CN102504451B - Preparation method of fluororesin/nanometer composite material - Google Patents
Preparation method of fluororesin/nanometer composite material Download PDFInfo
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- 239000000839 emulsion Substances 0.000 claims abstract description 50
- 239000002086 nanomaterial Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 21
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- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000013543 active substance Substances 0.000 claims description 19
- 239000008187 granular material Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- -1 nano zine oxide Chemical compound 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 9
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 9
- 150000003460 sulfonic acids Chemical class 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 239000000843 powder Substances 0.000 abstract description 6
- 239000002270 dispersing agent Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000004094 surface-active agent Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
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- 238000001556 precipitation Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
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Abstract
The invention discloses a preparation method for fluororesin/ a nanometer composite material. The preparation method comprises the following steps: 1) preparing fluororesin emulsion by 10-70% of fluororesin, 0.5-5% of surfactant I and the balance of water; 2) preparing nano dispersing agent by 1-10% of nano materials, 0.1-1% of surfactant II and the balance of water; 3) preparing composite emulsion by mixing the fluororesin emulsion and the nano dispersing agent according to the weight ratio being 100:10-100; and 4) conducting coprecipitation on the composite emulsion to obtain a precipitate, drying the precipitate to obtain composite powders, processing the composite powders to obtain the fluororesin/nanometer composite material. The fluororesin/nanometer composite material prepared by the method has the advantages of uniformity in dispersion, good performance and the like.
Description
Technical field
The invention belongs to Polymer Nanocomposites technical field, particularly a kind of fluoro-resin Nano-composite materials method.
Background technology
The features such as fluoro-resin has very excellent unreactiveness, high-low temperature resistant, frictional coefficient is little, dielectric properties are excellent are the current indispensable important materials of nearly all branch of industry centered by the industry such as chemical, mechanical.And prepare Polymer Nanocomposites by nano modification, be the feasible solution that significantly improves various types of resins performance, and obtained application and huge achievement widely.Although Performance of Fluoro Resins and Its is excellent, also there are some shortcomings.As poor in the wear resisting property of tetrafluoroethylene, its goods wear and tear under long-time continuous load, thereby have limited its range of application.In addition, heat conductivility and the conductivity of perfluoroethylene-propylene and polyvinylidene difluoride (PVDF) are poor, also limit their application.
For overcoming above-mentioned shortcoming, expand the range of application of fluoro-resin, researcher both domestic and external carries out a large amount of research to fluoro-resin, comprising nano-material modified fluoro-resin.Report utilizes nano aluminium oxide and nano zine oxide to improve the wear resistance of tetrafluoroethylene.In addition, can also utilize nano aluminum nitride to improve the heat conductivility of perfluoroethylene-propylene, utilize CNT (carbon nano-tube) to improve the conductivity of polyvinylidene difluoride (PVDF).Above-mentioned fluoro-resin nano composite material all can be in various degree the performance of raising goods, but the surface tension that fluoro-resin is extremely low causes nano material to be wherein difficult for dispersed, make stability and batch stability of matrix material be difficult to guarantee, hindered the commercial application of associated materials.
It is dispersed that nano material must be able to reach in resin, and keep dispersion stabilization, before Polymer Nanocomposites, makes demands.And nanoparticle due to high surface energy easy secondary agglomeration, will cause effectively bringing into play the performance of matrix material.Although numerous investigators carry out finishing to nano material, reduce its surface tension, thereby improve its dispersiveness; But the main preparation methods of fluoro-resin/nano material composite granule is dry blending at present, is difficult to obtain good dispersion effect.And the complete processing that adopts the advanced persons such as airflow milling can significantly improve the dispersiveness of nano material, but the method is subject to the restriction of specific equipment, implements difficulty larger.In addition, investigator also carries out the research that fluoro-resin/nano material composite granule is prepared in wet method blend, can partly improve the dispersing property of nano material, yet also has a certain distance with actual requirement.
Wet method blending technology is as follows: PTFE resin is mixed in runner milling with nano material, then add water, organic solvent and tensio-active agent in blend composition, the in the situation that of heating, apply certain shearing force, form conglomeration material dry.Because wet method blend is unfavorable for the dispersion of nano material, to such an extent as to the tensile strength of gained fluoro-resin nano composite material, elongation at break, wear resisting property are all not fully up to expectations.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of the fluororesin/nanometer composite material that a kind of technique is succinct, cost is low, adopt the method preparation and fluororesin/nanometer composite material there is the feature such as be uniformly dispersed, functional.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of fluororesin/nanometer composite material, comprise the following steps:
1), prepare fluoro-resin emulsion:
Fluoro-resin emulsion is combined by the composition of following weight content:
Fluoro-resin: 10～70% (being preferably 20～60%);
Tensio-active agent I:0.5～5% (being preferably 1～3%);
Surplus is water;
2), preparation nano material dispersion liquid:
Nano material dispersion liquid is combined by the composition of following weight content:
Nano material: 1～10% (being preferably 2～5%);
Tensio-active agent II:0.1～1% (being preferably 0.1～0.5);
Surplus is water;
3), preparation composite emulsion:
By fluoro-resin emulsion and nano material dispersion liquid, (be preferably 100: 10～40) weight ratio is obtained by mixing composite emulsion according to 100: 10～100;
4), above-mentioned composite emulsion first carries out co-precipitation, the throw out drying obtaining is processed, and obtains composite granule; Described composite granule passes through processing treatment again, obtains fluororesin/nanometer composite material.
Improvement as the preparation method of fluororesin/nanometer composite material of the present invention:
Fluoro-resin is tetrafluoroethylene, perfluoroethylene-propylene, polyvinylidene difluoride (PVDF) or ethylene-tetrafluoroethylene copolymer;
Tensio-active agent I and tensio-active agent II are perfluorinated sulfonic acid, Perfluorocaprylic Acid, perfluorinated sulfonic acid ammonium, ammonium perfluorocaprylate or polyoxyethylene nonylphenol ether;
Nano material is nano aluminium oxide, nano-silicon nitride, nano silicon oxide, nano-titanium oxide, nanometer silicon carbide, nano-graphite, nano molybdenum disulfide, nm-class boron nitride, nano zine oxide, CNT (carbon nano-tube), graphene oxide or Graphene; The particle diameter of above-mentioned nano material is 0.1～100nm.
Further improvement as the preparation method of fluororesin/nanometer composite material of the present invention:
Step 4) in:
Co-precipitation is: composite emulsion is stirred 10～120 minutes under the stirring velocity of 300～6000r/min, thereby realize breakdown of emulsion, after then precipitating completely; Obtain throw out.Drying treatment is to be dried 5～24 hours in 100～120 ℃.Processing treatment is mold pressing-sintering, extrudes or injection moulding.
In the present invention, to select identical material be best for tensio-active agent I and tensio-active agent II.
In the present invention, tensio-active agent (that is, tensio-active agent I and tensio-active agent II) can improve the dispersiveness of fluoro-resin in water, is the precondition of implementing co-precipitation.Tensio-active agent can also improve the avidity of nano material and fluoro-resin, thereby obtains the good fluororesin composite material of over-all properties.
In the present invention, stirring velocity during breakdown of emulsion is 300～6000r/min.Too low stirring velocity is difficult for reaching breakdown of emulsion condition, cannot obtain fluoro-resin powder; Too high stirring velocity causes fast emulsion breaking precipitation, is difficult to obtain the homodisperse composite granule of nano material.Therefore under the stirring velocity that, best demulsification technology parameter is 500～600r/min, stir 1～2 hour.
The wet method blend of informing in background technology is from major technique distinctive points of the present invention: except the selection of material and batching different, also comprise: first (1) wet method blend mixes PTFE resin with nano material, and co-precipitation rule of the present invention is mixed PTFE resin step by step with nano material; (2) wet method blend utilizes water and organic solvent, and coprecipitation method is only utilized water.
Adopt the inventive method preparation and fluororesin/nanometer composite material, its tensile strength can be up to 35.3 MPa, elongation at break up to 323%, wear resisting property is up to 0.013g.Therefore, fluororesin/nanometer composite material of the present invention can keep the fundamental characteristics (being chemical-resistant, contamination resistance etc.) of fluoro-resin, give the functions such as wear-resisting, the resistance to creep of fluoro-resin, conduction, heat conduction simultaneously, be applicable to the fields such as machinery, chemical industry, electronics, aviation.
In sum, the present invention will adopt emulsion blending method to prepare fluoro-resin/nano material composite emulsion, then by chemical coprecipitation technique, prepare the finely dispersed composite granule of nano material; Afterwards composite granule is carried out to processed and applied, can increase substantially the performance (tensile strength, elongation at break and wear resisting property) of fluoro-resin product.
Embodiment
Below in conjunction with case study on implementation, the present invention is further described.
% in all embodiment is % by weight below.
Fluoro-resin emulsion and nano material dispersion liquid configure respectively.
During fluoro-resin emulsion configuration, in the ratio of each component in the formula of fluoro-resin emulsion, weigh respectively the weight of fluoro-resin, tensio-active agent I and water; Again fluoro-resin and tensio-active agent I are added in water, by certain stirring velocity (100～400r/min) and churning time (0.5～7 hour), obtain uniform and stable fluoro-resin emulsion.Also commercially available fluoro-resin emulsion can be diluted to configuration according to a certain percentage, thereby obtain certain density fluoro-resin emulsion.
During the configuration of nano material dispersion liquid, in the ratio of each component in the formula of nano material dispersion liquid, weigh respectively the weight of nano material, tensio-active agent II and water; Again nano material and tensio-active agent II are added in water, by certain stirring velocity (100～500r/min) and churning time (4～10 hours), obtain uniform and stable nano material dispersion liquid.
Coprecipitation process is in stirring at low speed, load weighted nano material dispersion liquid is by a certain percentage added in fluoro-resin emulsion, press afterwards certain stirring velocity (stirring velocity of 300～6000r/min) by fluoro-resin and nano material breakdown of emulsion, obtain throw out and supernatant liquid, filter and be precipitated thing.
Throw out for example, for example,, 100～120 ℃ (being 110 ℃) lower vacuum-drying 5～24 hours (being 8h), is obtained to fluoro-resin/nano material composite granule.Composite granule through mold pressing-sintering, extrude, the technique such as injection moulding, obtain multiple fluoro-resin nano composite material.
The preparation method of embodiment 1, a kind of fluororesin/nanometer composite material, carries out following steps successively:
When 100r/min speed stirs, 60g tetrafluoroethylene, 1.5g perfluorinated sulfonic acid ammonium are slowly added in 38.5 grams of water, and stirring velocity is brought up to 200r/min, stir 5h, obtain dispersed and stable ptfe emulsion.
In addition, when 100r/min speed stirs, 5g nano aluminium oxide (particle diameter is 20nm), 0.5g perfluorinated sulfonic acid ammonium are slowly added in 94.5 grams of water, and stirring velocity is brought up to 300r/min, stir 5h, obtain dispersed and stable nano aluminium oxide dispersion liquid.
Then, when 100r/min speed stirs, 20g nano aluminium oxide dispersion liquid is slowly joined in 100g ptfe emulsion, stir 30min.Afterwards stirring velocity is brought up to 500r/min, stir 1h, thereby realize breakdown of emulsion; , there is supernatant liquid in emulsion precipitation to be composite completely rear (about 30min), filters and be precipitated thing.By throw out vacuum-drying 8h at 110 ℃, obtain tetrafluoroethylene/nano aluminium oxide composite granule.Composite granule mold pressing 5min, 380 ℃ of sintering 30min under 36MPa obtain tetrafluoroethylene/nano oxidized aluminum composite.
According to HG/T 2902-1997, GB-T 3960, detect respectively, the tensile strength of this matrix material is 32.1MPa, and elongation at break is 3 10%, and wear resisting property is 0.013g.
The preparation method of embodiment 2, a kind of fluororesin/nanometer composite material, carries out following steps successively:
When 100r/min speed stirs, 60g tetrafluoroethylene, 1.5g ammonium perfluorocaprylate are slowly added in 38.5 grams of water, and stirring velocity is brought up to 200r/min, stir 5h, obtain dispersed and stable ptfe emulsion.
In addition, when 100r/min speed stirs, 5g nano zine oxide (particle diameter is 100nm), 0.5g ammonium perfluorocaprylate are slowly added in 94.5 grams of water, and stirring velocity is brought up to 300r/min, stir 5h, obtain dispersed and stable nano zinc oxide fluid dispersion.
Then, when 100r/min speed stirs, 20g nano zinc oxide fluid dispersion is slowly joined in 100g ptfe emulsion, stir 30min.Afterwards stirring velocity is brought up to 500r/min, stir 1h, thereby realize breakdown of emulsion; , there is supernatant liquid in composite emulsion precipitation completely rear (about 30min), filters and be precipitated thing.By throw out vacuum-drying 8h at 110 ℃, obtain tetrafluoroethylene/nano zinc oxide composite powder.Composite granule mold pressing 5min, 380 ℃ of sintering 30min under 36MPa obtain tetrafluoroethylene/nano-zinc oxide composite material.
The tensile strength of this matrix material is 34.1MPa, and elongation at break is 323%, and wear resisting property is 0.015g.
The preparation method of embodiment 3, a kind of fluororesin/nanometer composite material, carries out following steps successively:
When 100r/min stirs, in commercially available 25g 50% perfluoroethylene-propylene emulsion (weight ratio of perfluoroethylene-propylene 50%, perfluorinated sulfonic acid 6%, water 44%), add 25g water, thereby obtain perfluoroethylene-propylene emulsion diluent.
When 100r/min speed stirs, by 4g CNT (carbon nano-tube) (multiple-wall carbon nanotube, diameter is 10nm, length-to-diameter ratio 1000), 0.1g perfluorinated sulfonic acid slowly adds in 95.9 grams of water, and stirring velocity is brought up to 400r/min, stir 8h, obtain dispersed and stable nano material dispersion liquid.
Then, when 100r/min speed stirs, 10g CNT (carbon nano-tube) dispersion liquid is slowly joined in the perfluoroethylene-propylene emulsion diluent of 100g, stir 30min.Afterwards stirring velocity is brought up to 600r/min, stir 2h, thereby realize breakdown of emulsion; , there is supernatant liquid in composite emulsion precipitation completely rear (about 50min), filters and be precipitated thing.By throw out vacuum-drying 8h at 110 ℃, obtain perfluoroethylene-propylene/CNT (carbon nano-tube) composite granule.Composite granule mold pressing 3min, 280 ℃ of sintering 30min under 30MPa obtain perfluoroethylene-propylene/nanometer carbon pipe composite material.
After testing:
The tensile strength of this matrix material is 18.5MPa, and elongation at break is 236%.
The preparation method of embodiment 4, a kind of fluororesin/nanometer composite material, carries out following steps successively:
When 120r/min speed stirs, 30g ethylene-tetrafluoroethylene copolymer, 1.0g ammonium perfluorocaprylate are slowly added in 69 grams of water, and stirring velocity is brought up to 250r/min, and stir 3h, obtain dispersed and stable ethylene-tetrafluoroethylene copolymer emulsion.
In addition, when 100r/min speed stirs, by 2g graphene oxide (diameter 1～5 μ m, thickness 0.8～1.2nm), 0.2g ammonium perfluorocaprylate slowly adds in 97.8 grams of water, and stirring velocity is brought up to 250r/min, stir 5h, obtain dispersed and stable graphene oxide dispersion liquid.
Then, when 100r/min speed stirs, 40g graphene oxide dispersion liquid is slowly joined in 100g ethylene-tetrafluoroethylene copolymer emulsion, stir 30min.Afterwards stirring velocity is brought up to 600r/min, stir 1h, thereby realize breakdown of emulsion; , there is supernatant liquid in composite emulsion precipitation completely rear (about 60min), filters and be precipitated thing.By throw out vacuum-drying 8h at 110 ℃, obtain ethylene-tetrafluoroethylene copolymer/graphene oxide composite granule.Composite granule, 320 ℃ of extrusion mouldings, obtains ethylene-tetrafluoroethylene copolymer/graphene oxide composite material.
After testing:
The tensile strength of this matrix material is 35.3MPa, and elongation at break is 315%.
Comparative example 1,
60g tetrafluoroethylene is mixed in runner milling high speed with 1g nano aluminium oxide (particle diameter is 20nm), in blend composition, add 500ml water, 20ml zellon and 1.6g perfluorinated sulfonic acid ammonium again, the in the situation that of heating, with 1500r/min shearing force, form conglomeration material dry.Take out powder mold pressing 5min, 380 ℃ of sintering 30min under 36MPa and obtain tetrafluoroethylene/nano oxidized aluminum composite.
The tensile strength of this matrix material is 25.6MPa, and elongation at break is 265.4%, and wear resisting property is 0.018mg.
Comparative example 2,
60g tetrafluoroethylene is mixed in runner milling high speed with 1g nano zine oxide (particle diameter is 100nm), in blend composition, add 500ml water, 20ml zellon and 1.6g ammonium perfluorocaprylate again, the in the situation that of heating, with 1500r/min shearing force, form conglomeration material dry.Take out powder mold pressing 5min, 380 ℃ of sintering 30min under 36MPa and obtain tetrafluoroethylene/nano oxidized aluminum composite.
The tensile strength of this matrix material is 30.4MPa, and elongation at break is 275.9%, and wear resisting property is 0.031mg.
Fluoro-resin nano composite material of the present invention can keep the fundamental characteristics of fluoro-resin, improves the mechanical property of fluoro-resin simultaneously, and gives the functions such as wear-resisting, the resistance to creep of fluoro-resin, conduction, heat conduction, is applicable to the fields such as machinery, chemical industry, electronics, aviation.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (3)
1. the preparation method of fluororesin/nanometer composite material, is characterized in that comprising the following steps:
1), prepare fluoro-resin emulsion:
Described fluoro-resin emulsion is combined by the composition of following weight content:
Fluoro-resin: 10 ~ 70%;
Tensio-active agent I: 0.5 ~ 5%;
Surplus is water;
2), preparation nano material dispersion liquid:
Described nano material dispersion liquid is combined by the composition of following weight content:
Nano material: 1 ~ 10%;
Tensio-active agent II: 0.1 ~ 1%;
Surplus is water;
Described tensio-active agent I and tensio-active agent II are perfluorinated sulfonic acid, Perfluorocaprylic Acid, perfluorinated sulfonic acid ammonium or ammonium perfluorocaprylate;
Described nano material is nano aluminium oxide, nano zine oxide, CNT (carbon nano-tube) or graphene oxide;
3), preparation composite emulsion:
Described composite emulsion is obtained by mixing according to 100:10～100 weight ratio by fluoro-resin emulsion and nano material dispersion liquid;
4), above-mentioned composite emulsion first carries out co-precipitation, the throw out drying obtaining is processed, and obtains composite granule; Described composite granule passes through processing treatment again, obtains fluororesin/nanometer composite material;
Described co-precipitation is: composite emulsion is stirred 10 ~ 120 minutes under the stirring velocity of 300 ~ 6000 r/min, thereby realize breakdown of emulsion, after then precipitating completely; Obtain throw out.
2. the preparation method of fluororesin/nanometer composite material according to claim 1, is characterized in that:
Described fluoro-resin is tetrafluoroethylene, perfluoroethylene-propylene, polyvinylidene difluoride (PVDF) or ethylene-tetrafluoroethylene copolymer.
3. the preparation method of fluororesin/nanometer composite material according to claim 2, is characterized in that:
Drying treatment in described step 4) is to be dried 5 ~ 24 hours in 100 ~ 120 ℃;
Processing treatment in described step 4) is mold pressing-sintering, extrudes or injection moulding.
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