CN105013342B - A kind of preparation method of super-hydrophobic polytetrafluoroethylfiber fiber film - Google Patents
A kind of preparation method of super-hydrophobic polytetrafluoroethylfiber fiber film Download PDFInfo
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- CN105013342B CN105013342B CN201410161929.2A CN201410161929A CN105013342B CN 105013342 B CN105013342 B CN 105013342B CN 201410161929 A CN201410161929 A CN 201410161929A CN 105013342 B CN105013342 B CN 105013342B
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- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000003075 superhydrophobic effect Effects 0.000 title abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 93
- 238000001816 cooling Methods 0.000 claims abstract description 43
- 238000004321 preservation Methods 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 238000010792 warming Methods 0.000 claims abstract description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 81
- -1 polytetrafluoroethylene Polymers 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000004804 winding Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 230000003466 anti-cipated effect Effects 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims 20
- 241001672694 Citrus reticulata Species 0.000 claims 1
- 239000012456 homogeneous solution Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 14
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000004821 distillation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001523 electrospinning Methods 0.000 description 7
- 239000000284 extract Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000012369 In process control Methods 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- Artificial Filaments (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of preparation methods of super-hydrophobic polytetrafluoroethylfiber fiber film, including spinning solution with liquid, system fibre, sintering, it is polyvinyl alcohol at fine carrier, solvent is water it is characterized by: ptfe emulsion is added after being configured to solution at fine carrier and solvent；Sintering is sintered using temperature programmed control zonal cooling, in the case where flowing atmosphere, in 90 DEG C~120 DEG C 30~120min of heat preservation, 260 DEG C~300 DEG C is warming up to from 90 DEG C~120 DEG C with the rate of 3~10 DEG C/min, in 260 DEG C~300 DEG C 30~120min of heat preservation；370 DEG C~390 DEG C are warming up to from 260 DEG C~300 DEG C with the rate of 2~8 DEG C/min, in 370 DEG C~390 DEG C 5~120min of heat preservation；Sintered cooling treatment, the cooling are cooled to 150~200 DEG C from 360 DEG C~400 DEG C in the case where flowing atmosphere, with the rate of 3~15 DEG C/min, in 150~200 DEG C of 30~120min of heat preservation, then natural cooling.
Description
Technical field
The present invention relates to a kind of preparation methods of separation membrane material for separation field, and in particular to a kind of hydrophobic membrane material
Preparation method.
Technical background
Hydrophobicity is the critical nature of polytetrafluoroethylene (PTFE) (PTFE) material, is that polytetrafluoroethylporous porous membrane is applied to membrane material
The main performance of material.Although polytetrafluoroethylene material has low-surface-energy, the water contact angle of smooth polytetrafluoroethylene (PTFE) plane
Between 98 to 112 °, hydrophobic performance is simultaneously bad.
Polytetrafluoroethylporous porous membrane preparation at present mostly uses bidirectional extending method.This method is to obtaining higher porosity
Film when, need to film carry out large scale stretching, can not Surface Structures controlled, and film thickness only more than ten microns with
Under, backing material is needed in use, and backing material itself often has one in heat resistance or chemical stability or hydrophobic performance
Foregone conclusion limit, thus limit the application of this biaxial stretching film.Stretch the shape for being often difficult to control film at high proportion simultaneously, therefore
Mainly based on plate membrane.Chinese patent CN1775847A, CN102007242A, CN101543734B, CN102151494A etc.
Patent is all based on the above stretch processes and carries out polytetrafluoroethylporous porous membrane preparation.
Support methods are to prepare the important method of polytetrafluoroethylene fibre, the patents such as CN101994161A and CN102282301A
The preparation of polytetrafluoroethylsuperfine superfine fiber is reported using electrostatic spinning technique.High temperature sintering is directed in these reports
The step of removing into fine carrier, but these sintering processes are concerned only with into the removal of fine template.Specifically: CN101994161A
Purpose be to prepare a kind of polytetrafluoroethylsuperfine superfine fiber, preparation method is to make carrier using polyvinyl alcohol, passes through Static Spinning
Silk method is weaved out polytetrafluoroethylene fibre precursor, post-processing approach be by polytetrafluoroethylene fibre precursor at 100~120 DEG C
It is 5~15 minutes dry, it is sintered 30~90 minutes at 280~350 DEG C；The purpose of sintering be in order to make polyvinyl alcohol decompose and
Removal.And a kind of improved method for being mainly to provide polytetrafluoroethylene (PTFE) pad of CN102282301A, its purpose is to improve electricity
The technological parameter (spinning fluid viscosity) of spinning pads precursor to obtain the polytetrafluoroethylene fibre of uniform diameter, is sintered at 400 DEG C
Polytetrafluoroethylene fibre pad is obtained, the ash content of carrier (fibre-forming polymer) is less than 5%.CN101994161A and CN102282301A
Etc. patents using electrostatic spinning technique to polytetrafluoroethylsuperfine superfine fiber (pad), only account for how obtaining polytetrafluoroethylene (PTFE) ultra-fine
Fiber (pad), it may be said that have to conventional polytetrafluoroethylsuperfine superfine fiber (pad).
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of polytetrafluoroethylene film, by controlling containing at the poly- of fine carrier
The post-processing sintering condition of tetrafluoroethene precursor film, by the method precision of temperature programmed control control sintering condition and cooling condition with
Obtain the superfine fibre reticular membrane that fibre morphology remains intact and has beading structure, the special construction of this nanoscale with
Superfine fibre forms the hydrophobic surface with multistage coarse structure together.Thus there is ultra-hydrophobicity.
The purpose of the present invention is realized by following technical measures:
A kind of preparation method of polytetrafluoroethylene film, including spinning solution is with liquid, system is fine, is sintered, it is characterised in that: it is carried at fibre
Ptfe emulsion is added after being configured to solution in body and solvent, is polyvinyl alcohol at fine carrier, solvent is water；Sintering uses journey
Sequence temperature control zonal cooling sintering, in the case where flowing atmosphere, in 90 DEG C~120 DEG C 30~120min of heat preservation, with the speed of 3~10 DEG C/min
Rate is warming up to 260 DEG C~300 DEG C from 90 DEG C~120 DEG C, in 260 DEG C~300 DEG C 30~120min of heat preservation；With 2~8 DEG C/min's
Rate is warming up to 370 DEG C~390 DEG C from 260 DEG C~300 DEG C, in 370 DEG C~390 DEG C 5~120min of heat preservation；Sintered cooling
Processing, the cooling are cooled to 150~200 DEG C from 360 DEG C~400 DEG C in the case where flowing atmosphere, with the rate of 3~15 DEG C/min,
In 150~200 DEG C of 30~120min of heat preservation, then natural cooling.
By controlling the post-processing sintering condition containing the polytetrafluoroethylene (PTFE) precursor film at fine carrier, under stress,
Under carrier protective effect, polytetrafluoroethylgranule granule starts reorientation arrangement, then decomposes in appropriate opportunity carrier, polytetrafluoroethyl-ne
Alkene particle is further orientated rearrangement, forms catenate superfine fibre reticular structure.It is carried out using the process control condition
The super-hydrophobic polytetrafluoroethylfiber fiber film with special construction can be made in preparation.If not in process control condition of the invention
Under, it is sintered 30-90 minutes as CN101994161A is set forth at 280-350 DEG C, then can not obtain with multilevel roughness, water
150 ° of contact angle or more of super-hydrophobic polytetrafluoroethylfiber fiber film, and film is without flexibility.If in addition not using process control (such as
CN102282301A is sintered at 400 DEG C and obtains polytetrafluoroethylene fibre pad, and the ash content of carrier (fibre-forming polymer) is less than 5%.)
The original form that then cannot keep fiber, causes fiber to collapse to flat.By controlling sintered cooling condition, further
Reduce the micro-fractures on fiber, forms seamless fiber surface, the intensity and toughness of reinforcing fiber.
Preferably, above-mentioned sintering using temperature programmed control zonal cooling be sintered, in the case where flowing atmosphere, with 2~15 DEG C/min from
Room temperature is to 90 DEG C~120 DEG C, in 100 DEG C~120 DEG C 50~100min of heat preservation, with the rate of 5~8 DEG C/min from 100 DEG C
~120 DEG C are warming up to 280 DEG C~300 DEG C, in 280 DEG C~300 DEG C 60~120min of heat preservation；With the rate of 4~7 DEG C/min from
280 DEG C~300 DEG C are warming up to 380 DEG C~390 DEG C, in 380 DEG C~390 DEG C 30~80min of heat preservation.
The preparation method of above-mentioned polytetrafluoroethylene film includes preforming step before being sintered after system is fine, it is described it is preforming be by
Polytetrafluoroethylene (PTFE) precursor film is wrapped on branch hold mode, controls polytetrafluoroethylene (PTFE) film thickness by winding layer number and average pore size is big
It is small.The stress orientation that the winding of fiber is superimposed with conducive to sintering process.
The mass concentration of polyvinyl alcohol water solution is 0.5%~30%, and polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight ratio are 1: 1
~50.
Specifically, a kind of preparation method of polytetrafluoroethylene film, comprising the following steps:
(1) preparation of spinning solution；It is the uniform molten of 0.5%~30% mass concentration that polyvinyl alcohol, which is dissolved in water to be made into concentration,
Liquid, then ptfe emulsion is added in stirring, obtains uniform mixed liquor；Polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight ratio are 1:
1~50；
(2) system is fine；Fiber is prepared to the spinning solution progress spinning prepared in (1) using the method for spinning or stretching to be gathered
Tetrafluoroethene precursor film；
(3) preforming: it is anticipated that use specification, by (2) it is obtained obtain polytetrafluoroethylene (PTFE) precursor film winding
On the branch hold mode of respective shapes, the film of the different shapes and specification such as flat, tubular type, hollow fiber form or rolling is formed, is led to
Cross winding layer number control film thickness；
(4) it is sintered；Preforming polytetrafluoroethylene (PTFE) precursor film obtained in (3) is put into high temperature furnace together with branch hold mode even
Continue and is sintered under conditions of being passed through flowing atmosphere；Sintering is sintered using temperature programmed control zonal cooling, with the speed of 3~10 DEG C/min
Rate is from room temperature to 120 DEG C~200 DEG C, in 120 DEG C~200 DEG C 30~120min of heat preservation；With the rate of 2~8 DEG C/min from
120 DEG C~200 DEG C are warming up to 360 DEG C~400 DEG C, in 360 DEG C~400 DEG C 5~120min of heat preservation.
(5) cooling: in the case where flowing atmosphere, to be cooled to 150~200 from 360 DEG C~400 DEG C with the rate of 3~15 DEG C/min
DEG C, in 150~200 DEG C of 30~120min of heat preservation, then natural cooling.
Above-mentioned flowing atmosphere is that air, nitrogen or inert gas are at least one.
Beneficial effect
1. the unique polytetrafluoroethylene film of structure has been made in the present invention, with what is formed in a crisscross manner by beading fiber filament
Hole three-dimensional communication structure, is the hydrophobic surface that one of formation has multistage coarse structure, and beading fiber filament refers to polytetrafluoro
Mutually the fiber filament to be formed is cohered in point and/or face between ethylene particle；Hole is in labyrinth hole, and maximum diameter of hole is 1.0 μm, minimum aperture
Diameter is 0.01 μm, and average pore size is 0.1 μm~0.5 μm；Fiber filament is nanofiber, and average diameter is 500 ± 50nm.
2. the present invention is fabulous to solve the problems, such as that fiber is givey in the sintering of polytetrafluoroethylene (PTFE) precursor film, and obtains
There is beading superfine fibre reticular membrane, stick to each other is become from unordered stacking between fiber, fibre morphology and surface are intact,
Intensity and toughness also improve a lot, and are able to bear certain vacuum pressure (can under 0.8kPa vacuum degree still stably operable).
3. polytetrafluoroethylporous porous membrane obtained by the present invention has special super-hydrophobicity structure, obtained PTFE fiber
Surface forms a large amount of rough surfaces, surface water contact angle >=150 °, and porosity is up to 80% or more.
4, for the polytetrafluoroethylporous porous membrane obtained by the present invention without support, thickness is controllable, is applied to membrane distillation process, leads to
Measure > 20L/m2H, rejection is 99% or more.
5, the invention proposes before sintering winding process carry out it is preforming, can to the shape and thickness of final products film
It is controlled, while guaranteeing high porosity (80% or more), thickness needed for providing film and intensity.In contrast to obtain
High porosity and the stretch processes that stretch at high proportion, the obtained polytetrafluoroethylene film of the method for the present invention is without support, shape
Formula multiplicity, thickness are controllable.
6, polytetrafluoroethylene (PTFE) super-hydrophobic film preparation method provided by the invention makes carrier using sintering condition rate-determining steps
It is decomposed on appropriate opportunity, and polytetrafluoroethylgranule granule melting orientation is reset, and has obtained having beading superfine fibre reticular membrane, this
The special construction of kind nanoscale forms the hydrophobic surface with multistage coarse structure together with superfine fibre.Thus have super thin
Aqueous energy.
7, the invention avoids the uses of lubricant in biaxial tension etc., and there is no the removing problem of lubricant, technique letters
Single, without squeezing out, the Complicated Flows such as press mold pollute small.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of polytetrafluoroethylene film made from preparation method of the present invention；It can be seen from attached drawing
Observe: polytetrafluoroethylene film of the invention has the hole three-dimensional communication structure formed in a crisscross manner by beading fiber filament, hole
Gap is in labyrinth hole, and even pore distribution is connected to, and nanofiber form is uniform intact.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment can only be used
In invention is further explained, it should not be understood as limiting the scope of the invention, the people that is skilled in technique in the field
Member can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
Embodiment 1
The ptfe emulsion of solid content 60% is added drop-wise in the polyvinyl alcohol water solution that mass fraction is 12% and is stirred
It mixes uniformly, is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 5cm cylinder
On branch hold mode, wind 5 layers, and be sent in tube furnace lead to nitrogen, sintering process temperature programmed control, with 10 DEG C/min from room temperature to
110 DEG C, 110 DEG C of heat preservation 90min, 290 DEG C, 290 DEG C of heat preservation 100min are warming up to from 110 DEG C with 7 DEG C/min heating rate, from
290 DEG C are warming up to 380 DEG C, and heating rate is 6 DEG C/min, keeps the temperature 60min.
It is cooling: under the flowing atmosphere of nitrogen, to be cooled to 180 DEG C from 373 DEG C with the rate of 8 DEG C/min, kept the temperature at 180 DEG C
80min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the cylindric polytetrafluoroethylene film with a thickness of 185 μm, cutting off can
Obtain flat porous membrane.175 ° of the film hydrophobic contact angle, porosity 88%, 0.45 μm of average pore size, tensile strength
585psi, elongation 388%, when for membrane distillation operation, flux 42L/m2H, rejection 99.7%.
Embodiment 2
The ptfe emulsion of solid content 60% is added drop-wise in the polyvinyl alcohol water solution that mass fraction is 9% and is stirred
Uniformly, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 5cm cylinder branch
On hold mode, 5 layers are wound, and is sent in tube furnace and leads to nitrogen, sintering process temperature programmed control, with 2 DEG C/min from room temperature to 90
DEG C, 90 DEG C of heat preservation 120min are warming up to 260 DEG C from 90 DEG C with 10 DEG C/min heating rate, 260 DEG C of heat preservation 120min, from 260 DEG C
375 DEG C are warming up to, heating rate is 8 DEG C/min, keeps the temperature 115min.
It is cooling: under the flowing atmosphere of air, to be cooled to 200 DEG C from 390 DEG C with the rate of 15 DEG C/min, protected at 200 DEG C
Warm 30min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the cylindric polytetrafluoroethylene film with a thickness of 175um, cutting off can
Obtain flat porous membrane.162 ° of the film hydrophobic contact angle, porosity 82%, 0.45 μm of average pore size, tensile strength
470psi, elongation 320%, when for membrane distillation operation, flux 26L/m2H, rejection 99.5%.
Embodiment 3
The ptfe emulsion of solid content 60% is added drop-wise in the polyvinyl alcohol water solution that mass fraction is 5% and is stirred
Uniformly, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 5cm cylinder branch
On hold mode, 5 layers are wound, and is sent in tube furnace and leads to nitrogen, sintering process temperature programmed control, with 5 DEG C/min from room temperature to 100
DEG C, 100 DEG C of heat preservation 110min are warming up to 275 DEG C from 100 DEG C with 10 DEG C/min heating rate, 275 DEG C of heat preservation 110min, from 275
380 DEG C DEG C are warming up to, heating rate is 3 DEG C/min, keeps the temperature 90min.
It is cooling: under the flowing atmosphere of air, to be cooled to 190 DEG C from 376 DEG C with the rate of 5 DEG C/min, kept the temperature at 190 DEG C
40min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the cylindric polytetrafluoroethylene film with a thickness of 189um, cutting off can
Obtain flat porous membrane.165 ° of the film hydrophobic contact angle, porosity 82%, 0.25 μm of average pore size, tensile strength
485psi, elongation 335%, when for membrane distillation operation, flux 30L/m2H, rejection 99.5%.
Embodiment 4
The ptfe emulsion of solid content 60% is added drop-wise in the polyvinyl alcohol water solution that mass fraction is 7% and is stirred
Uniformly, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 5cm cylinder branch
On hold mode, 6 layers are wound, and is sent to blowing air in tube furnace, sintering process temperature programmed control, with 8 DEG C/min from room temperature to 100
DEG C, 100 DEG C of heat preservation 100min are warming up to 280 DEG C from 100 DEG C with 8 DEG C/min heating rate, 280 DEG C of heat preservation 120min, from 280
385 DEG C DEG C are warming up to, heating rate is 4 DEG C/min, keeps the temperature 80min.
It is cooling: under the flowing atmosphere of argon gas, to be cooled to 150 DEG C from 388 DEG C with the rate of 15 DEG C/min, protected at 150 DEG C
Warm 120min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the cylindric polytetrafluoroethylene film with a thickness of 220um, cut off
Flat porous membrane can be obtained.165 ° of the film hydrophobic contact angle, porosity 85%, 0.45 μm of average pore size, tensile strength
495psi, elongation 345%, when for membrane distillation operation, flux 32L/m2H, rejection 99.2%.
Embodiment 5
The ptfe emulsion of solid content 60% is added drop-wise in the polyvinyl alcohol water solution that mass fraction is 13% and is stirred
It mixes uniformly, is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 0.5cm circle
On cylinder branch hold mode, 5 layers are wound, and is sent in Muffle furnace and leads to nitrogen, sintering process temperature programmed control, with 15 DEG C/min from room temperature
To 120 DEG C, 120 DEG C of heat preservation 30min, 295 DEG C, 295 DEG C of heat preservation 120min are warming up to from 120 DEG C with 3 DEG C/min heating rate, from
295 DEG C are warming up to 390 DEG C, and heating rate is 2 DEG C/min, keeps the temperature 10min.
It is cooling: under the flowing atmosphere of nitrogen, to be cooled to 160 DEG C from 385 DEG C with the rate of 12 DEG C/min, protected at 160 DEG C
Warm 100min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the tubular membrane with a thickness of 178um.The film hydrophobic contact angle
171 °, porosity 85%, 0.5 μm of average pore size, tensile strength 500psi, elongation 340% is operated for tubular membrane membrane distillation
When, flux 35L/m2H, rejection 99.6%.
Embodiment 6
The ptfe emulsion of solid content 60% is added drop-wise in the polyvinyl alcohol water solution that mass fraction is 8% and is stirred
Uniformly, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 0.5cm cylinder
On branch hold mode, wind 5 layers, and be sent in tube furnace lead to argon gas, sintering process temperature programmed control, with 12 DEG C/min from room temperature to
115 DEG C, 115 DEG C of heat preservation 50min, 300 DEG C are warming up to from 115 DEG C with 5 DEG C/min heating rate, 300 DEG C of heat preservation 60min, from 300
390 DEG C DEG C are warming up to, heating rate is 6 DEG C/min, keeps the temperature 30min.
It is cooling: under the flowing atmosphere of argon gas, to be cooled to 170 DEG C from 380 DEG C with the rate of 10 DEG C/min, protected at 170 DEG C
Warm 90min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the tubular membrane with a thickness of 178um.The film hydrophobic contact angle
175 °, porosity 89%, 0.35 μm of average pore size, tensile strength 515psi, elongation 355% is grasped for tubular membrane membrane distillation
When making, flux 37L/m2H, rejection 99.6%.
Embodiment 7
The ptfe emulsion of solid content 60% is added drop-wise in the polyvinyl alcohol water solution that mass fraction is 4% and is stirred
Uniformly, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 0.1cm cylinder
On branch hold mode, wind 6 layers, and be sent to blowing air in tube furnace, sintering process temperature programmed control, with 9 DEG C/min from room temperature to
110 DEG C, 110 DEG C of heat preservation 80min, 285 DEG C are warming up to from 110 DEG C with 6 DEG C/min heating rate, 285 DEG C of heat preservation 70min, from 285
380 DEG C DEG C are warming up to, heating rate is 5 DEG C/min, keeps the temperature 60min.
It is cooling: under the flowing atmosphere of nitrogen, to be cooled to 185 DEG C from 370 DEG C with the rate of 9 DEG C/min, kept the temperature at 185 DEG C
70min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the hollow-fibre membrane with a thickness of 214um.The film hydrophobic contact angle
175 °, porosity 85%, 0.4 μm of average pore size, tensile strength 650psi, elongation 370% is used for hollow-fibre membrane membrane distillation
When operation, flux 41L/m2H, rejection 99.9%.
Claims (7)
1. a kind of preparation method of polytetrafluoroethylene film, including spinning solution is with liquid, system is fine, is sintered, it is characterised in that: at fine carrier
Ptfe emulsion is added after being configured to solution with solvent, is polyvinyl alcohol at fine carrier, solvent is water；Sintering uses program
Temperature control zonal cooling sintering, in the case where flowing atmosphere, in 90 DEG C~120 DEG C 30~120min of heat preservation, with the rate of 3~10 DEG C/min
260 DEG C~300 DEG C are warming up to from 90 DEG C~120 DEG C, in 260 DEG C~300 DEG C 30~120min of heat preservation；With the speed of 2~8 DEG C/min
Rate is warming up to 370 DEG C~390 DEG C from 260 DEG C~300 DEG C, in 370 DEG C~390 DEG C 5~120min of heat preservation；At sintered cooling
Reason, the cooling are cooled to 150~200 DEG C from 360 DEG C~400 DEG C in the case where flowing atmosphere, with the rate of 3~15 DEG C/min,
150~200 DEG C of 30~120min of heat preservation, then natural cooling.
2. the preparation method of polytetrafluoroethylene film as described in claim 1, the sintering is burnt using temperature programmed control zonal cooling
Knot, in the case where flow atmosphere, with 2~15 DEG C/min from room temperature to 90 DEG C~120 DEG C, 100 DEG C~120 DEG C heat preservations 50~
100min is warming up to 280 DEG C~300 DEG C from 100 DEG C~120 DEG C with the rate of 5~8 DEG C/min, keeps the temperature at 280 DEG C~300 DEG C
60~120min；380 DEG C~390 DEG C are warming up to from 280 DEG C~300 DEG C with the rate of 4~7 DEG C/min, at 380 DEG C~390 DEG C
Keep the temperature 30~80min.
3. the preparation method of polytetrafluoroethylene film as claimed in claim 1 or 2 includes preforming step before being sintered after system is fine,
It is described it is preforming be that polytetrafluoroethylene (PTFE) precursor film is wrapped on branch hold mode.
4. the mass concentration of the preparation method of polytetrafluoroethylene film as claimed in claim 1 or 2, polyvinyl alcohol water solution is
0.5%~30%, polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight ratio are 1:1~50.
5. the preparation method of polytetrafluoroethylene film as claimed in claim 3, the mass concentration of polyvinyl alcohol water solution is 0.5%
~30%, polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight ratio are 1:1~50.
6. the preparation method of polytetrafluoroethylene film as described in claim 1, comprising the following steps:
(1) preparation of spinning solution: polyvinyl alcohol is dissolved in water and is made into the homogeneous solution that concentration is 0.5%~30% mass concentration, then
Ptfe emulsion is added in stirring, obtains uniform mixed liquor；Polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight ratio are in 1:1~50；
(2) system is fine: preparing fiber to the spinning solution progress spinning prepared in (1) using the method for spinning or stretching and obtains polytetrafluoro
Ethylene precursor film；
(3) preforming: it is anticipated that use specification, the polytetrafluoroethylene (PTFE) precursor film that obtains obtained in (2) is wrapped in phase
It answers on the branch hold mode of shape, forms the film of flat, tubular type, hollow fiber form or rolling different shape and specification, pass through winding
The number of plies controls film thickness；
(4) it is sintered: preforming polytetrafluoroethylene (PTFE) precursor film obtained in (3) being put into high temperature furnace together with branch hold mode and is continuously being led to
It becomes a mandarin and is sintered under conditions of taking offence atmosphere；Sintering using temperature programmed control zonal cooling be sintered, with the rate of 3~10 DEG C/min from
Room temperature is to 120 DEG C~200 DEG C, in 120 DEG C~200 DEG C 30~120min of heat preservation；With the rate of 2~8 DEG C/min from 120 DEG C
~200 DEG C are warming up to 360 DEG C~400 DEG C, in 360 DEG C~400 DEG C 5~120min of heat preservation；
(5) cooling: in the case where flowing atmosphere, 150~200 DEG C are cooled to from 360 DEG C~400 DEG C with the rate of 3~15 DEG C/min,
150~200 DEG C of 30~120min of heat preservation, then natural cooling.
7. the preparation method of polytetrafluoroethylene film as described in claim 1, the flowing atmosphere is air, nitrogen or indifferent gas
Body is at least one.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN101994161A (en) * | 2009-08-25 | 2011-03-30 | 东丽纤维研究所（中国）有限公司 | Method for preparing polytetrafluoroethylene superfine fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN101994161A (en) * | 2009-08-25 | 2011-03-30 | 东丽纤维研究所（中国）有限公司 | Method for preparing polytetrafluoroethylene superfine fiber |
Non-Patent Citations (1)
| Title |
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| 热处理对PTFE牵伸性能的影响;郭占军等;《纺织学报》;20100630;第31卷(第6期);第21-24页 |
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