CN104845009A - Fluorine resin/graphene composite material with isolation structure and preparation method and application thereof - Google Patents
Fluorine resin/graphene composite material with isolation structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorine resin/graphene composite material and a preparation method and an application thereof. The fluorine resin/graphene composite material is distributed in a three-dimensional isolation network way, the size of fluorine resin is 50nm to 500mum, the fluorine resin is filled into a graphene three-dimensional network, and the content of the graphene in the fluorine resin/graphene composite material in volume is 0.01% to 10%. The preparation method comprises the following steps of (1) mixing and stirring graphene oxide and high-fluorine resin which is dispersed in the liquid medium, and adding a flocculating agent to flocculate, so as to obtain fluorine resin/graphene oxide core-shell particles; (2) performing refluxing reaction on the fluorine resin/graphene oxide core-shell particles and a graphene oxide reducing agent, so as to obtain fluorine resin/graphene core-shell particles; (3) finally, performing hot pressing and forming. The fluorine resin/graphene composite material has the advantages that the lower percolation concentration and higher conductivity are realized, the preparation method is simple, the operation is easy, the energy consumption is low, the repeatability is good, the cost is low, and the fluorine resin/graphene composite material can be widely applied into the preparation of conductive material.
Description
Technical field
The invention belongs to conductive polymer composites preparing technical field, be specifically related to a kind of fluoro-resin/graphene composite material with isolation structure and preparation method thereof and application.
Background technology
Graphene has high specific conductivity (~ 10
6and specific surface area (~ 2160m S/cm)
2/ g), in conductive polymer composites, there is great application prospect.
At present, the ordinary method preparing polymer graphite alkene matrix material mainly contains: solution method, scorification and situ aggregation method.Although solution method gained matrix material exceedes, to ooze concentration lower, and graphene oxide must process, and to avoid reuniting in reduction process, and this method needs to use a large amount of organic solvent, the higher and easy contaminate environment of cost.Stankovich etc. first use phenylisocyanate modified graphene oxide, then solution coprecipitation method is utilized to prepare polystyrene/graphene matrix material, exceed that to ooze concentration be 0.1vol% (Stankovich S., et al.Nature.2006,442:282).Scorification often uses thermal reduction Graphene for filler, and energy consumption is comparatively large, and graphene dispersion is poor, and matrix material exceedes that to ooze concentration higher.Polyethylene terephthalate/the graphene composite material that utilized melt-blending process to prepare such as Zhang, exceedes and oozes concentration up to 0.47vol% (Zhang H., et al., Polymer.2010,51:1191).Because graphene oxide reduction degree is lower in situ aggregation method, gained Electrical Conductivity of Composites is lower.Feng etc. utilize situ aggregation method to obtain polyethylene terephthalate/graphene composite material, and when Graphene addition is 3wt%, specific conductivity is only ~ and 10
-4s/m (Feng R., et al.Journal of Materials Chemistry.2011,21:3931).
In a word, utilize matrix material prepared by these ordinary methods, often there is higher conduction and exceed and ooze concentration or lower specific conductivity, this is because Graphene is easily reunited in macromolecule matrix, and in random dispersion state, electrical property advantage and the structural advantage of Graphene can not be given full play to.Therefore, how to make Graphene effectively build conductive network, to give full play to Graphene advantage, become the key of preparation polymer graphite alkene conducing composite material.
Isolation structure matrix material is the perfect Construct question solving Graphene network then, improves the conductivity of matrix material.Isolation structure refers to that filler is pushed between polymer particle and by it and arranges and the three-dimensional net structure (Kusy, R.P., et al.Nature-Physical Science.1971,229:58) of formation.Because filler grain is forced ordered arrangement by polymer particle, therefore more easily form conductive network, reduce matrix material and exceed and ooze concentration.Ou etc. find in polymethylmethacrylate/carbon black, when carbon black be random dispersion, conduct electricity and exceed that to ooze concentration be 2.7vol%, and during in isolation structure, be only 0.26vol% (Ou R., et al.Journal of Physical Chemistry B.2006,110:22365.).
Preparation polymer graphite alkene isolation structure matrix material generally includes two steps: the preparation of polymer/Graphene core-shell particle; And hot-formingly prepare matrix material.Wherein, the preparation of polymer/Graphene core-shell particle is the key preparing composite material of core-shell structure, is also the focus that each researchist pays close attention to.Chinese patent application CN 102585335A utilizes evaporating solvent method, namely by the solvent in evaporate to dryness polyethylene and graphene oxide mixed dispersion liquid, obtains polyethylene/graphene oxide core-shell particle, obtains polyethylene/core-shell particle after chemical reduction.Chinese patent application CN 103087386A utilizes evaporating solvent method equally, and utilizes thermal reduction to obtain ultra-high molecular weight polyethylene/graphite alkene core-shell particle.The graphene oxide dispersion being mixed with ps particle by a stage reduction method, is namely directly carried out chemical reduction by Chinese patent CN 103554702A, obtains polystyrene/graphene core-shell particle after filtration.Evaporating solvent method and a stage reduction method, although polymer/Graphene core-shell particle can be obtained, the more difficult control of preparation process.In the former evaporating solvent process, a large amount of graphene oxide can deposit on the wall; And in the latter's reduction process, Graphene will form aggregate under van der Waals interaction, affect polymer/Graphene nucleocapsid structure homogeneity.
Summary of the invention
An object of the present invention is to provide a kind of fluoro-resin/graphene composite material with isolation structure and preparation method thereof, and this matrix material has three-dimensional isolation structure and low exceeding oozes.
Fluoro-resin/graphene composite material provided by the present invention is that fluoro-resin/Graphene core-shell particle obtains after hot-forming, Graphene is isolated by fluoro-resin, in three-dimensional isolation network shape distribution, the average particle size particle size of fluoro-resin is 50nm ~ 500 μm, fluoro-resin is full of in described Graphene three-dimensional network, wherein, the volume content of Graphene in fluoro-resin/graphene composite material is 0.01vol% ~ 10vol%.
Described fluoro-resin is selected from least one in polyvinylidene difluoride (PVDF), voltalef, ethylene-tetrafluoroethylene copolymer, ethylene-trifluoroethylene-vinyl chloride copolymer, fluorinated ethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer and hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-perfluoroalkyl vinyl ether multipolymer.
In described fluoro-resin/graphene composite material, the volume content of Graphene specifically can be 0.037vol% ~ 3.53vol%.
Described fluoro-resin/graphene composite material is prepared by following preparation method.
The preparation method of fluoro-resin/graphene composite material provided by the present invention, comprises the steps:
1) fluoro-resin/graphene oxide core-shell particle is prepared: by the fluoro-resin that is scattered in liquid medium and graphene oxide mix and blend, add flocculation agent again, carry out flocculation treatment, graphene oxide is flocculated on fluororesin surface, obtains fluoro-resin/graphene oxide core-shell particle;
2) prepare fluoro-resin/Graphene core-shell particle: the fluoro-resin be scattered in liquid medium/graphene oxide core-shell particle and graphene oxide reductive agent are carried out back flow reaction, obtain fluoro-resin/Graphene core-shell particle;
3) prepare fluoro-resin/graphene composite material: to step 2) in fluoro-resin/Graphene core-shell particle of obtaining carry out hot-forming, obtain fluoro-resin/graphene composite material.
In above-mentioned preparation method, step 1) in, described fluoro-resin is selected from least one in polyvinylidene difluoride (PVDF), voltalef, ethylene-tetrafluoroethylene copolymer, ethylene-trifluoroethylene-vinyl chloride copolymer, fluorinated ethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer and hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-perfluoroalkyl vinyl ether multipolymer.
Described fluoro-resin is through the fluoro-resin of surface modification treatment, described surface modification treatment specifically can using plasma modification, radiation modification, at least one in photochemical modification and chemical surface graft modification.To make fluoro-resin and graphene oxide better combine.As: the polyvinylidene difluoride (PVDF) particulate of Modified by Acrylamide Graft, amino modified fluorinated ethylene propylene particulate etc.
Described liquid medium is the liquid solvent that can not dissolve described fluoro-resin, specifically can be selected from least one in water, ethanol, DMF and acetone.Obviously, for fluorinated resin particle in guarantee process fully can contact with graphene oxide particulate, the piling height being scattered in the fluoro-resin in liquid medium should lower than the liquid level of dispersion system.
The volume content of described graphene oxide in described fluoro-resin/graphene oxide core-shell particle is 0.01 ~ 10vol%.
Described graphene oxide specifically can graphene oxide dry powder, the form of aqueous dispersions can also add, be preferably graphene oxide aqueous dispersions.
Described mix and blend carries out under normal temperature (25 DEG C), and churning time is 0.1 ~ 24h.
Described flocculation agent is selected from least one in sodium-chlor, SODIUMNITRATE, sodium sulfate, Repone K, saltpetre, potassium sulfate, hydrochloric acid, nitric acid, sulfuric acid, sodium hydroxide and potassium hydroxide.
Described flocculation agent specifically can the form of flocculant aqueous solution add, and the volumetric molar concentration of described flocculant aqueous solution is not less than 0.1mol/L, specifically can be 0.1-0.3mol/L.
The feed postition of described flocculation agent specifically can be and progressively adds, until dispersion medium clear, shows that graphene oxide all flocculates and forms sediment on fluorinated resin particle
Described flocculation treatment is carried out at normal temperatures.
In above-mentioned preparation method, step 1) in, also comprise and gains after described flocculation treatment are filtered successively, wash and the step of drying, wherein, the temperature of described drying is 50 ~ 100 DEG C, is specially 60 DEG C, time is 0.1 ~ 48h, with products weight without till considerable change.
In above-mentioned preparation method, step 2) in, described liquid medium is the liquid solvent that can not dissolve described fluoro-resin/graphene oxide core-shell particle, specifically can be selected from least one in water, ethanol, DMF and acetone.
Described graphene oxide reductive agent is selected from least one in hydrazine hydrate, dimethylhydrazine, phenylhydrazine, sodium borohydride, lithium aluminum hydride, hydroiodic acid HI and xitix.
The excessive use of described graphene oxide reductive agent, to ensure the abundant reduction of graphene oxide.Specifically according to the degree of oxidation of graphene oxide, then can require and cost consideration according to chemical reaction, determine concrete consumption.
The temperature of reaction of described back flow reaction is 50-150 DEG C, and specifically can be 100 DEG C, the reaction times is 1 ~ 24h, specifically can be 6h.The temperature and time of back flow reaction is specifically chosen in this limited range according to liquid medium used.
In above-mentioned preparation method, step 2) in, also comprise and gains after described back flow reaction are filtered successively, wash and the step of drying.This step can repeatedly, so that the impurity on gains surface after cleaning described back flow reaction.
In above-mentioned preparation method, step 3) in, describedly hot-formingly adopt with the following method: described fluoro-resin/Graphene core-shell particle is placed in compression molding on tabletting machine, and forming shape is determined according to mold shape, wherein, described hot-forming condition is as follows: forming pressure is not less than 1MPa; Molding time is 3 ~ 60min; For crystallization fluoro-resin, mold temperature is for being greater than its fusing point 5 ~ 70 DEG C, and for amorphous fluoro-resin, mold temperature is for being greater than its second-order transition temperature 30 ~ 100 DEG C;
In addition, the present invention's preparation-obtained fluoro-resin/Graphene core-shell particle also belongs to protection scope of the present invention preparing the application in electro-conductive material.
In the present invention's preparation-obtained fluoro-resin/Graphene core-shell particle, Graphene filler is forced in the exclusion finite space between particles by high molecular polymer particulate, in three-dimensional isolation network shape distribution, more easily form conductive network, there is lower exceeding and ooze concentration and higher specific conductivity, exceed and ooze that concentration is minimum can reach 10
-4the order of magnitude, the antistatic standard 10 of Conductivity Ratio
-6the high several order of magnitude of S/m.
The preparation method of the present invention's preparation-obtained fluoro-resin/Graphene core-shell particle, process is simple, be easy to control, energy consumption is low, reproducible, with low cost.
Accompanying drawing explanation
Fig. 1 is the digital photograph of fluoro-resin and graphene oxide liquid mixture in embodiment 1: before flocculation (a); After flocculation (b).
Fig. 2 is the stereoscan photograph of fluoro-resin in embodiment 2-7/Graphene core-shell particle, and Graphene volume ratio is respectively: 0 (a, b); 0.73vol% (c, d); 1.44vol% (e); 3.53vol% (f).
Fig. 3 is the optical microscope photograph in fluoro-resin in embodiment 2-7/graphene composite material transverse section, and Graphene volume ratio is respectively: 0 (a); 0.037vol% (b); 0.37vol% (c); 3.53vol% (d).
Fig. 4 is the change curve of specific conductivity with Graphene content of fluoro-resin/graphene composite material in embodiment 2-7.
Embodiment
Be described method of the present invention below by specific embodiment, but the present invention is not limited thereto, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, prepare fluoro-resin/graphene composite material:
Adopt the polyvinylidene difluoride (PVDF) particulate of Modified by Acrylamide Graft, its number average bead diameter is 100 μm.Preparation process is divided into three steps: the polyvinylidene difluoride (PVDF)/preparation of graphene oxide core-shell particle, the reduction of graphene oxide and hot-forming.
A) 2.0g modified polyvinilidene fluoride particulate is placed in 25ml water, after ultrasonic disperse 0.5h, adds aqueous dispersions (solid content 20mg, the graphene oxide density 2.2g/cm of the graphene oxide of 25ml
3, volume is about 9.09 × 10
-3cm
3) in, after stirring 2h under normal temperature, the sodium nitrate aqueous solution of the 0.2mol/L of 50ml is added in above-mentioned mixed solution, repeatedly after filtration washing drying, obtain polyvinylidene difluoride (PVDF)/graphene oxide core-shell particle, make the volume fraction of graphene oxide be 0.73vol%.Add NaNO
3front and back, the change of mixed solution as shown in the digital photograph of Fig. 1, wherein flocculation before (a); After flocculation (b), as can be seen from Figure 1: before flocculation, upper strata dispersion liquid is brown; After flocculation, because the flocculation of graphene oxide is separated out, dispersion liquid becomes clear, and bottom settlings thing is homogeneous yellow.
B) polyvinylidene difluoride (PVDF)/graphene oxide core-shell particle is scattered in 50ml water, the massfraction adding 20 μ L is the hydrazine hydrate aqueous solution of 85%, back flow reaction 6h at 100 DEG C, with deionized water filtration washing repeatedly, through baking oven 60 DEG C of dry 24h, obtained polyvinylidene difluoride (PVDF)/Graphene core-shell particle.
C) polyvinylidene difluoride (PVDF)/Graphene core-shell particle is placed on tabletting machine is suppressed into flaky composite material, forming pressure 10MPa, molding time 6min, mold temperature 190 DEG C, Graphene content is 0.73vol%, and through conducting performance test, the specific conductivity of gained matrix material is 0.87S/m.
Embodiment 2-7, prepare fluoro-resin/graphene composite material:
Adopt the polyvinylidene difluoride (PVDF) particulate of the Modified by Acrylamide Graft in embodiment 1, changing graphene oxide addition is 1mg, 2mg, 6mg, 10mg, 40mg and 100mg.Massfraction is that the addition of the hydrazine hydrate aqueous solution of 85% is respectively 1 μ L, 2 μ L, 6 μ L, 10 μ L, 40 μ L and 100 μ L.Other steps and condition in the same manner as in Example 1, obtain polyvinylidene difluoride (PVDF)/Graphene core-shell particle that Graphene volume fraction is 0.037vol%, 0.073vol%, 0.22vol%, 0.37vol%, 1.44vol% and 3.53vol% respectively.
Choosing filler Graphene content is 0, 0.73vol%, polyvinylidene difluoride (PVDF)/Graphene the core-shell particle of 1.44vol% and 3.53vol% carries out surface sweeping electron microscopic observation, as shown in Figure 2, wherein, in Fig. 2 a and Fig. 2 b, Graphene content is 0, in Fig. 2 c and Fig. 2 d, Graphene content is 0.73vol%, in Fig. 2 e, Graphene content is 1.44vol%, in Fig. 2 f, Graphene content is 1.44vol%, can learn from Fig. 2: graphene coated defines core-shell particles at polyvinylidene difluoride (PVDF) particle surface, and along with the increase of Graphene content, core-shell particles surface becomes coarse, illustrate that the amount of the Graphene modified is more.
Choosing filler Graphene content is 0, 0.037vol%, the Polyvinylidene fluoride/graphene composite of 0.37vol% and 3.53vol% carries out transverse section observation by light microscope, as shown in Figure 3, wherein, in Fig. 3 a, Graphene content is 0, in Fig. 2 b, Graphene content is 0.037vol%, in Fig. 2 c, Graphene content is 0.37vol%, in Fig. 2 d, Graphene content is 3.53vol%, can learn from Fig. 3: Graphene is isolation network structure distribution, Graphene is in the composite by the isolated formation network structure of polyvinylidene difluoride (PVDF), along with Graphene content increases, network thickness becomes large.
Conducting performance test is carried out to the Polyvinylidene fluoride/graphene composite of different Graphene content, test result as shown in Figure 4, can learn from Fig. 4: composite material conductive behavior meets percolation, when Graphene content is 0.037vol%, Electrical Conductivity of Composites is up to 1.71 × 10
-4s/m, higher than antistatic threshold value 10
-6s/m two orders of magnitude; When Graphene content is 2.45vol%, Electrical Conductivity of Composites reaches 6.8s/m.And carry out the Fitting Calculation by following power law rule formula and exceed and ooze concentration, obtain exceeding and ooze concentration and be only 0.031vol%.
σ
c＝σf[(φ-φ
p)/(1-φ
p)]
t
Embodiment 8, prepare fluoro-resin/graphene composite material:
Liquid dispersion medium water in embodiment 1, with embodiment 1, is only changed into the mixed solvent of water and ethanol by other step and condition, and both mass ratioes are 1: 1, prepare Polyvinylidene fluoride/graphene composite, make Graphene content be 0.73vol%, after tested, its specific conductivity is 0.87S/m.
Embodiment 9, prepare fluoro-resin/graphene composite material:
Other step and condition are with embodiment 1, only the graphene oxide reductive agent hydrazine hydrate in embodiment 1 is changed to the sodium borohydride of 20mg, prepare fluoro-resin/graphene composite material, wherein Graphene content is 0.73vol%, after tested, its specific conductivity is 0.79S/m.
Embodiment 10, prepare fluoro-resin/graphene composite material:
Other step and condition are with embodiment 1, only the flocculation agent SODIUMNITRATE in embodiment 1 is changed to 50ml, 0.1mol/L aqueous hydrochloric acid, prepares fluoro-resin/graphene composite material, wherein Graphene content is 0.73vol%, after tested, its specific conductivity is 0.79S/m.
Embodiment 11, prepare fluoro-resin/graphene composite material:
Flocculation agent SODIUMNITRATE in embodiment 1, with embodiment 1, is only changed to 50ml, 0.2mol/L potassium chloride solution, prepares fluoro-resin/graphene composite material by other step and condition, wherein, Graphene content is 0.73vol%, and after tested, its specific conductivity is 0.87S/m.
Embodiment 12, prepare fluoro-resin/graphene composite material:
The number average bead diameter of the acrylic amide modified polyvinylidene difluoride (PVDF) in embodiment 1, with embodiment 1, is only changed to 100nm, prepares fluoro-resin/graphene composite material by other step and condition, and wherein Graphene content is 0.73vol%, and after tested, its specific conductivity is 0.52S/m.
Embodiment 13, prepare fluoro-resin/graphene composite material:
Other steps and condition are with embodiment 1, fluoro-resin matrix in embodiment 1 is changed into the amino modified ethylene-tetrafluoroethylene copolymer particle that number average bead diameter is 400 μm, hot-forming temperature changes 300 DEG C into, and final gained matrix material Graphene content is 0.63vol%, and specific conductivity is 1.01S/m.
Embodiment 14, prepare fluoro-resin/graphene composite material:
Other step and condition, with embodiment 13, only change amino modified fluorinated ethylene propylene number average bead diameter into 1.6 μm, prepare fluoro-resin/graphene composite material, and wherein Graphene content is 0.73vol%, and after tested, its specific conductivity is 0.72S/m.
Embodiment 15, prepare fluoro-resin/graphene composite material:
Other step and condition are with embodiment 1, fluoro-resin matrix in embodiment 1 is changed into the amino modified ethylene-tetrafluoroethylene copolymer particle that number average bead diameter is about 100 μm, hot-forming temperature is 300 DEG C, final gained matrix material Graphene content is 0.70vol%, and its specific conductivity is 0.87S/m.
Claims (9)
1. fluoro-resin/graphene composite material, described fluoro-resin/graphene composite material is that fluoro-resin/Graphene core-shell particle obtains after hot-forming, Graphene is isolated by fluoro-resin, distribute in three-dimensional network shape, the average particle size particle size of fluoro-resin is 50nm ~ 500 μm, fluoro-resin is full of in described Graphene three-dimensional network, and wherein, the volume content of Graphene in fluoro-resin/graphene composite material is 0.01% ~ 10%.
2. fluoro-resin/graphene composite material according to claim 1, is characterized in that: described fluoro-resin is selected from least one in polyvinylidene difluoride (PVDF), voltalef, ethylene-tetrafluoroethylene copolymer, ethylene-trifluoroethylene-vinyl chloride copolymer, fluorinated ethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-perfluoroalkyl vinyl ether multipolymer and viton;
The preparation method of described fluoro-resin/graphene composite material according to any one of claim 1-8 and preparing.
3. the preparation method of the fluoro-resin/graphene composite material described in claim 1 or 2, comprises the steps:
1) fluoro-resin/graphene oxide core-shell particle is prepared: by the fluoro-resin that is scattered in liquid medium and graphene oxide mix and blend, then add flocculation agent, carry out flocculation treatment, obtain fluoro-resin/graphene oxide core-shell particle;
2) prepare fluoro-resin/Graphene core-shell particle: the fluoro-resin be scattered in liquid medium/graphene oxide core-shell particle and graphene oxide reductive agent are carried out back flow reaction, obtain fluoro-resin/Graphene core-shell particle;
3) prepare fluoro-resin/graphene composite material: to step 2) in fluoro-resin/Graphene core-shell particle of obtaining carry out hot-forming, obtain fluoro-resin/graphene composite material.
4. preparation method according to claim 3, it is characterized in that: step 1) in, described fluoro-resin is selected from least one in polyvinylidene difluoride (PVDF), voltalef, ethylene-tetrafluoroethylene copolymer, ethylene-trifluoroethylene-vinyl chloride copolymer, fluorinated ethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer and hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-perfluoroalkyl vinyl ether multipolymer;
The volume content of described graphene oxide in described fluoro-resin/graphene oxide core-shell particle is 0.01 ~ 10%;
Described liquid medium is the liquid solvent that can not dissolve described fluoro-resin;
Described mix and blend carries out at normal temperatures, and churning time is 0.1 ~ 24h;
Described flocculation treatment is carried out at normal temperatures.
5. the preparation method according to claim 3 or 4, is characterized in that: described liquid medium is selected from least one in water, ethanol, DMF and acetone;
Described flocculation agent is selected from least one in sodium-chlor, SODIUMNITRATE, sodium sulfate, Repone K, saltpetre, potassium sulfate, hydrochloric acid, nitric acid, sulfuric acid, sodium hydroxide and potassium hydroxide;
Described fluoro-resin is through the fluoro-resin of surface modification treatment, at least one in the modification of described surface modification treatment using plasma, radiation modification, photochemical modification and chemical surface graft modification.
6. the preparation method according to any one of claim 3-5, is characterized in that: described graphene oxide adds with the form of graphene oxide dry powder or graphene oxide aqueous dispersions;
Described flocculation agent adds with the form of flocculant aqueous solution, and the volumetric molar concentration of described flocculant aqueous solution is not less than 0.1mol/L;
The feed postition of described flocculation agent is for progressively to add, until dispersion medium clear.
Step 1) in, also comprise and filter successively gains after described flocculation treatment, wash and the step of drying, wherein, the temperature of described drying is 50 ~ 100 DEG C, and the time is 0.1-48h.
7. the preparation method according to any one of claim 3-6, it is characterized in that: step 2) in, described liquid medium is the liquid solvent that can not dissolve described fluoro-resin/graphene oxide core-shell particle, described liquid solvent is selected from least one in water, ethanol, DMF and acetone;
Described graphene oxide reductive agent is selected from least one in hydrazine hydrate, dimethylhydrazine, phenylhydrazine, sodium borohydride, lithium aluminum hydride, hydroiodic acid HI and xitix;
The temperature of reaction of described back flow reaction is 50-150 DEG C, and the reaction times is 1 ~ 24h;
Step 2) in, also comprise and gains after described back flow reaction are filtered successively, wash and the step of drying.
8. the preparation method according to any one of claim 3-7, it is characterized in that: step 3) in, describedly hot-formingly adopt with the following method: described fluoro-resin/Graphene core-shell particle is placed in compression molding on tabletting machine, forming shape is determined according to mold shape, wherein, described hot-forming condition is as follows: forming pressure is not less than 1MPa; Molding time is 3 ~ 60min; For crystallization fluoro-resin, mold temperature is for being greater than its fusing point 5 ~ 70 DEG C, and for amorphous fluoro-resin, mold temperature is for being greater than its second-order transition temperature 30 ~ 100 DEG C.
9. fluoro-resin/the graphene composite material described in claim 1 or 2 is preparing the application in electro-conductive material.
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| CN111592844A (en) * | 2020-05-19 | 2020-08-28 | 上海嘉好胶粘制品有限公司 | Hot-melt pressure-sensitive adhesive for high-temperature adhesive tape and preparation method thereof |
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