CN110105756A - A kind of high tenacity high thermal conductivity PBONF based coextruded film and preparation method thereof - Google Patents
A kind of high tenacity high thermal conductivity PBONF based coextruded film and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of high tenacity high thermal conductivity PBONF based coextruded films and preparation method thereof, belong to heat-conductive composite material technical field.High tenacity high thermal conductivity PBONF based coextruded film provided by the invention, including PBONF and heat conducting nanometer material；The PBONF forms tridimensional network, and heat conducting nanometer material is located in tridimensional network；The PBONF has forked geometry.High tenacity high thermal conductivity PBONF based coextruded film provided by the invention has many advantages, such as low-density, high tenacity and high heat conductance, it can replace current aviation alloyed aluminium, for aerospace flight vehicle loss of weight, while providing higher radiating efficiency and excellent structural reliability.
Description
Technical field
The present invention relates to heat-conductive composite material technical field more particularly to a kind of high tenacity high thermal conductivity PBONF base THIN COMPOSITEs
Film and preparation method thereof.
Background technique
With military affairs, automobile, aerospace flight vehicle high power electronic equipment towards miniaturization, it is integrated, at high speed
Direction is fast-developing, and electronic equipment has a large amount of accumulation of heat in the process of running, if dissipated not in time, is easy to reduce electronics
The service life of device even results in electronic device failure.Therefore, lightweight, high tenacity, highly heat-conductive material are developed for improving
The heat management of next-generation high power electronic device is of great significance.
Currently, most widely used heat sink material is metal, especially aluminium alloy, this is because in various metals and its conjunction
In golden material, aluminium alloy has preferable toughness, higher thermal conductivity, for example, 7075 type aluminium alloy of aviation electronics heat transmission
Tensile toughness is 81.2MJ/m3, thermal conductivity 130W/mK, but the density of 7075 type aluminium alloys is higher, is 2.8g/cm3, therefore,
Seek other lightweights, high tenacity, high-heat-conductive composite material to be of great significance instead of aluminium alloy.
Some nano materials (such as graphene nanometer sheet (GNS), carbon nanotube (CNT), boron nitride nanosheet (BNNS) or
Boron nitride nano-tube (BNNT)) thermal conductivity and low density with superelevation, but the toughness of these pure nano material films is low,
Therefore, it is difficult to replace aluminium alloy to be used for next-generation electronic device.
In order to make above-mentioned nano material that aluminium alloy be replaced to be used for next-generation electronic device, a few thing person is in these nanometer of material
Polymer is introduced in material film, is prepared for polymer matrix composite, the mechanical property of these polymer matrix composites is
It improves.However, the polymer wrapped heat conducting nanometer material introduced, has blocked the phonon transmission between nano material, has caused compound
The heating conduction of material drastically reduces.
Recently, some researchs, which further report, mixes heat conducting nanometer material and high strength fibre element nanofiber, and
It is filtered into laminated film.It only is locally isolated heat conducting nanometer material due to cellulose nano-fibrous, the heat of these laminated films
Conductance increases, and is better than polymer matrix composite.However, the thermal conductivity of these cellulose nano-fibrous based coextruded films is outstanding
It is that toughness is still far below aviation aluminum alloy material.
Therefore, it is based on heat conducting nanometer material, it is still a major challenge that design, which is prepared and can replace the laminated film of aluminium alloy,.
Summary of the invention
The purpose of the present invention is to provide a kind of high tenacity high thermal conductivity PBONF (to refer to polyparaphenylene's benzo dioxazole Nanowire
Dimension) based coextruded film and preparation method thereof, high tenacity high thermal conductivity PBONF based coextruded film provided by the invention have low-density,
The advantages that high tenacity and high heat conductance, can replace current aviation alloyed aluminium.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of high tenacity high thermal conductivity PBONF based coextruded film, the PBONF based coextruded film includes
PBONF and heat conducting nanometer material；The PBONF forms tridimensional network, and heat conducting nanometer material is located in tridimensional network；
The PBONF has forked geometry.
Preferably, the quality of the heat conducting nanometer material is the 30~90% of PBONF based coextruded film quality；It is described thermally conductive
Nano material is one of graphene nanometer sheet, carbon nanotube, boron nitride nanosheet and boron nitride nano-tube or a variety of.
Preferably, the diameter of the PBONF is 5~20nm.
The present invention provides the preparation method of high tenacity high thermal conductivity PBONF based coextruded film described in above-mentioned technical proposal, packets
Include following steps:
(1) methane sulfonic acid, trifluoroacetic acid and polyparaphenylene's benzo dioxazole micrometer fibers are mixed, sodium salt is added, obtains
The dispersion liquid of sodium salt and PBONF；
(2) methane sulfonic acid, trifluoroacetic acid are mixed with heat conducting nanometer material, obtains the dispersion liquid of heat conducting nanometer material；
(3) by point of heat conducting nanometer material in the dispersion liquid of sodium salt and PBONF in the step (1) and the step (2)
Dispersion liquid is uniformly mixed, and dispersion liquid after mixing is poured into mold, mold is sealed with film, forms gel after standing；
(4) gel of the step (3) and water are subjected to exchange of solvent, obtain high tenacity high thermal conductivity PBONF base after dry
Laminated film；
The step (1) and step (2) do not have chronological order.
Preferably, the diameter of polyparaphenylene's benzo dioxazole micrometer fibers is 5~15 μm in the step (1).
Preferably, the sodium salt in the step (1) is one of sodium phosphate, sodium sulphate and sodium acetate or a variety of.
Preferably, the mass ratio of methane sulfonic acid and trifluoroacetic acid is 1:0.6~1.6 in the step (1)；Methane sulfonic acid and
The mass ratio of the gross mass of trifluoroacetic acid, polyparaphenylene's benzo dioxazole micrometer fibers and sodium salt is 1:0.009~0.015:
0.06~0.11.
Preferably, the mass ratio of methane sulfonic acid and trifluoroacetic acid is 1:0.6~1.6 in the step (2)；Methane sulfonic acid and
The gross mass of trifluoroacetic acid and the mass ratio of heat conducting nanometer material are 1:0.002~0.017.
Preferably, in the step (3) dispersion liquid of the dispersion liquid and heat conducting nanometer material of sodium salt and PBONF mass ratio
For 1:1~3.
Preferably, the time stood in the step (3) is 4~for 24 hours, temperature is 0~25 DEG C.
The present invention provides a kind of high tenacity high thermal conductivity PBONF based coextruded film, the PBONF based coextruded film includes
PBONF and heat conducting nanometer material；The PBONF forms tridimensional network, and heat conducting nanometer material is located in tridimensional network；
The PBONF has forked geometry.PBONF of the invention forms tridimensional network, and heat conducting nanometer material is located at three
It ties up in reticular structure, when laminated film is stretched, heat conducting nanometer material is slided and discharged together with PBONF network heterogeneous
The hiding length of PBONF network out, wherein π-π the active force between PBONF is destroyed and (sacrifices key), the elongation of PBONF network
The local deformation hardening that will lead to laminated film with orientation, since the high interconnectivity and heat conducting nanometer material of PBONF network are (by one
Multiple PBONF of a heat conducting nanometer material crosslinking) multi-functional crosslinking, differential hardening continues to lead to the strong of adjacent PBONF network
Strong elongation and orientation, therefore be diffused into lot of materials, finally, heat conducting nanometer material and PBONF are drawn out, generate big fracture
Strain and superhigh tenacity；In addition, PBONF is instead of part heat conducting nanometer material, therefore obtained laminated film has lightweight
Feature；PBONF is compared with other fibers thermal conductivity with higher, and the tridimensional network of PBONF is not by heat conducting nanometer material in addition
It is completely isolated, therefore obtained laminated film has good thermal conductivity.
Embodiment the result shows that, the density of high tenacity high thermal conductivity PBONF based coextruded film provided by the invention is low,
1.3~1.8g/cm3In range, hence it is evident that be lower than aluminium alloy (2.8g/cm3)；The tensile toughness of PBONF based coextruded film of the invention
It is good, in 10~100MJ/m3In range, close to 7075 type aluminium alloy (81.2MJ/m of aviation3)；PBONF base THIN COMPOSITE of the invention
The thermal conductivity of film is high, is partially more than 7075 type aluminium alloy (130W/mK) of aviation within the scope of 30~300W/mK.The PBONF base
Laminated film can replace current aviation alloyed aluminium, be aerospace flight vehicle loss of weight, while provide higher radiating efficiency and
Excellent structural reliability.
Detailed description of the invention
Fig. 1 is the GNS/PBONF hydrogel in the embodiment of the present invention 1；
Fig. 2 is the GNS/PBONF laminated film of the embodiment of the present invention 1；
Fig. 3~4 are the SEM figure after the GNS/PBONF hydrogel freeze-drying of the embodiment of the present invention 1；
Fig. 5 is the SEM figure of the GNS/PBONF laminated film of the embodiment of the present invention 1；
Fig. 6 is the CNT/PBONF hydrogel in the embodiment of the present invention 4；
Fig. 7 is the CNT/PBONF laminated film of the embodiment of the present invention 4；
Fig. 8 is the BNNS/PBONF hydrogel in the embodiment of the present invention 5；
Fig. 9 is the BNNS/PBONF laminated film of the embodiment of the present invention 5.
Specific embodiment
The present invention provides a kind of high tenacity high thermal conductivity PBONF based coextruded film, the PBONF based coextruded film includes
PBONF and heat conducting nanometer material；The PBONF forms tridimensional network, and heat conducting nanometer material is located in tridimensional network；
The PBONF has forked geometry.
In the present invention, the diameter of the PBONF is preferably 5~20nm, further preferably 9~18nm.
In the present invention, the heat conducting nanometer material be preferably graphene nanometer sheet, carbon nanotube, boron nitride nanosheet and
One of boron nitride nano-tube is a variety of.The present invention does not have particular/special requirement to the dimensions of the heat conducting nanometer material, adopts
With dimensions well known to those skilled in the art.In the present invention, the quality of the heat conducting nanometer material is preferably
The 30~90% of PBONF based coextruded film quality, further preferably 40~70%, most preferably 40%.In the present invention, when
The heat conducting nanometer material is CNT, and when the quality of CNT is the 40% of PBONF based coextruded film quality, obtained PBONF base is multiple
The tensile toughness for closing film is up to 72MJ/m3, thermal conductivity 165W/mK, density is down to 1.4g/cm3, aviation can be substituted completely
7075 type aluminium alloys.When the heat conducting nanometer material selects GNS, the quality of GNS be PBONF based coextruded film quality 40~
When 60%, the ratio toughness (divided by the later toughness of density) and specific thermal conductivity of obtained PBONF based coextruded film with 7075 types
Aluminium alloy is suitable.Specific: the specific heat conductance of 7075 type aluminium alloys is 46.4Wm-1K-1cm3g-1, it is 29J g than toughness-1；GNS
When content is 40%, specific heat conductance is 59.3Wm-1K-1cm3g-1, it is 28.8J g than toughness-1；When GNS content is 50%, specific heat
Conductance is 63.7W m-1K-1cm3g-1, it is 29.4J g than toughness-1；When GNS content is 60%, specific heat conductance is 80.6W m-1K- 1cm3g-1, it is 22.5J g than toughness-1。
The present invention does not have particular/special requirement to the thickness of the PBONF based coextruded film, can need to be adjusted depending on the application.
In a specific embodiment of the present invention, the PBONF based coextruded film with a thickness of 15~35 μm.
PBONF in high tenacity high thermal conductivity PBONF based coextruded film of the present invention forms tridimensional network, thermally conductive to receive
Rice material is located in tridimensional network, thermally conductive when laminated film is stretched since PBONF has forked geometry
Nano material is slided together with PBONF network heterogeneous and releases the hiding length of PBONF network, wherein between PBONF
π-π active force be destroyed (sacrifice key), the elongation of PBONF network and orientation will lead to the local deformation hardening of laminated film,
Due to PBONF network high interconnectivity and heat conducting nanometer material (by a heat conducting nanometer material be crosslinked multiple PBONF) it is more
Function crosslinking, differential hardening continues the strong elongation for leading to adjacent PBONF network and orientation, therefore is diffused into lot of materials,
Finally, heat conducting nanometer material and PBONF are drawn out, big breaking strain and superhigh tenacity are generated；In addition, PBONF is instead of portion
Divide heat conducting nanometer material, therefore obtained laminated film has the characteristics that lightweight；PBONF is compared with other fibers thermal conductivity with higher
Rate, the tridimensional network of PBONF is not completely isolated by heat conducting nanometer material in addition, therefore obtained laminated film has well
Thermal conductivity.
The present invention also provides the preparation method of high tenacity high thermal conductivity PBONF based coextruded film described in above-mentioned technical proposal,
The following steps are included:
(1) methane sulfonic acid, trifluoroacetic acid and polyparaphenylene's benzo dioxazole micrometer fibers are mixed, sodium salt is added, obtains
The dispersion liquid of sodium salt and PBONF；
(2) methane sulfonic acid, trifluoroacetic acid are mixed with heat conducting nanometer material, obtains the dispersion liquid of heat conducting nanometer material；
(3) by point of heat conducting nanometer material in the dispersion liquid of sodium salt and PBONF in the step (1) and the step (2)
Dispersion liquid is uniformly mixed, and dispersion liquid after mixing is poured into mold, mold is sealed with film, forms gel after standing；
(4) gel of the step (3) and water are subjected to exchange of solvent, obtain high tenacity high thermal conductivity PBONF base after dry
Laminated film；
The step (1) and step (2) do not have chronological order.
The present invention mixes methane sulfonic acid, trifluoroacetic acid and polyparaphenylene's benzo dioxazole micrometer fibers, and sodium salt is added, obtains
To the dispersion liquid of sodium salt and PBONF.
The present invention preferably first mixes methane sulfonic acid and trifluoroacetic acid, acid mixed solution is obtained, then again by acidic mixed
Liquid is mixed with polyparaphenylene's benzo dioxazole micrometer fibers.In the present invention, the mass ratio of the methane sulfonic acid and trifluoroacetic acid
Preferably 1:0.6~1.6；The mass concentration of the methane sulfonic acid is preferably >=99.0%；The mass concentration of the trifluoroacetic acid is excellent
Select > 99.5%.In the present invention, the diameter of polyparaphenylene's benzo dioxazole micrometer fibers is preferably 5~15 μm, into one
Preferably 10~13 μm of step.The present invention does not have particular/special requirement to the hybrid mode of the methane sulfonic acid and trifluoroacetic acid, can incite somebody to action
The two is uniformly mixed.In the present invention, the mixing of the acid mixed solution and polyparaphenylene's benzo dioxazole micrometer fibers
Preferably it is stirred.After methane sulfonic acid, trifluoroacetic acid and polyparaphenylene's benzo dioxazole micrometer fibers are mixed, the present invention is excellent
Choosing continues stirring 6~for 24 hours.The present invention does not have particular/special requirement to the rate of the stirring, and use is well known to those skilled in the art
Stirring rate.The present invention mixes methane sulfonic acid, trifluoroacetic acid with polyparaphenylene's benzo dioxazole micrometer fibers, and acidity is mixed
Liquid is closed by micron order fiber spin-off into nanofiber, and forms bifurcation structure, at the same time, yet forms the three dimensional network of PBONF
Shape structure.
In the present invention, the sodium salt is preferably one of sodium phosphate, sodium sulphate and sodium acetate or a variety of.In the present invention
In, the mass ratio of the gross mass of the methane sulfonic acid and trifluoroacetic acid, polyparaphenylene's benzo dioxazole micrometer fibers and sodium salt is excellent
It is selected as 1:0.009~0.015:0.06~0.11, further preferably 1:0.01~0.013:0.07~0.10.In the present invention
In, the addition of the sodium salt can increase the ionic strength of fiber dispersion, inhibit its electrostatic repulsion, and promote its π-π mutual
Effect and the gelation of subsequent step.Since to be unfavorable for acid mixed solution micro- by polyparaphenylene's benzo dioxazole for the addition of sodium salt
Rice fiber spin-off is at nanofiber, therefore, it is necessary to first mix acid solution with polyparaphenylene's benzo dioxazole micrometer fibers, is formed equal
Sodium salt is added after even dispersion liquid.
The present invention mixes methane sulfonic acid, trifluoroacetic acid with heat conducting nanometer material, obtains the dispersion liquid of heat conducting nanometer material.
The present invention preferably first mixes methane sulfonic acid and trifluoroacetic acid, acid mixed solution is obtained, then again by acidic mixed
Liquid is mixed with heat conducting nanometer material.The present invention does not have particular/special requirement to the hybrid mode of the methane sulfonic acid and trifluoroacetic acid, adopts
With hybrid mode well known to those skilled in the art.In the present invention, the acid mixed solution and heat conducting nanometer material
Mixing is preferably ultrasonic mixing；The power of the ultrasonic mixing is preferably 200~400W, and the time of the ultrasonic mixing is preferably
2~4h.In the present invention, it is multiple to correspond to high tenacity high thermal conductivity PBONF base described in above-mentioned technical proposal for the type of the Heat Conduction Material
Close the type of heat conducting nanometer material in film.
In the present invention, the mass ratio of the methane sulfonic acid and trifluoroacetic acid is preferably 1:0.6~1.6；The methyl sulphur
Acid and the gross mass of trifluoroacetic acid and the mass ratio of heat conducting nanometer material are preferably 1:0.002~0.017, and further preferably 1:
0.005~0.013.
After obtaining the dispersion liquid of sodium salt and PBONF, the dispersion liquid of heat conducting nanometer material, the present invention by the sodium salt and
The dispersion liquid of PBONF is uniformly mixed with the dispersion liquid of heat conducting nanometer material, and by dispersion liquid reverse mould tool after mixing, use is thin
Film seals mold, and gel is formed after standing.
In the present invention, the mass ratio of the dispersion liquid of the dispersion liquid and heat conducting nanometer material of the sodium salt and PBONF is preferred
For 1:1~3, further preferably 1:1.5~2.5.
The present invention pours into dispersion liquid after mixing in mold, and drawout comes mixed liquor in a mold, later with thin
Film seals mold.The present invention does not have particular/special requirement to the shape and specification of the mold, using known to those skilled in the art
The mold for preparing film.Present invention preferably employs flat molds, in favor of obtaining film in homogeneous thickness.The present invention couple
The material of the film is not reacted without particular/special requirement with the mixed liquor of two kinds of dispersion liquids.Present invention film is close by mold
Envelope, is on the one hand beneficial to prevent solvent evaporation, on the other hand can avoid the gelation that the moisture in air accelerates dispersion mixing liquid.
After the water in air enters dispersion mixing liquid, gelation can be accelerated, be unfavorable for forming the gel of outer shape rule.
In the present invention, the time of the standing be preferably 4~for 24 hours, further preferably 6~20h；The temperature of standing is excellent
It is selected as 0~25 DEG C, further preferably 5~20 DEG C.During standing of the present invention, under the action of sodium salt, mixed liquor hair
Raw gelation, forms the gel of outer shape rule.
After obtaining gel, the gel and water are carried out exchange of solvent by the present invention, obtain high tenacity high thermal conductivity after dry
PBONF based coextruded film.
The present invention preferably removes the film of mold, and gel is immersed in the water, and then carries out exchange of solvent with water.The present invention
There is no particular/special requirement to the specific embodiment of the exchange of solvent, using exchange of solvent mode well known to those skilled in the art
?.The present invention does not have particular/special requirement to the number of the exchange of solvent, can all exchange the acid solution in gel.?
In specific embodiments of the present invention, the number of the exchange of solvent is preferably 4 times.The present invention carries out exchange of solvent, is replaced with water
Acid solution in gel, forms hydrogel, forms a film so that subsequent solvent evaporates.Hydrogel is dried in the present invention, obtains
To high tenacity high thermal conductivity PBONF based coextruded film.In the present invention, the temperature of the drying is preferably 20~40 DEG C, dry
Time is preferably 40~120h.In the present invention, the atmosphere of the drying is preferably air atmosphere.Drying process of the present invention
Heat conducting nanometer material meeting layer upon layer, forms a kind of layer structure with network of fibers.
Below with reference to embodiment to high tenacity high thermal conductivity PBONF based coextruded film provided by the invention and preparation method thereof into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
GNS/PBONF laminated film
(1) commercialization polyparaphenylene's benzo dioxazole micrometer fibers 0.216g is weighed, 7mL methane sulfonic acid and 7mL are added to
In the mixed acid of trifluoroacetic acid, mechanical stirring 8h is subsequently added into 1.5g sodium sulphate, forms the PBONF dispersion liquid of sulfur acid sodium；
(2) GNS0.216g is weighed, is added in the mixed acid of 11mL methane sulfonic acid and 11mL trifluoroacetic acid, in 400W function
Ultrasound 3h under rate, forms uniform GNS dispersion liquid；
(3) the GNS dispersion liquid that the sulfur acid sodium PBONF dispersion liquid and step (2) prepared step (1) are prepared mixes,
Mechanical stirring 2h under the revolving speed of 1000rpm is poured into 5.5 centimetres of diameter of flat plastic ware, and one layer of guarantor is covered on plastic ware
Fresh film is converted to gel in 5 DEG C of standing 8h；
(4) trifluoroacetic acid, methane sulfonic acid and sodium sulphate by the soak in step (3) in distilled water, in gel
It diffuses into water, water diffuses into gel, changes water after impregnating 4h, recycles 4 times altogether, obtains GNS/PBONF hydrogel (as schemed
Shown in 1)；
(5) by the 25 DEG C of dry 100h in air of the GNS/PBONF hydrogel in step (4), obtaining GNS mass fraction is
50% PBONF based coextruded film (as shown in Figure 2), film thickness are 26 μm, tensile toughness 45.5MJ/m3, thermal conductivity
For 98.7W/mK, density 1.55g/cm3。
After the GNS/PBONF hydrogel that 1 step of embodiment (4) obtains is freeze-dried, it is scanned Electronic Speculum observation,
As a result as shown in figure 3, Fig. 3 is shown, GNS is evenly distributed in three-dimensional PBONF network.To the GNS/PBONF water after freeze-drying
Observation is further amplified in gel, as a result as shown in Figure 4.Fig. 4 shows that PBONF network is closely adhered to the surface GNS.
To the finally obtained laminated film of embodiment 1 be scanned Electronic Speculum observation, as a result as shown in figure 5, Fig. 5 show it is compound
Film has apparent ordered lamellar structure.
Embodiment 2
Unlike the first embodiment, the mass fraction of GNS is 40%；Obtained PBONF based coextruded film with a thickness of 24
μm, tensile toughness 42.4MJ/m3, thermal conductivity 87.2W/mK, density 1.47g/cm3。
Embodiment 3
Unlike the first embodiment, the mass fraction of GNS is 60%；Obtained PBONF based coextruded film with a thickness of 30
μm, tensile toughness 34.4MJ/m3, thermal conductivity 123.4W/mK, density 1.53g/cm3。
Embodiment 4
CNT/PBONF laminated film
(1) commercialization polyparaphenylene's benzo dioxazole micrometer fibers 0.216g is weighed, 4mL methane sulfonic acid and 6mL are added to
In the mixed acid of trifluoroacetic acid, mechanical stirring 8h is subsequently added into 1.5g sodium phosphate, forms the PBONF dispersion liquid of phosphoric acid sodium；
(2) CNT0.144g is weighed, is added in the mixed acid of 10.4mL methane sulfonic acid and 15.6mL trifluoroacetic acid,
Ultrasound 2h, forms uniform CNT dispersion under 400W power；
(3) CNT dispersion that the phosphoric acid sodium PBONF dispersion liquid and step (2) prepared step (1) are prepared mixes,
Mechanical stirring 2h under the revolving speed of 1000rpm is poured into 9 centimetres of diameter of flat plastic ware, and one layer of covering is fresh-keeping on plastic ware
Film is converted to gel in 20 DEG C of standings for 24 hours；
(4) trifluoroacetic acid, methane sulfonic acid and sodium phosphate by the soak in step (3) in distilled water, in gel
It diffuses into water, water diffuses into gel, changes water after impregnating 4h, recycles 4 times altogether, obtains CNT/PBONF hydrogel (as schemed
Shown in 6)；
(5) by the 40 DEG C of dry 48h in air of the CNT/PBONF hydrogel in step (4), obtaining CNT mass fraction is
40% PBONF based coextruded film (as shown in Figure 7), film thickness are 22 μm, tensile toughness 72.0MJ/m3, thermal conductivity
For 165W/mK, density 1.4g/cm3。
Embodiment 5
BNNS/PBONF laminated film
(1) commercialization polyparaphenylene's benzo dioxazole micrometer fibers 0.216g is weighed, 6mL methane sulfonic acid and 4mL are added to
In the mixed acid of trifluoroacetic acid, mechanical stirring for 24 hours, is subsequently added into 1.5g sodium acetate, forms the PBONF dispersion liquid containing sodium acetate；
(2) BNNS 0.504g is weighed, is added in the mixed acid of 15.6mL methane sulfonic acid and 10.4mL trifluoroacetic acid,
Ultrasound 4h under 400W power, forms uniform BNNS dispersion liquid；
(3) the BNNS dispersion liquid that the dispersion liquid of PBONF containing sodium acetate and step (2) prepared step (1) are prepared mixes,
Mechanical stirring 3h under the revolving speed of 2000rpm is poured into 9 centimetres of diameter of flat plastic ware, and one layer of covering is fresh-keeping on plastic ware
Film is converted to gel in 0 DEG C of standing 4h；
(4) trifluoroacetic acid, methane sulfonic acid and sodium acetate by the soak in step (3) in distilled water, in gel
It diffuses into water, water diffuses into gel, changes water after impregnating 4h, recycles 4 times altogether, obtains BNNS/PBONF hydrogel (such as
Shown in Fig. 8)；
(5) by the 40 DEG C of dry 48h in air of the BNNS/PBONF hydrogel in step (4), BNNS mass fraction is obtained
For 70% PBONF based coextruded film (as shown in Figure 9), film thickness is 35 μm, tensile toughness 23.4MJ/m3, thermal conductivity
Rate is 35W/mK, density 1.65g/cm3。
Embodiment 6
BNNT/PBONF laminated film
(1) commercialization polyparaphenylene's benzo dioxazole micrometer fibers 0.216g is weighed, 5mL methane sulfonic acid and 5mL are added to
In the mixed acid of trifluoroacetic acid, mechanical stirring 48h is subsequently added into 1.5g sodium sulphate, forms the PBONF dispersion liquid of sulfur acid sodium；
(2) BNNT 0.093g is weighed, is added in the mixed acid of 13mL methane sulfonic acid and 13mL trifluoroacetic acid, in 400W
Ultrasound 2h under power, forms uniform BNNT dispersion liquid；
(3) the BNNT dispersion liquid that the sulfur acid sodium PBONF dispersion liquid and step (2) prepared step (1) are prepared mixes,
Mechanical stirring 2h under the revolving speed of 2000rpm is poured into 5.5 centimetres of diameter of flat plastic ware, and one layer of guarantor is covered on plastic ware
Fresh film is converted to gel in 10 DEG C of standing 12h；
(4) trifluoroacetic acid, methane sulfonic acid and sodium sulphate by the soak in step (3) in distilled water, in gel
It diffuses into water, water diffuses into gel, changes water after impregnating 4h, recycles 4 times altogether, obtains BNNT/PBONF hydrogel；
(5) by the 40 DEG C of dry 48h in air of the BNNT/PBONF hydrogel in step (4), BNNT mass fraction is obtained
For 30% PBONF based coextruded film, film thickness is 28 μm, tensile toughness 38MJ/m3, thermal conductivity 58W/mK is close
Degree is 1.3g/cm3。
In Examples 1 to 6, extension test is tested on Shimadzu AGS-X electronic universal tester, the size of batten
Are as follows: long 45mm, wide 2mm, rate of extension 1mm/min.
The test method of thermal conductivity is as follows: being shone at 25 DEG C by laser using LFA467 (NETZSCH, Germany)
Method measures thermal diffusion coefficient in the face of composite material, then calculates thermal conductivity according to formula 1:
K=α Cpρ formula 1
In formula 1, α and ρ are the thermal diffusion coefficient and density of nanocomposite respectively；ρ is calculated by weight method；CpIt is ratio
Thermal capacitance, and measured using differential scanning calorimetry (DSC).
As seen from the above embodiment, the present invention provides a kind of high tenacity high thermal conductivity PBONF based coextruded film and its preparations
Method, high tenacity high thermal conductivity PBONF based coextruded film provided by the invention have low-density, high tenacity and high heat conductance etc. excellent
Point can replace current aviation alloyed aluminium, be aerospace flight vehicle loss of weight, while providing higher radiating efficiency and excellent
Structural reliability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of high tenacity high thermal conductivity PBONF based coextruded film, which is characterized in that the PBONF based coextruded film includes PBONF
And heat conducting nanometer material；The PBONF forms tridimensional network, and heat conducting nanometer material is located in tridimensional network；It is described
PBONF has forked geometry.
2. high tenacity high thermal conductivity PBONF based coextruded film according to claim 1, which is characterized in that the heat conducting nano
The quality of material is the 30~90% of PBONF based coextruded film quality；The heat conducting nanometer material is graphene nanometer sheet, carbon is received
One of mitron, boron nitride nanosheet and boron nitride nano-tube are a variety of.
3. high tenacity high thermal conductivity PBONF based coextruded film according to claim 1, which is characterized in that the PBONF's is straight
Diameter is 5~20nm.
4. the preparation method of any one of claims 1 to 3 high tenacity high thermal conductivity PBONF based coextruded film, which is characterized in that
The following steps are included:
(1) methane sulfonic acid, trifluoroacetic acid and polyparaphenylene's benzo dioxazole micrometer fibers are mixed, sodium salt is added, obtains sodium salt
With the dispersion liquid of PBONF；
(2) methane sulfonic acid, trifluoroacetic acid are mixed with heat conducting nanometer material, obtains the dispersion liquid of heat conducting nanometer material；
(3) by the dispersion liquid of heat conducting nanometer material in the dispersion liquid of sodium salt and PBONF in the step (1) and the step (2)
It is uniformly mixed, dispersion liquid after mixing is poured into mold, mold is sealed with film, forms gel after standing；
(4) gel of the step (3) and water are subjected to exchange of solvent, it is compound to obtain high tenacity high thermal conductivity PBONF base after dry
Film；
The step (1) and step (2) do not have chronological order.
5. the preparation method according to claim 4, which is characterized in that polyparaphenylene's benzo dioxazole in the step (1)
The diameter of micrometer fibers is 5~15 μm.
6. the preparation method according to claim 4, which is characterized in that the sodium salt in the step (1) is sodium phosphate, sulfuric acid
One of sodium and sodium acetate are a variety of.
7. the preparation method according to claim 4, which is characterized in that methane sulfonic acid and trifluoroacetic acid in the step (1)
Mass ratio be 1:0.6~1.6；The gross mass of methane sulfonic acid and trifluoroacetic acid, polyparaphenylene's benzo dioxazole micrometer fibers and
The mass ratio of sodium salt is 1:0.009~0.015:0.06~0.11.
8. the preparation method according to claim 4, which is characterized in that methane sulfonic acid and trifluoroacetic acid in the step (2)
Mass ratio be 1:0.6~1.6；The mass ratio of the gross mass and heat conducting nanometer material of methane sulfonic acid and trifluoroacetic acid is 1:
0.002~0.017.
9. the preparation method according to claim 4, which is characterized in that the dispersion liquid of sodium salt and PBONF in the step (3)
Mass ratio with the dispersion liquid of heat conducting nanometer material is 1:1~3.
10. the preparation method according to claim 4, which is characterized in that the time stood in the step (3) is 4~
For 24 hours, temperature is 0~25 DEG C.
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