film filming process is realized; the graphene and the PPDA have excellent electric and heat conductivity, and a channel through which micromolecular matters pass through the composite thin film is greatly extended, so that the purpose of improving blocking, and electric and heat conductivity of the TPU thin film is realized.
Description
Technical field
The invention belongs to technical field of high-molecule composite preparation, and in particular to a kind of redox graphene-poly- right
Phenylenediamine/TPU laminated films.
Background technology
Graphene is by monolayer Sp2Hydbridized carbon atoms are tightly packed into bi-dimensional cellular shape lattice structure material with carbon element.Graphene
Special monoatomic layer structures shape its unique physical property, such as high intensity, high-moduluss, high thermal conductivity, high electronics is moved
Shifting rate, high-specific surface area and high obstructing performance etc..Graphene is to have now known one of material interior-heat conductance highest material, heat
Conductance is up to 5300W/ (mK).Unique electronic and physical characteristics that Graphene is showed so as to compound in polymer
There is important application prospect in material.
P-phenylenediamine is the aromatic amine with reproducibility, oxidizable in atmosphere.Poly- p-phenylenediamine has phenyl ring and quinoid
Alternate hierarchic structure, its electric conductivity is relatively low similar to nigrosine, conductivity is crossed, and about 6 × 10-6S/cm, using Graphene
Doped polymer composite is remarkably improved the conductivity of polymer.
Polyurethane Thermoplastic Elastomer（TPU）The one kind being made up of diisocyanate, polyhydric alcohol and short chain glycol
Heating can be plastified, solvent can dissolve（AB）nType block linear polymer.Polyurethane is a kind of height with extensive use
Molecular material, is mainly used in the aspects such as automobile, building, pavement material, mine, exploitation, electronics and space flight.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 macromolecular materials, polyurethane material thermal conductivity itself
Rate is low, with very high sheet resistance, static charge accumulation is easily produced in use, is to cause the safety such as fire, blast
The important hidden danger of accident.
Graphene oxide（GO）Although surface has an oxygen-containing functional groups such as carboxyl, hydroxyl, epoxy radicals, it is sonicated after energy
It is enough to realize peeling off and dispersed in water and in DMF, but dispersibility is general, stands a moment, and GO will be deposited on the bottom of DMF
Portion.In current domestic and foreign literature, antistatic treatment is carried out to TPU mainly by a large amount of white 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.It is of the invention successfully new to prepare
Comprehensive TPU nano composite materials provide new approach, while also compound for Future Development novel high-performance polymer nanocomposite
Material provides new thinking and explores so that the present invention, with innovation research value, has in actual applications academicly
Extensive economic results in society and strategic value.
The content of the invention
The present invention, by the poly- p-phenylenediamine of in-situ polymerization on graphene oxide, makes for not enough and defect of the prior art
The standby GO-PPDA powder being dispersed in DMF solution for obtaining energy stable and uniform, is combined after then being reduced with TPU, obtains one
Redox graphene-poly- p-phenylenediamine/TPU laminated films are planted, the thin-film material has good obstruct, heat conduction, antistatic
Performance, with extensive economic results in society and strategic value.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of redox graphene-poly- p-phenylenediamine/TPU laminated films, it adopts improvement Hummers methods to prepare graphite oxide
Alkene, then in ice-water bath, thereon after the poly- p-phenylenediamine of in-situ polymerization, Jing hydrazine hydrate reductions, then be scattered in DMF,
After supersound process, the TPU swollen in DMF is poured into, the redox graphene-poly- is obtained using solution coating film-forming process
P-phenylenediamine/TPU laminated films.
The preparation method of the redox graphene-poly- p-phenylenediamine/TPU laminated films, comprises the following steps that：
1）Graphite is carried out after cold treatment, in being placed in low-temp reaction bath, concentrated sulphuric acid is slowly added to while stirring, and in 3h in batches
Potassium permanganate is added, after low-temp reaction 0.5h, 50 DEG C is again heated to, continues to react 12h, be subsequently adding deionized water, stirred
15min, and Deca hydrogen peroxide, Jing pickling, are washed to neutrality, and lyophilizing obtains the graphene oxide of sheet；
2）By graphene oxide ultrasonic disperse in deionized water, in low-temp reaction bath p-phenylenediamine monomer and persulfuric acid are added
Ammonium initiator, less than 4 DEG C low temperature polymerizations react 24h, then stand 2h, and deionized water and absolute ethanol washing freeze to colourless
It is dry, obtain GO-PPDA powder；
3）Gained GO-PPDA powder ultrasonics are scattered in deionized water, hydrazine hydrate is subsequently adding, 90 DEG C are heated to, 3h is reacted,
2h is stood, then deionized water and absolute ethanol washing obtain RGO-PPDA nanometer powders to colourless, lyophilizing；
4）By step 3）In the RGO-PPDA nanometer powders that obtain, in being added to DMF solution, 100W 1 ~ 2h of ultrasonic disperse are poured into
The TPU in DMF is swollen in, 2 ~ 5h, then 100W 1 ~ 2h of ultrasonic disperse are stirred under room temperature, stood 1 ~ 2h and exclude air；
5）Film, it is 0.06 ~ 0.08mm to control film thickness, and RGO-PPDA/TPU laminated films are obtained after solvent fully volatilizees.
Step 2）Middle graphene oxide is 1 with the mass ratio of p-phenylenediamine monomer:2.7-1:10.8；P-phenylenediamine monomer with
The mol ratio of Ammonium persulfate. is 1:0.67.
Step 3）Middle GO-PPDA powder is 1 with the mass volume ratio of hydrazine hydrate:1~1:3 g/mL.
Step 5）In gained RGO-PPDA/TPU laminated films, the content of RGO-PPDA is 0.1 ~ 1.5wt%.
Gained redox graphene-poly- p-phenylenediamine/TPU laminated films can be used to prepare water storage bag, oil storage bag or instrument
Device packaging bag.
The beneficial effects of the present invention is：
（1）The present invention poly- p-phenylenediamine of in-situ polymerization, GO-PPDA nano composite materials of formation on sheet graphene oxide
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 and
DMF belongs to organic amine together, can form a large amount of hydrogen bonds, greatly improves GO-PPDA dispersibility in DMF, is more beneficial for it poly-
It is dispersed in compound matrix, and the RGO-PPDA nano composite materials obtained by hydrazine hydrate reduction is disperseed in DMF
Performance is equally fine, and then can realize the fine dispersion in TPU matrixes in solution coating film forming procedure, significantly improves
The compatibility between inorganic filler and polymeric matrix.
（2）So far, hydrazine hydrate reduction graphene oxide is a kind of fairly simple, efficient method of reducing, can be preferably
Redox graphene, and give full play to the excellent mechanical property of Graphene, barrier property and electric property etc..Therefore, its
The redox graphene of preparation/poly- p-phenylenediamine can be consolidated and be evenly distributed in TPU matrixes, and with its tight knot
Close, three-dimensional conductive network is formed in TPU matrixes, the antistatic property and heat conductivility of material can be improved.
（3）TPU laminated film safety and environmental protections prepared by the present invention, dust-proof, anti-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, the present invention adapts to work as
The demand in modern market, preparation method is scientific and reasonable, strong operability, drastically increases TPU value-added contents of product, and extends it
Range of application, with extensive market prospect and significant social benefit.
Description of the drawings
Fig. 1 is GO（A）With GO-PPDA（B）SEM figure.
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）Deployment conditions figure in DMF.
Fig. 4 is that the GO-PPDA/TPU laminated films of different quality containing and the oxygen of RGO-PPDA/TPU laminated films are saturating
Cross rate situation of change figure.
Fig. 5 is the GO-PPDA/TPU laminated films of different quality containing and the volume electricity of RGO-PPDA/TPU laminated films
Resistance rate situation of change figure.
Fig. 6 is the GO-PPDA/TPU laminated films of different quality containing and the thermal conductivity of RGO-PPDA/TPU laminated films
Situation of change figure.
Specific embodiment
A kind of preparation method of redox graphene-poly- p-phenylenediamine/TPU laminated films, comprises the following steps that：
1）Graphite is carried out after cold treatment, in being placed in low-temp reaction bath, concentrated sulphuric acid is slowly added to while stirring, and in 3h in batches
Potassium permanganate is added, at 4 DEG C after low-temp reaction 0.5h, 50 DEG C is again heated to, continues to react 12h, be subsequently adding deionized water, stirred
Mix 15min, and the hydrogen peroxide of Deca 30%, Jing pickling, be washed to neutrality, lyophilizing obtains the graphene oxide of sheet；
2）By graphene oxide ultrasonic disperse in deionized water, in low-temp reaction bath p-phenylenediamine monomer and persulfuric acid are added
Ammonium initiator, less than 4 DEG C low temperature polymerizations react 24h, then stand 2h, and deionized water and absolute ethanol washing freeze to colourless
It is dry, obtain GO-PPDA powder；Wherein, graphene oxide and the mass ratio of p-phenylenediamine monomer are 1:2.7-1:10.8；To benzene two
Amine monomers are 1 with the mol ratio of Ammonium persulfate.:0.67；
3）Gained GO-PPDA powder ultrasonics are scattered in deionized water, hydrazine hydrate, GO-PPDA powder and hydration is subsequently adding
The mass volume ratio of hydrazine is 1:1~1:3 g/mL, are heated to 90 DEG C, react 3h, stand 2h, then deionized water and dehydrated alcohol
Wash to colourless, lyophilizing, obtain RGO-PPDA nanometer powders；
4）By step 3）In the RGO-PPDA nanometer powders that obtain, in being added to DMF solution, 100W 1 ~ 2h of ultrasonic disperse are poured into
The TPU in DMF is swollen in, 2 ~ 5h, then 100W 1 ~ 2h of ultrasonic disperse are stirred under room temperature, stood 1 ~ 2h and exclude air；
5）Film, it is 0.06 ~ 0.08mm to control film thickness, and RGO-PPDA contents are obtained after solvent fully volatilizees for 0.1 ~ 1.5%
RGO-PPDA/TPU laminated films.
Fig. 1 is graphene oxide GO（A）With GO-PPDA（B）SEM figure.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 that graphene oxide
C/O is the relative raising of relative amount that the C/O of 0.556, GO-PPDA is carbon in 1.197, GO-PPDA, is because that graphite oxide is dilute
Contain carbon in the poly- p-phenylenediamine of surface in situ growth, and it is not oxygen-containing, therefore C/O is made than significantly rising；And the C/O of RGO-PPDA
1.398 are reached, the value of its C/O is further raised, be because under the strong reducing action of hydrazine hydrate, the hydroxyl of surface of graphene oxide
The oxy radicals such as base, carboxyl, epoxy radicals 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）In being dispersed in 10mL DMF solutions respectively, obtained concentration
Situation map of the dispersion liquid of 1mg/mL Jing ultrasound 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 due to having amido in poly- p-phenylenediamine and DMF, being mixed due to similar, enhancing GO-PPDA and RGO-
Dispersibility of the PPDA in DMF, for later stage GO-PPDA and RGO-PPDA, uniform and stable dispersion provides guarantee in TPU.
In order that content of the present invention easily facilitates understanding, with reference to specific embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
1）Improve Hummers methods and prepare graphene oxide：First 1g graphite is carried out after cold treatment, is slowly added in low-temp reaction bath
Enter the concentrated sulphuric acids of 45mL 98% and 5mL strong phosphoric acid, stirring and evenly mixing, and 7g potassium permanganate is dividedly in some parts in nitration mixture in 3h, then it is low
Reaction system is moved to and be heated in water-bath 50 DEG C by temperature after reaction half an hour, is continued to be reacted and add after 12h 1000mL deionizations
Water, obtains rufous graphite suspension, continues to stir the hydrogen peroxide of Deca 30% after 15min, obtains brown graphite suspending liquid, most
Afterwards pickling is carried out with 3% hydrochloric acid solution, then be washed to neutrality, obtain graphene oxide gel, graphene oxide gel is carried out
Frozen dried, is obtained fluffy graphene oxide（GO）Solid；
2）The synthesis of GO-PPDA composites：1.53 g Ammonium persulfate .s are added in 25mL HCl, is stirred to being completely dissolved, put
Enter and cool down in ice bath 5 min, in pouring separatory funnel into；100mg GO solids are added to the beaker of the HCl of 75mL 1mol/L
In, and the ultrasonic disperse 1h under 100W, in pouring flask into, 1.08g p-phenylenediamine monomers are added, less than 4 DEG C ice are put into together
Magnetic stirring 0.5h in bath, then controls rate of addition, and ammonium persulfate solution is dripped in 0.5-1.0h, continues to react
24h, stands 2h, and deionized water and the multiple washing and filtering of dehydrated alcohol, to filtrate clear, colorless in neutrality, is then placed in freezing
In dry machine, lyophilizing obtains the nanometer GO-PPDA powder of black；
3）The synthesis of RGO-PPDA composites：Take step 2）Obtained nanometer GO-PPDA powder 100mg in round-bottomed flask, plus
Enter 100mL deionized waters, ultrasonic disperse 1h is subsequently adding 0.2 mL hydrazine hydrates, is heated to 90 DEG C, and heating reflux reaction 3h is quiet
2h, and deionized water and the multiple washing and filtering of dehydrated alcohol are put, to filtrate clear, colorless in neutrality, freeze dryer is then placed in
In, lyophilizing obtains the RGO-PPDA nanometer powders of black；
4）The preparation of mixing liquid：Weigh 0.015g RGO-PPDA nanometer powders to be scattered in 40mL DMF solutions, 100W's
Ultrasonic disperse 1h in ultrasonic cleaner, is subsequently added thereto to 7.5g TPU, and above-mentioned mixed system is put into into 70 DEG C of vacuum
Swelling 20h in drying baker, after and then the mixed system being stirred into 5h until TPU is completely dissolved on machine mixer, is placed in
Ultrasonic disperse 1h in the ultrasonic cleaner of 100W, and 1h is stood to guarantee fully to remove the bubble in mixing liquid；
5）Film：Sheet glass is placed on film applicator, then gained mixing liquid is applied on the glass sheet, control applies thickness
Spend for 0.08mm；After the completion of coating, sheet glass is dried into 24h in 90 DEG C of baking oven, obtain 0.2% RGO-PPDA/TPU THIN COMPOSITEs
Film.
Embodiment 2
Step 4）Middle addition 0.038g RGO-PPDA nanometer powders, other conditions parameter is same as Example 1, finally gives
0.5% RGO-PPDA/TPU laminated films.
Embodiment 3
Step 4）Middle addition 0.060g RGO-PPDA nanometer powders, other conditions parameter is same as Example 1, finally gives
0.8% RGO-PPDA/TPU laminated films.
Embodiment 4
Step 4）Middle addition 0.076g RGO-PPDA nanometer powders, other conditions parameter is same as Example 1, finally gives 1%
RGO-PPDA/TPU laminated films.
Embodiment 5
Step 4）Middle addition 0.015g nanometer GO-PPDA powder, other conditions parameter is same as Example 1, finally gives 0.2%
GO-PPDA/TPU laminated films.
Embodiment 6
Step 4）Middle addition 0.038g nanometer GO-PPDA powder, other conditions parameter is same as Example 1, finally gives 0.5%
GO-PPDA/TPU laminated films.
Embodiment 7
Step 4）Middle addition 0.060g nanometer GO-PPDA powder, other conditions parameter is same as Example 1, finally gives 0.8%
GO-PPDA/TPU laminated films.
Embodiment 8
Step 4）Middle addition 0.076g nanometer GO-PPDA powder, other conditions parameter is same as Example 1, finally gives 1%
GO-PPDA/TPU laminated films.
Fig. 4 is that the GO-PPDA/TPU laminated films of different quality containing and the oxygen of RGO-PPDA/TPU laminated films are saturating
Cross rate situation of change figure.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 the cm of minimum 137.6923•(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, also can be clearly seen that from Fig. 4, when mass fraction is identical, RGO-
PPDA/TPU thin film is lower than the OTR oxygen transmission rate of GO-PPDA/TPU thin film, and barrier property is more preferable.When addition mass fraction exceedes
When 0.8%, the OTR oxygen transmission rate of laminated film begins to decline.
Fig. 5 is the GO-PPDA/TPU laminated films of different quality containing and the volume electricity of RGO-PPDA/TPU laminated films
Resistance rate（ρv）Situation of change figure.Can be obtained by Fig. 5, with the increase of GO-PPDA and RGO-PPDA mass fractions, laminated film ρvOccur
Significantly decline, when their mass fractions reach 0.8%, the Log (ρ of composite material filmv) 5.987 and 4.825 are respectively,
Compare pure TPU film（12.543）7 orders of magnitude and 8 orders of magnitude are have dropped respectively, continue to increase GO-PPDA and RGO-PPDA
Mass fraction, laminated film ρvThere is no significant change, value is oozed about between 0.5% ~ 0.8% in its conduction Chongqing of deducibility,
Continuous conductive path or network are now basically formed in compound system, the laminated film of formation has good conduction
Property.Meanwhile, also can be clearly seen that from Fig. 5, when mass fraction is identical, RGO-PPDA/TPU thin film is thinner than GO-PPDA/TPU
The ρ of filmvAbout low an order of magnitude, illustrates that RGO-PPDA/TPU thin film has more excellent antistatic property, anti-quiet
The application in conductive film field has bigger potentiality.
Fig. 6 is the GO-PPDA/TPU laminated films of different quality containing and the thermal conductivity of RGO-PPDA/TPU laminated films
Situation of change figure.As seen in Figure 6, the thermal conductivity of laminated film is with the increasing of GO-PPDA and RGO-PPDA mass fractions
Plus and increase, when GO-PPDA and RGO-PPDA mass fractions reach 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 improve than pure TPU [0.213 W/ (mK)], illustrates compound
The thermal conductivity of thin film is greatly improved, and greatly extends application of the TPU film in terms of heat conduction.Meanwhile, from Fig. 6 also easily
Go out, when mass fraction is identical, RGO-PPDA/TPU thin film is higher than the thermal conductivity of GO-PPDA/TPU thin film, heat conductivility is more preferable,
Illustrate that RGO-PPDA/TPU thin film also more has prospect in terms of heat conduction.
Laminated film safety and environmental protection provided by the present invention, is particularly useful for making TPU medical mattress, TPU biogas storages
Bag, TPU paddle the field that the packaging etc. of class product, precision instrument has higher requirements to the obstruct 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, drastically increases the attached of TPU products
It is value added, and its range of application is extended, with extremely vast potential for future development and economic results in society.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (8)
1. a kind of redox graphene-poly- p-phenylenediamine/TPU laminated films, it is characterised in that：In ice-water bath, in oxidation
The poly- p-phenylenediamine of in-situ polymerization on Graphene, then Jing hydrazine hydrate reductions, then be scattered in DMF, after supersound process, pour into
The TPU in DMF is swollen in, the redox graphene-poly- p-phenylenediamine/TPU is obtained using solution coating film-forming process multiple
Close thin film.
2. redox graphene-poly- p-phenylenediamine/TPU laminated films according to claim 1, it is characterised in that：Its system
Preparation Method is comprised the following steps that：
1）Using the graphene oxide for improving Hummers methods preparation sheet；
2）By gained graphene oxide ultrasonic disperse in deionized water, in low-temp reaction bath p-phenylenediamine monomer and mistake are added
Ammonium persulfate initiator, low temperature polymerization reaction 24h, then stand 2h, deionized water and absolute ethanol washing to colourless, lyophilizing,
Obtain GO-PPDA powder；
3）Gained GO-PPDA powder ultrasonics are scattered in deionized water, hydrazine hydrate is subsequently adding, 90 DEG C are heated to, 3h is reacted,
2h is stood, then deionized water and absolute ethanol washing obtain RGO-PPDA nanometer powders to colourless, lyophilizing；
4）By step 3）In the RGO-PPDA nanometer powders that obtain be added in DMF solution, 100W 1 ~ 2h of ultrasonic disperse are poured into molten
The swollen TPU in DMF, stirs 2 ~ 5h under room temperature, then at 100W 1 ~ 2h of ultrasonic disperse, stand 1 ~ 2h and exclude air；
5）Film, it is 0.06 ~ 0.08mm to control film thickness, and RGO-PPDA/TPU laminated films are obtained after solvent fully volatilizees.
3. redox graphene-poly- p-phenylenediamine/TPU laminated films according to claim 2, it is characterised in that：Step
2）Middle graphene oxide is 1 with the mass ratio of p-phenylenediamine monomer:2.7-1:10.8.
4. redox graphene-poly- p-phenylenediamine/TPU laminated films according to claim 2, it is characterised in that：Step
2）Middle p-phenylenediamine monomer is 1 with the mol ratio of Ammonium persulfate.:0.67.
5. redox graphene-poly- p-phenylenediamine/TPU laminated films according to claim 2, it is characterised in that：Step
2）The temperature of middle low temperature polymerization reaction is below 4 DEG C.
6. redox graphene-poly- p-phenylenediamine/TPU laminated films according to claim 2, it is characterised in that：Step
3）Middle GO-PPDA powder is 1 with the mass volume ratio of hydrazine hydrate:1~1:3 g/mL.
7. redox graphene-poly- p-phenylenediamine/TPU laminated films according to claim 2, it is characterised in that：Step
5）In gained RGO-PPDA/TPU laminated films, the content of RGO-PPDA is 0.1 ~ 1.5wt%.
8. a kind of redox graphene as claimed in claim 1-poly- p-phenylenediamine/TPU laminated films are in water storage bag, oil storage bag
Or the application on instrumentation package bag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710016213.7A CN106674989B (en) | 2017-01-10 | 2017-01-10 | A kind of poly- p-phenylenediamine of redox graphene -/TPU laminated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710016213.7A CN106674989B (en) | 2017-01-10 | 2017-01-10 | A kind of poly- p-phenylenediamine of redox graphene -/TPU laminated film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106674989A true CN106674989A (en) | 2017-05-17 |
| CN106674989B CN106674989B (en) | 2019-02-22 |
Family
ID=58850538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710016213.7A Active CN106674989B (en) | 2017-01-10 | 2017-01-10 | A kind of poly- p-phenylenediamine of redox graphene -/TPU laminated film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674989B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084553A (en) * | 2017-12-27 | 2018-05-29 | 福州大学 | The preparation method of graphene nanobelt-poly- p-phenylenediamine/EVA laminated films |
| CN115072714A (en) * | 2022-06-07 | 2022-09-20 | 苏州大学 | Amine compound modified graphene film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20160231271A1 (en) * | 2013-09-30 | 2016-08-11 | Tongji University | Lead ion sensors, methods of making and uses 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 |
-
2017
- 2017-01-10 CN CN201710016213.7A patent/CN106674989B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20160231271A1 (en) * | 2013-09-30 | 2016-08-11 | Tongji University | Lead ion sensors, methods of making and uses thereof |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084553A (en) * | 2017-12-27 | 2018-05-29 | 福州大学 | The preparation method of graphene nanobelt-poly- p-phenylenediamine/EVA laminated films |
| CN115072714A (en) * | 2022-06-07 | 2022-09-20 | 苏州大学 | Amine compound modified graphene film and preparation method thereof |
| CN115072714B (en) * | 2022-06-07 | 2023-10-13 | 苏州大学 | Amine compound modified graphene film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106674989B (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Morsi et al. | Reinforcement of the optical, thermal and electrical properties of PEO based on MWCNTs/Au hybrid fillers: nanodielectric materials for organoelectronic devices | |
| Gao et al. | High-efficiency electromagnetic interference shielding realized in nacre-mimetic graphene/polymer composite with extremely low graphene loading | |
| Liu et al. | Microencapsulated phase change material modified by graphene oxide with different degrees of oxidation for solar energy storage | |
| CN105086425B (en) | Layered laminate functionalization graphene nanobelt/TPU composites and its preparation | |
| Wan et al. | Nitrile functionalized halloysite nanotubes/poly (arylene ether nitrile) nanocomposites: Interface control, characterization, and improved properties | |
| Chuang et al. | Influences of surface modification of nano-silica by silane coupling agents on the thermal and frictional properties of cyanate ester resin | |
| Zhang et al. | Thermal and electrical conductivity enhancement of graphite nanoplatelets on form-stable polyethylene glycol/polymethyl methacrylate composite phase change materials | |
| Huang et al. | Facile preparation of halloysite/polyaniline nanocomposites via in situ polymerization and layer-by-layer assembly with good supercapacitor performance | |
| Liu et al. | Smart monodisperse polystyrene/polyaniline core–shell structured hybrid microspheres fabricated by a controlled releasing technique and their electro-responsive characteristics | |
| Krasia-Christoforou | Organic–inorganic polymer hybrids: synthetic strategies and applications | |
| He et al. | Preparation and properties of polyethylene glycol/unsaturated polyester resin/graphene nanoplates composites as form-stable phase change materials | |
| Cao et al. | Fabrication and properties of graphene oxide-grafted-poly (hexadecyl acrylate) as a solid-solid phase change material | |
| Yang et al. | Synthesis of novel sunflower-like silica/polypyrrole nanocomposites via self-assembly polymerization | |
| WO2016041310A1 (en) | Waterproof and oxygen-insulation sealing film and preparation method and use thereof | |
| CN104640809A (en) | Cross-linked graphene networks | |
| Liu et al. | Polyethyleneimine-modified graphene oxide/PNIPAm thermoresponsive hydrogels with rapid swelling/deswelling and improved mechanical properties | |
| Xiao et al. | Strategy to enhance conductivity of polystyrene/graphene composite foams via supercritical carbon dioxide foaming process | |
| Du et al. | Synthesis and properties of poly (4, 4′-oxybis (benzene) disulfide)/graphite nanocomposites via in situ ring-opening polymerization of macrocyclic oligomers | |
| CN103897183A (en) | Binary carbon material-conductive polymer composite nano gas-sensitive thin film and preparation method thereof | |
| Tao et al. | 3D Graphene–sponge skeleton reinforced polysulfide rubber nanocomposites with improved electrical and thermal conductivity | |
| Wang et al. | Synthesis of HNTs@ PEDOT composites via in situ chemical oxidative polymerization and their application in electrode materials | |
| CN103834051A (en) | Barrier anti-static TPU (Thermoplastic Polyurethane) composite material film and preparation method thereof | |
| Ge et al. | Large cyclic deformability of microcellular TPU/MWCNT composite film with conductive stability, and electromagnetic interference shielding and self-cleaning performance | |
| Su et al. | Synthesis of high-k and low dielectric loss polymeric composites from crosslinked divinylbenzene coated carbon nanotubes | |
| CN106543478A (en) | A kind of preparation and flame retardance of polymer application of graphene-supported fullerene hybrid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200806 Address after: No. 3001, south section of Century Avenue, Luoshan street, Jinjiang City, Quanzhou City, Fujian Province Patentee after: FUJIAN CHENQI NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: Minhou County of Fuzhou City, Fujian province 350108 Street Town Road No. 2 University City School District of Fuzhou University Patentee before: FUZHOU University |