CN109081936A - A kind of fluoropolymer cellular material and preparation method thereof - Google Patents
A kind of fluoropolymer cellular material and preparation method thereof Download PDFInfo
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- CN109081936A CN109081936A CN201710447574.7A CN201710447574A CN109081936A CN 109081936 A CN109081936 A CN 109081936A CN 201710447574 A CN201710447574 A CN 201710447574A CN 109081936 A CN109081936 A CN 109081936A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention provides a kind of preparation method of fluoropolymer cellular material comprising fluoropolymer: a) being placed in closed container by following steps, and the temperature of closed container is risen to 150 DEG C~340 DEG C；B) pressure for being passed through supercritical carbon dioxide to closed container into closed container reaches 10MPa~40MPa, and keeps predetermined time T at this pressure, is uniformly distributed in supercritical carbon dioxide in fluoropolymer；C) release is carried out to the closed container, makes the supercritical carbon dioxide foaming in the fluoropolymer, obtains fluoropolymer cellular material, wherein the release speed of the closed container is greater than 8MPa/s.The present invention also provides a kind of fluoropolymer cellular materials.
Description
Technical field
The present invention relates to technical field of polymer materials more particularly to a kind of fluoropolymer cellular material and its preparation sides
Method.
Background technique
Fluorinated polymer material is that the hydrogen atom in a kind of monomer molecule is all replaced or partially substituted spy by fluorine atom
Kind high molecular polymer.Because of the lower polarizability of fluorine atom, strong electronegativity, lesser van der Waals radius and very strong key
Can, the excellent characteristics such as heat-resisting, resistant to chemical etching, weather-proof, fire-retardant are presented in fluorinated polymer material.However, fluoropolymer material
The density of material is commonly greater than 1.7g/cm3, single volume mass is far longer than common engineering plastics, leads to its cost of material much
Higher than other plastics, and limit the popularization and application of fluorinated polymer material.
Research finds that high molecular foam material is a kind of material haveing excellent performance, and density is greatly lowered, simultaneously
With good mechanical performance, thermodynamic property, processing performance and certain property.
The preparation method of high molecular foam material is broadly divided into two kinds at present: chemical blowing and physical blowing.Chemical blowing
General use can decompose the organic compound for generating gas as foaming agent at high temperature.The use of chemical foaming agent exists serious
Environment and hazard to person.Physical blowing, which refers to, plays hair by the expansion of compressed gas, the volatilization of liquid or dissolution of solid etc.
The effect of bubble.Supercritical carbon dioxide is a kind of excellent gas phase physical blowing agent.Such as Chinese publication
(CN101580600A) disclose a kind of perfluoroethylene-propylene microcellular foam material, using postcritical CO 2 fluid come into
Row foaming, however in this method, due to perfluoroethylene-propylene 40 degrees Celsius at a temperature of be solid-state, supercritical carbon dioxide exists
Diffusion in perfluoroethylene-propylene matrix is slower, takes a long time (2 hours or more), and exists and mix the defects of uneven,
It is difficult to obtain high porosity, equally distributed perfluoroethylene-propylene foamed material, technique timeliness is low.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of fluoropolymer cellular materials and preparation method thereof.
The fluoropolymer cellular material not only has high opening rate, but also distribution of cells is uniform.The preparation method used time is short, preparation effect
Rate is high.
The present invention provides a kind of preparation method of fluoropolymer cellular material comprising following steps:
A) fluoropolymer is placed in closed container, and the temperature of closed container is risen to 150 DEG C~360 DEG C；
B) pressure for being passed through supercritical carbon dioxide to closed container into closed container reaches 10MPa~40MPa, and
Predetermined time T is kept under the pressure, is uniformly distributed in supercritical carbon dioxide in fluoropolymer；
C) release is carried out to the closed container, makes the supercritical carbon dioxide foaming in the fluoropolymer, obtains
Fluoropolymer cellular material, wherein the release speed of the closed container is greater than 8MPa/s.
The present invention also provides a kind of fluoropolymer cellular materials obtained using above-mentioned preparation method, which is characterized in that
The fluoropolymer cellular material includes multiple apertures, and the pore size of the aperture is 1 nanometer~100 microns, described to contain
The density of fluoropolymer cellular material is 0.3~1.4g/cm3。
Compared to the prior art, this preparation method has the advantage that
By the way that the temperature of closed container is risen to 150 DEG C~360 DEG C, so that fluoropolymer becomes soft phase at high temperature.
After being passed through supercritical carbon dioxide, supercritical carbon dioxide is rapidly dissolvable and is spread in the fluoropolymer of soft phase, with
Form equally distributed complex.Release is carried out to the closed container with higher release speed (being greater than 8MPa/s) again, makes to surpass
Carbon dioxide expanded, the escape of critical state, promote complex growth to form multiple abscesses in fluoropolymer matrix, obtain
Fluoropolymer cellular material with multiple abscesses.
Compared with the prior art, the time mixed between supercritical carbon dioxide and fluoropolymer in this method is shorter,
As long as supercritical carbon dioxide can be realized and be uniformly distributed for 8 minute.Swelling (CN101580600A) in compared to existing 2 hours,
Preparation time is greatly reduced, preparation efficiency is improved.
Can by adjusting closed container temperature, be passed through the pressure of closed container, predetermined time T after supercritical carbon dioxide
And release speed, and realize and the foaming process of supercritical carbon dioxide is adjusted, to obtain the bubble with different pore size
The fluoropolymer cellular material in hole.After being passed through supercritical carbon dioxide the temperature of closed container be 150 DEG C~300 DEG C, it is close
The pressure for closing container is that 25MPa~40MPa, predetermined time T are greater than 10 minutes and release speed is greater than 10MPa/s, and hole can be obtained
Diameter is less than the abscess of 100nm；After being passed through supercritical carbon dioxide the temperature of closed container be 180 DEG C~360 DEG C, closed container
Pressure be that 10MPa~40MPa, predetermined time T are greater than 8 minutes and release speed and are greater than 8MPa/s, aperture can be obtained less than 100
The abscess of micron.
Compared to traditional preparation method, fluoropolymer-containing percent opening made from the preparation method is high, and cell wall is thin, material
Material density is low, and (density of material is 0.3~1.4g/cm3), thus, which can be widely applied to packaging, building, prevents
The fields such as shield, shielding, decoration, medical treatment.
Detailed description of the invention
Fig. 1 is that the profile scanning Electronic Speculum (SEM) for the polyvinylidene fluoride nanometer cellular material that the embodiment of the present invention 1 obtains is shone
Piece；
Fig. 2 is the section SEM photograph for the perfluoroethylene-propylene nano-cellular material that the embodiment of the present invention 4 obtains；
Fig. 3 is the section SEM photograph for the Kynoar microcellular foam material that the embodiment of the present invention 6 obtains；
Fig. 4 is the section SEM photograph for the Kynoar microcellular foam material that the embodiment of the present invention 8 obtains；
Fig. 5 is the section SEM photograph for the perfluoroethylene-propylene microcellular foam material that the embodiment of the present invention 9 obtains；
Fig. 6 is the section SEM photograph for the perfluoroethylene-propylene microcellular foam material that the embodiment of the present invention 10 obtains；
Fig. 7 is Kynoar/perfluoroethylene-propylene microcellular foam material section SEM that the embodiment of the present invention 12 obtains
Photo.
Specific embodiment
Below in conjunction with the attached drawing in embodiment of the present invention, the technical solution in embodiment of the present invention is carried out clear
Chu is fully described by, it is clear that described embodiment is only some embodiments of the invention, rather than whole realities
Apply mode.Based on the embodiment in the present invention, those of ordinary skill in the art institute without creative efforts
The every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation methods of fluoropolymer cellular material comprising following steps:
A) fluoropolymer is placed in closed container, and the temperature of closed container is risen to 150 DEG C~360 DEG C；
B) pressure for being passed through supercritical carbon dioxide to closed container into closed container reaches 10MPa~40MPa, and
Predetermined time T is kept under the pressure, is uniformly distributed in supercritical carbon dioxide in fluoropolymer；
C) release is carried out to the closed container, makes the supercritical carbon dioxide foaming in the fluoropolymer, obtains
Fluoropolymer cellular material, wherein the release speed of the closed container is greater than 8MPa/s.
In step a), by increasing to the temperature in closed container, fluoropolymer can be made to be essentially soft phase, with
It is mixed conducive to the supercritical carbon dioxide of step b) with fluoropolymer-containing, and makes supercritical carbon dioxide " dissolution " in fluorine-containing poly-
It closes in object, and is evenly distributed.It is understood that being somebody's turn to do " dissolution " is not for real meaning salt is soluble in water general molten
Solution, but a kind of special dissolved state.Exactly because the temperature of the closed container increases, fluoropolymer is in soft phase, because
Supercritical carbon dioxide, can uniformly be dissolved in fluoropolymer by this in shorter predetermined time T (being more than or equal to 8 minutes)；
This compares the existing swelling treatment time up to a few hours, and the time is greatly saved, improves preparation efficiency.
Temperature in the closed container can be set according to the fluoropolymer-containing specific type, as long as making fluorine-containing poly-
Closing object is in soft phase.For example, for the lower limit temperature in the closed container, when fluoropolymer is polyvinylidene fluoride
When alkene, then the temperature in the closed container rises to 160 DEG C~180 DEG C, and Kynoar can be made in soft phase；Work as fluoropolymer
When object is perfluoroethylene-propylene, then the temperature in the closed container rises to 260 DEG C~280 DEG C, can make the Kynoar be in
Soft phase.Certainly, for the ceiling temperature in the closed container, the ceiling temperature of the closed container cannot cause fluorine-containing poly-
Object is closed to melt completely.For example, when fluoropolymer is Kynoar, ceiling temperature is no more than 210 DEG C；When fluorine-containing poly-
When conjunction object is perfluoroethylene-propylene, ceiling temperature is no more than 360 DEG C
The fluoropolymer is Kynoar and/or perfluoroethylene-propylene.
In view of the process of foaming, compared to the fluoropolymer before foaming, obtained fluoropolymer after foaming
The volume of object cellular material increases rapidly, therefore, it is necessary to limit the fluoropolymer in the shared volume of the closed container
Below certain certain value.In the present invention, when making a reservation for obtain abscess aperture as nanoscale, then the fluoropolymer-containing volume is limited
Less than the 30% of the volume of the closed container；When making a reservation for obtain abscess aperture as micron order, then the fluoropolymer is limited
Volume be less than the closed container volume 20%.
Further when expecting the biggish abscess in aperture such as micron order, then the temperature of the closed container can be set as 180
DEG C~340 DEG C.
The closed container can be autoclave.It further include one to closed container before increasing the temperature of closed container
It is inside passed through carbon dioxide, excludes the air in closed container.
In step b), when expecting the lesser abscess in aperture such as nanoscale, then it can be passed through into closed container overcritical
The pressure of carbon dioxide to closed container reaches 25MPa~40MPa, and predetermined time T is more than or equal to 10 minutes at this time；
When expecting the biggish abscess in aperture such as micron order, then supercritical carbon dioxide can be passed through into closed container to closed container
Pressure reaches 10MPa~40MPa, and predetermined time T is more than or equal to 8 minutes at this time.
In step c), when expecting the biggish abscess in aperture such as micron order, then the release speed of the closed container is
Greater than 8MPa/s.When expecting the lesser abscess in aperture such as nanoscale, then the release speed of the closed container be greater than
10MPa/s.
In fact, the predetermined time T of pressure, dissolution in the temperature of closed container, closed container, release speed these
Between parameter, when a Parameters variation and other several parameter constants, the foam structure of different pore size can be obtained, and realize abscess
The adjustment of aperture and density of material.
The present invention also provides a kind of fluoropolymer cellular materials obtained using above-mentioned preparation method.Please refer to Fig. 1~
7, the fluoropolymer cellular material includes multiple apertures, and the pore size of the aperture is 1 nanometer~100 microns, described
The density of fluoropolymer cellular material is 0.3~1.4g/cm3.Can be formed between the multiple aperture it is interconnected, it is described to open
The hole wall in hole is relatively thin.
Compared to the prior art, this preparation method has the advantage that
By the way that the temperature of closed container is risen to 150 DEG C~360 DEG C, so that fluoropolymer becomes soft phase at high temperature.
After being passed through supercritical carbon dioxide, supercritical carbon dioxide is rapidly dissolvable and is spread in the fluoropolymer of soft phase, with
Form equally distributed complex.Release is carried out to the closed container with higher release speed (being greater than 8MPa/s) again, makes to surpass
Carbon dioxide expanded, the escape of critical state, promote complex growth to form multiple abscesses in the soft phase matrix of fluoropolymer,
Obtain the fluoropolymer cellular material with multiple abscesses.
Compared with the prior art, the time mixed between supercritical carbon dioxide and fluoropolymer in this method is shorter,
As long as supercritical carbon dioxide can be realized and be uniformly distributed for 8 minute.Swelling (CN101580600A) in compared to existing 2 hours,
Preparation time is greatly reduced, preparation efficiency is improved.
Compared to traditional preparation method, fluoropolymer-containing percent opening made from the preparation method is higher, and cell wall is thin,
Density of material is low, and (density of material is 0.3~1.4g/cm3), thus, which can be widely applied to packaging, building, prevents
The fields such as shield, shielding, decoration, medical treatment.
The preparation method of fluoropolymer cellular material of the invention is illustrated combined with specific embodiments below:
Embodiment 1
Kynoar powder is processed into sheet material through single screw rod extrusion device by step (1).Kynoar sheet material is set
In the autoclave of connection supercritical carbon dioxide device, it is passed through carbon dioxide, low pressure purge 3min.Reset autoclave temp
To 185 DEG C.
Step (2) is filled with autoclave to 30MPa pressure after temperature reaches, by supercritical carbon dioxide fluid.And constant temperature
Constant pressure keeps 20min.
Step (3) opens autoclave pressure-relief valve, is unloaded with the speed of 12MPa/s and is depressed into normal pressure, obtains polyvinylidene fluoride nanometer
Cellular material.
As shown in Figure 1, the average pore size of polyvinylidene fluoride nanometer cellular material is 68nm, density of material 1.098g/
cm3。
Embodiment 2
Kynoar powder is processed into sheet material through double screw extruder by step (1).Kynoar sheet material is set
In the autoclave of connection supercritical carbon dioxide device, it is passed through carbon dioxide, low pressure purge 4min.Reset autoclave temp
To 170 DEG C.
Step (2) is filled with autoclave to 25MPa pressure after temperature reaches, by supercritical carbon dioxide fluid.And constant temperature
Constant pressure keeps 35min.
Step (3) opens autoclave pressure-relief valve, is unloaded with the speed of 10MPa/s and is depressed into normal pressure, obtains polyvinylidene fluoride nanometer
Cellular material.
After tested, the average pore size of gained polyvinylidene fluoride nanometer cellular material is 32nm, density of material 1.213g/
cm3。
Embodiment 3
Kynoar powder is hot pressed into sheet material through 200 DEG C, 10MPa, 10min by step (1).By Kynoar sheet material
It is placed in the autoclave of connection supercritical carbon dioxide device, is passed through carbon dioxide, low pressure purge 5min.Reset high pressure kettle temperature
Degree is to 195 DEG C.
Step (2) is filled with autoclave to 35MPa pressure after temperature reaches, by supercritical carbon dioxide fluid.And constant temperature
Constant pressure keeps 15min.
Step (3) opens autoclave pressure-relief valve, is unloaded with the speed of 15MPa/s and is depressed into normal pressure, obtains polyvinylidene fluoride nanometer
Cellular material.
After tested, the average pore size of gained polyvinylidene fluoride nanometer cellular material is 81nm, density of material 1.028g/
cm3。
Embodiment 4
Perfluoroethylene-propylene is hot pressed into sheet material through 300 DEG C, 10MPa, 15min by step (1).By perfluoroethylene-propylene sheet material
It is placed in the autoclave of connection supercritical carbon dioxide device, is passed through carbon dioxide, low pressure purge 3min.Reset high pressure kettle temperature
Degree is to 260 DEG C.
Step (2) is filled with autoclave to 30MPa pressure after temperature reaches, by supercritical carbon dioxide fluid.And constant temperature
Constant pressure keeps 15min.
Step (3) opens autoclave pressure-relief valve, is unloaded with the speed of 12MPa/s and is depressed into normal pressure, obtained perfluoroethylene-propylene and receive
Rice cellular material.
As shown in Fig. 2, the average pore size of perfluoroethylene-propylene nano-cellular material is 66nm, density of material 1.352g/
cm3。
Embodiment 5
Perfluoroethylene-propylene sheet material obtained by embodiment (4) step (1) is placed in connection supercritical carbon dioxide dress by step (1)
In the autoclave set, it is passed through carbon dioxide, low pressure purge 5min.Autoclave temp is reset to 280 DEG C.
Step (2) is filled with autoclave to 35MPa pressure after temperature reaches, by supercritical carbon dioxide fluid.And constant temperature
Constant pressure keeps 12min.
Step (3) opens autoclave pressure-relief valve, is unloaded with the speed of 15MPa/s and is depressed into normal pressure, obtained perfluoroethylene-propylene and receive
Rice cellular material.
After tested, the average pore size of perfluoroethylene-propylene nano-cellular material is 63nm, density of material 1.353g/cm3。
Embodiment 6
Step (1) by Kynoar powder by 200 DEG C of moulding press, 10MPa, hot pressing 10min, be made it is closely knit it is poly- partially
Vinyl fluoride sheet material.PVDF sheet material is put into autoclave, supercritical carbon dioxide device is connected, is passed through carbon dioxide, low pressure purge 3
Minute.Resetting autoclave temp is 200 DEG C.
Step (2) temperature is filled with supercritical carbon dioxide fluid to pressure after stablizing be 20MPa；Constant temperature and pressure is kept
16min。
Step (3) opens autoclave relief valve and obtains polyvinylidene fluoride with 10MPa/s decompression rate fast pressure relief to normal pressure
Alkene microcellular foam material.
As shown in figure 3, the density of gained Kynoar microcellular foam material is 0.429g/cm3, average pore size is 17 μ
M, cell density are 2.75 × 109/cm3。
Embodiment 7
Step (1) is by being made closely knit Kynoar sheet material described in embodiment 6.Kynoar sheet material is put into high pressure
Kettle connects supercritical carbon dioxide device, is passed through carbon dioxide, and low pressure purge 4 minutes.Resetting autoclave temp is 210 DEG C.
It is 15MPa that step (2) is filled with supercritical carbon dioxide fluid to pressure after temperature is stablized, and constant temperature and pressure is kept
20min。
Step (3) opens autoclave relief valve and obtains Kynoar with 8MPa/s decompression rate fast pressure relief to normal pressure
Microcellular foam material.
After tested, the density of gained Kynoar microcellular foam material is 0.357g/cm3, average pore size is 47 μm, bubble
Hole density is 1.17 × 109/cm3。
Embodiment 8
Step (1) is by being made closely knit Kynoar sheet material described in embodiment 6.Kynoar sheet material is put into high pressure
Kettle connects supercritical carbon dioxide device, is passed through carbon dioxide, and low pressure purge 5 minutes.Resetting autoclave temp is 190 DEG C.
Step (2) temperature is filled with supercritical carbon dioxide fluid to pressure after stablizing be 35MPa；Constant temperature and pressure is kept
30min。
Step (3) opens autoclave relief valve and obtains Kynoar with 9MPa/s decompression rate fast pressure relief to normal pressure
Microcellular foam material.
As shown in figure 4, gained Kynoar microcellular foam material is compound foam structure, density of material 0.482g/
cm3。
Embodiment 9
Perfluoroethylene-propylene pellet is put into autoclave by step (1), is connected supercritical carbon dioxide device, is passed through titanium dioxide
Carbon, low pressure purge 5 minutes.Resetting autoclave temp is 280 DEG C.
Step (2) temperature is filled with supercritical carbon dioxide fluid to pressure after stablizing be 30MPa；Constant temperature and pressure is kept
12min。
Step (3) opens autoclave relief valve and obtains perfluoroethylene with 13MPa/s decompression rate fast pressure relief to normal pressure
Propylene microcellular foam material.
As shown in figure 5, the density of gained perfluoroethylene-propylene microcellular foam material is 0.734g/cm3, material average pore size
It is 40 μm.
Embodiment 10
By 300 DEG C of moulding press, 10MPa, hot pressing 10min, closely knit gather is made in perfluoroethylene-propylene pellet by step (1)
Perfluoroethylene-propylene (copolymer) sheet material.Perfluoroethylene-propylene sheet material is put into autoclave, supercritical carbon dioxide device is connected, is passed through titanium dioxide
Carbon, low pressure purge 4 minutes.Resetting autoclave temp is 300 DEG C.
Step (2) temperature is filled with supercritical carbon dioxide fluid to pressure after stablizing be 24MPa；Constant temperature and pressure is kept
20min。
Step (3) opens autoclave relief valve and obtains perfluoroethylene with 12MPa/s decompression rate fast pressure relief to normal pressure
Propylene microcellular foam material.
As shown in fig. 6, gained perfluoroethylene-propylene microcellular foam material average pore size is 21 μm.
Embodiment 11
Closely knit perfluoroethylene-propylene piece is made by single screw extrusion machine extrusion in perfluoroethylene-propylene pellet by step (1)
Material.Perfluoroethylene-propylene sheet material is put into autoclave, supercritical carbon dioxide device is connected, is passed through carbon dioxide, low pressure purge 4
Minute.Resetting autoclave temp is 320 DEG C.
Step (2) temperature is filled with supercritical carbon dioxide fluid to pressure after stablizing be 15MPa；Constant temperature and pressure is kept
40min。
Step (3) opens autoclave relief valve and obtains perfluoroethylene third with 9MPa/s decompression rate fast pressure relief to normal pressure
Alkene microcellular foam material.
After tested, gained perfluoroethylene-propylene microcellular foam material average pore size is 38 μm.
Embodiment 12
Step (1) by perfluoroethylene-propylene and Kynoar in 7:3 ratio after mixing, extruding pelletization is made poly-
Perfluoroethylene-propylene (copolymer)/polyvinylidene fluoride composite material.Composite material is put into autoclave, connects supercritical carbon dioxide device, is led to
Enter carbon dioxide, low pressure purge 5 minutes.Resetting autoclave temp is 265 DEG C.
Step (2) temperature is filled with supercritical carbon dioxide fluid to pressure after stablizing be 35MPa；Constant temperature and pressure is kept
30min。
Step (3) opens autoclave relief valve and obtains polyvinylidene fluoride with 15MPa/s decompression rate fast pressure relief to normal pressure
Alkene/perfluoroethylene-propylene microcellular foam material.
As shown in fig. 7, be gained Kynoar/perfluoroethylene-propylene microcellular foam material average pore size be 7.5 μm, material
Material density is 1.121g/cm3。
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (8)
1. a kind of preparation method of fluoropolymer cellular material comprising following steps:
A) fluoropolymer is placed in closed container, and the temperature of closed container is risen to 150 DEG C~360 DEG C；
B) pressure for being passed through supercritical carbon dioxide to closed container into closed container reaches 10MPa~40MPa, and in the pressure
Predetermined time T is kept under power, is uniformly distributed in supercritical carbon dioxide in fluoropolymer；
C) release is carried out to the closed container, makes the supercritical carbon dioxide foaming in the fluoropolymer, obtains fluorine-containing
Polymer cells material, wherein the release speed of the closed container is greater than 8MPa/s.
2. a kind of preparation method of fluoropolymer cellular material as described in claim 1, which is characterized in that institute in step a)
Stating fluoropolymer is Kynoar and/or perfluoroethylene-propylene.
3. a kind of preparation method of fluoropolymer cellular material as described in claim 1, which is characterized in that institute in step a)
State fluoropolymer-containing volume is less than the volume of the closed container 30%.
4. a kind of preparation method of fluoropolymer cellular material as described in claim 1, which is characterized in that institute in step a)
The temperature for stating closed container is 180 DEG C~360 DEG C.
5. a kind of preparation method of fluoropolymer cellular material as described in claim 1, which is characterized in that in step b) to
The pressure for being passed through supercritical carbon dioxide to closed container in closed container reaches 25MPa~40MPa.
6. a kind of preparation method of fluoropolymer cellular material as described in claim 1, which is characterized in that institute in step b)
Predetermined time T is stated more than or equal to 8 minutes.
7. a kind of preparation method of fluoropolymer cellular material as described in claim 1, which is characterized in that institute in step c)
The release speed for stating closed container is greater than 10MPa/s.
8. a kind of using the fluoropolymer cellular material obtained such as any one of claim 1 to 7 preparation method, feature exists
In the fluoropolymer cellular material includes multiple apertures, and the pore size of the aperture is 1 nanometer~100 microns, described
The density of fluoropolymer cellular material is 0.3g/cm3~1.4g/cm3。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574744A (en) * | 2020-05-22 | 2020-08-25 | 湖州长园特发科技有限公司 | Preparation method of clean environment-friendly polyvinylidene fluoride foamed sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821273A (en) * | 1996-05-22 | 1998-10-13 | E. I. Du Pont De Nemours And Company | Extrusion foaming of fluoropolymers |
| CN101580600A (en) * | 2009-06-18 | 2009-11-18 | 上海交通大学 | Method for preparing perfluoroethylene-propylene microcellular foam material |
| CN102504322A (en) * | 2011-11-07 | 2012-06-20 | 中国科学院宁波材料技术与工程研究所 | Method for preparing supercritical fluid reinforced fluorine-containing polymer product |
-
2017
- 2017-06-14 CN CN201710447574.7A patent/CN109081936A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821273A (en) * | 1996-05-22 | 1998-10-13 | E. I. Du Pont De Nemours And Company | Extrusion foaming of fluoropolymers |
| CN101580600A (en) * | 2009-06-18 | 2009-11-18 | 上海交通大学 | Method for preparing perfluoroethylene-propylene microcellular foam material |
| CN102504322A (en) * | 2011-11-07 | 2012-06-20 | 中国科学院宁波材料技术与工程研究所 | Method for preparing supercritical fluid reinforced fluorine-containing polymer product |
Non-Patent Citations (1)
| Title |
|---|
| LARISSAZIRKEL ET AL.: "Foaming of thin films of a fluorinated ethylene propylene copolymer using supercritical carbon dioxide", 《THE JOURNAL OF SUPERCRITICAL FLUIDS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574744A (en) * | 2020-05-22 | 2020-08-25 | 湖州长园特发科技有限公司 | Preparation method of clean environment-friendly polyvinylidene fluoride foamed sheet |
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