CN107837692A - A kind of preparation method of polytetrafluoroethylene (PTFE) super-hydrophobic film - Google Patents
A kind of preparation method of polytetrafluoroethylene (PTFE) super-hydrophobic film Download PDFInfo
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- CN107837692A CN107837692A CN201710777925.0A CN201710777925A CN107837692A CN 107837692 A CN107837692 A CN 107837692A CN 201710777925 A CN201710777925 A CN 201710777925A CN 107837692 A CN107837692 A CN 107837692A
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- ptfe
- polytetrafluoroethylene
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 97
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 87
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000003075 superhydrophobic effect Effects 0.000 title description 6
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims abstract description 85
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 239000000835 fiber Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000010792 warming Methods 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000009987 spinning Methods 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 241001672694 Citrus reticulata Species 0.000 claims description 2
- 230000003466 anti-cipated effect Effects 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 230000005661 hydrophobic surface Effects 0.000 abstract description 4
- 239000002352 surface water Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 238000009413 insulation Methods 0.000 description 11
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 238000004821 distillation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000001523 electrospinning Methods 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid 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
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 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
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0004—Organic membrane manufacture by agglomeration of particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/04—Hydrophobization
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Sintered the invention provides a kind of preparation method of poly tetrafluoroethylene, including into fine carrier system is fine, it is characterised in that：Sintering is sintered using temperature programmed control zonal cooling, and in the case where flowing atmosphere, with 3~10 DEG C/min speed from room temperature to 120 DEG C~200 DEG C, 30~120min is incubated at 120 DEG C~200 DEG C；360 DEG C~400 DEG C are warming up to from 120 DEG C~200 DEG C with 2~8 DEG C/min speed, 5~120min is incubated at 360 DEG C~400 DEG C；Cooling treatment is carried out after sintering, it is described to be cooled under flowing atmosphere, 150~200 DEG C are cooled to from 360 DEG C~400 DEG C with 3~15 DEG C/min speed, is incubated 30~120min at 150~200 DEG C, then natural cooling；The polytetrafluoroethylene (PTFE) thickness is 165 201 μm.The present invention, which has been made, has beading superfine fibre poly tetrafluoroethylene, forms the hydrophobic surface with multistage coarse structure together；Surface water contact angle >=150 °, porosity are up to more than 80%；And solving the givey problem of fiber in polytetrafluoroethylene (PTFE) precursor film sintering, fibre morphology and surface are intact, and intensity and toughness also improve a lot, and can bear certain vacuum pressure.
Description
The present patent application is application number 201410162962.7, the applying date 2014 year 04 month 22 days, denomination of invention " one
The divisional application of the preparation method of kind polytetrafluoroethylene (PTFE) super-hydrophobic film ".
Technical field
The present invention relates to a kind of preparation method of the separation membrane material for separation field, and in particular to a kind of hydrophobic membrane material
Preparation method.
Technical background
Hydrophobicity is polytetrafluoroethylene (PTFE)（PTFE）The critical nature of material, it is that polytetrafluoroethylporous porous membrane is applied to membrane material
The main performance of material.Although polytetrafluoroethylmaterial material has low-surface-energy, the water contact angle of smooth polytetrafluoroethylene (PTFE) plane
Between 98 to 112 °, hydrophobic performance is simultaneously bad.
At present prepared by polytetrafluoroethylporous porous membrane to use bidirectional extending method more.This method will expect higher porosity
Film when, it is necessary to film carry out large scale stretching, can not Surface Structures be controlled, and thickness only more than ten microns with
Under, backing material is needed in use, and backing material often has one in heat resistance or chemical stability or hydrophobic performance in itself
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 Flat Membrane.Chinese patent CN1775847A, CN102007242A, CN101543734B, CN102151494A etc.
Patent is all based on above stretch processes and carries out polytetrafluoroethylporous porous membrane preparation.
Support methods are to prepare the important method of polytetrafluoroethylene fibre, the patent such as CN101994161A and CN102282301A
Reported using preparation of the electrostatic spinning technique to polytetrafluoroethylsuperfine superfine fiber.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, its 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
Dry 5~15 minutes, sintered 30~90 minutes at 280~350 DEG C；The purpose of sintering be in order that polyvinyl alcohol decompose and
Remove.And CN102282301A is mainly to provide a kind of improved method of polytetrafluoroethylene (PTFE) pad, its purpose is to improve electricity
The technological parameter of spinning（Spinning fluid viscosity）To obtain the polytetrafluoroethylene fibre of uniform diameter pad precursor, sintered at 400 DEG C
Obtain polytetrafluoroethylene fibre pad, carrier（Fibre-forming polymer）Ash content be less than 5%.CN101994161A and CN102282301A
Etc. patent 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）.
The content of the invention
It is an object of the invention to provide a kind of preparation method of poly tetrafluoroethylene, by controlling containing gathering into fine carrier
The post processing sintering condition of tetrafluoroethene precursor film, by the accurate control sintering condition of the method for temperature programmed control 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 poly tetrafluoroethylene, including sintered into fine carrier system is fine, it is characterised in that：Sintering uses program control
Warm zonal cooling sintering, in the case where flowing atmosphere, with 3~10 DEG C/min speed from room temperature to 120 DEG C~200 DEG C, 120
DEG C~200 DEG C of 30~120min of insulation；360 DEG C~400 DEG C are warming up to from 120 DEG C~200 DEG C with 2~8 DEG C/min speed,
360 DEG C~400 DEG C 5~120min of insulation；Carry out cooling treatment after sintering, it is described to be cooled under flowing atmosphere, with 3~15 DEG C/
Min speed is cooled to 150~200 DEG C from 360 DEG C~400 DEG C, and 30~120min is incubated at 150~200 DEG C, then naturally cold
But；The polytetrafluoroethylene (PTFE) thickness is 165-201 μm.By controlling the post processing containing the polytetrafluoroethylene (PTFE) precursor film into fine carrier
Sintering condition, under stress, under carrier protective effect, polytetrafluoroethylgranule granule starts reorientation arrangement, then exists
Appropriate opportunity carrier decomposes, and polytetrafluoroethylgranule granule is further orientated rearrangement, forms catenate superfine fibre network structure.Adopt
With described programme-control condition prepare and the super-hydrophobic polytetrafluoroethylfiber fiber film with special construction can be made.If no
Under the conditions of the programme-control of the present invention, 30-90 minutes are sintered as CN101994161A is set forth at 280-350 DEG C, then can not
With multilevel roughness, more than 150 ° of water contact angle super-hydrophobic polytetrafluoroethylfiber fiber film is obtained, and film is without flexible.Separately
If do not use programme-control outside（Polytetrafluoroethylene fibre pad, carrier are obtained as CN102282301A is sintered at 400 DEG C（Into fibre
Polymer）Ash content be less than 5%.）Original form of fiber can not be then kept, causes fiber to collapse to flat.Burnt by controlling
Cooling condition after knot, further reduce the micro-fractures on fiber, form seamless fiber surface, the intensity of reinforcing fiber and
Toughness.
The preparation method of above-mentioned poly tetrafluoroethylene, includes preforming step before being sintered after system is fine, it is described it is preforming be by
Polytetrafluoroethylene (PTFE) precursor film winding 5-6 circles pass through winding layer numerical control polytetrafluoroethylene (PTFE) film thickness and average hole on branch hold mode
Footpath size.The winding of fiber is superimposed with the stress orientation beneficial to sintering process.The support membrane is cylindric, a diameter of 0.1-
5cm。
Specifically, a kind of preparation method of poly tetrafluoroethylene, comprises the following steps：
（1）Preparation of spinning solution；Water-soluble polymer is dissolved in water and is made into the homogeneous solution that concentration is 0.5%~30% mass concentration,
Then stirring adds ptfe emulsion, obtains uniform mixed liquor；Into fine carrier and polytetrafluoroethylene (PTFE) dry weight ratio 1:1~
50；
（2）System is fine；Using the method pair of spinning or stretching（1）The spinning solution progress spinning of middle preparation prepares fiber and obtains polytetrafluoro
Ethene precursor film；
（3）It is preforming：It is anticipated that use specification, will（2）In obtained by the polytetrafluoroethylene (PTFE) precursor film that obtains be wrapped in phase
Answer on the branch hold mode of shape, the film of the different shapes such as flat, tubular type, hollow fiber form or rolling and specification is formed, by twining
Winding layer numerical control film is thick；
（4）Sintering；Will（3）In obtained preforming polytetrafluoroethylene (PTFE) precursor film be put into high temperature furnace together with branch hold mode and continuously leading to
Become a mandarin to take offence and be sintered under conditions of atmosphere；Sintering using temperature programmed control zonal cooling sinter, with 3~10 DEG C/min speed from
Room temperature is incubated 30~120min to 120 DEG C~200 DEG C, at 120 DEG C~200 DEG C；With 2~8 DEG C/min speed from 120 DEG C
~200 DEG C are warming up to 360 DEG C~400 DEG C, and 5~120min is incubated at 360 DEG C~400 DEG C；
（5）Cooling：In the case where flowing atmosphere, 150~200 DEG C are cooled to from 360 DEG C~400 DEG C with 3~15 DEG C/min speed,
150~200 DEG C are incubated 30~120min, then natural cooling.
Above-mentioned flowing atmosphere is that nitrogen, air or inert gas are at least one.
Beneficial effect
1. the poly tetrafluoroethylene of unique structure has been made in the present invention, have by the crisscross hole formed of beading filament
Three-dimensional communication structure, is the hydrophobic surface that one of formation has multistage coarse structure, and beading filament refers to polytetrafluoroethylene (PTFE)
Mutually the filament to be formed is cohered in point and/or face between particle；Hole is in labyrinth hole, and maximum diameter of hole is 1.0 μm, and minimum-value aperture is
0.01 μm, average pore size is 0.1 μm~0.5 μm；Filament is nanofiber, and average diameter is 500 ± 50 nm.
2. the present invention is fabulous to solve the givey problem of fiber in polytetrafluoroethylene (PTFE) precursor film sintering, and
Having arrived has beading superfine fibre reticular membrane, is changed into inter-adhesive from unordered stacking between fiber, fibre morphology and surface are complete
Good, intensity and toughness also improve a lot, and can bear certain vacuum pressure（It can still stablize under 0.7kPa vacuums and grasp
Make）.
3. the polytetrafluoroethylporous porous membrane obtained by the present invention, there is 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 more than 80%.
4th, for the polytetrafluoroethylporous porous membrane obtained by the present invention without support, thickness is controllable, applied to membrane distillation process, leads to
Amount>20L/m2H, rejection is more than 99%.
5th, the winding process of the invention proposed before sintering is carried out preforming, can to the shape and thickness of final products film
It is controlled, is ensureing high porosity（More than 80%）While, there is provided thickness and intensity needed for film.In contrast to obtain
High porosity and the stretch processes stretched at high proportion, the poly tetrafluoroethylene obtained by the inventive method is without support, shape
Formula is various, and thickness is controllable.
6th, polytetrafluoroethylene (PTFE) super-hydrophobic film preparation method provided by the invention, using sintering condition rate-determining steps, makes carrier
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 with super thin
Water-based energy.
7th, present invention, avoiding the use of lubricant in biaxial tension etc., in the absence of the removing problem of lubricant, technique letter
It is single, it is small without the Complicated Flows such as extrusion, press mold, pollution.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that the present embodiment can only be used
It is further described in the present invention, it is impossible to be interpreted 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 the invention described above.
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 stirred,
It is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.
It is wound on diameter 5cm cylinder branch hold modes, winds 5 layers, and is sent in tube furnace and leads to nitrogen, sintering process program control
Temperature, from room temperature to 140 DEG C of programming rates, 7 DEG C/min, 140 DEG C of insulation 80min, 373 DEG C are warming up to from 140 DEG C, programming rate is
8 DEG C/min, after reaching sintering temperature, i.e. 373 DEG C of sintering stage temperature, it is incubated 100min.
Cooling：Under the flowing atmosphere of nitrogen, 180 DEG C are cooled to from 373 DEG C with 8 DEG C/min speed, in 180 DEG C of insulations
80min, then natural cooling.
Extract cylinder branch hold mode after being taken out after cooling out, obtain the cylindric poly tetrafluoroethylene that thickness is 180 μm, cutting off can
Obtain flat porous membrane.174 ° of the film hydrophobic contact angle, porosity 89%, 0.5 μm, tensile strength 498psi of average pore size,
Elongation 375%, when being operated for membrane distillation, flux 28L/m2H, rejection 99.5%.
Embodiment 2
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 9% and stirred,
It is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.
It is wound on diameter 5cm cylinder branch hold modes, winds 5 layers, and is sent in tube furnace and leads to nitrogen, sintering process program control
Temperature, from room temperature to 150 DEG C of programming rates, 6 DEG C/min, 70min is incubated at 150 DEG C, is warming up to 390 DEG C from 150 DEG C, programming rate
For 6 DEG C/min, after reaching sintering temperature, i.e. 392 DEG C of sintering stage temperature is incubated 10min.
Cooling：Under the flowing atmosphere of air, 200 DEG C are cooled to from 390 DEG C with 15 DEG C/min speed, in 200 DEG C of guarantors
Warm 30min, then natural cooling.
Extract cylinder branch hold mode after being taken out after cooling out, obtain the cylindric poly tetrafluoroethylene that thickness is 201um, cutting off can
Obtain flat porous membrane.170 ° of the film hydrophobic contact angle, porosity 85%, 0.45 μm of average pore size, tensile strength
455psi, elongation 308%, when being operated for membrane distillation, flux 25L/m2H, rejection 99.3%.
Embodiment 3
The ptfe emulsion of solid content 60% is added drop-wise in the sodium alginate aqueous solution that mass fraction is 5% and stirred,
It is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.
It is wound on diameter 5cm cylinder branch hold modes, winds 5 layers, and is sent in tube furnace and leads to nitrogen, sintering process program control
Temperature, from room temperature to 180 DEG C of programming rates, 4 DEG C/min, 180 DEG C of insulation 40min, 376 DEG C are warming up to from 180 DEG C, programming rate is
3 DEG C/min, after reaching sintering temperature, i.e. 376 DEG C of sintering stage temperature, it is incubated 80min.
Cooling：Under the flowing atmosphere of air, 190 DEG C are cooled to from 376 DEG C with 5 DEG C/min speed, in 190 DEG C of insulations
40min, then natural cooling.
Extract cylinder branch hold mode after being taken out after cooling out, obtain the cylindric poly tetrafluoroethylene that thickness is 179um, cutting off can
Obtain flat porous membrane.163 ° of the film hydrophobic contact angle, porosity 82%, 0.2 μm, tensile strength 465psi of average pore size,
Elongation 310%, when being operated for membrane distillation, flux 26L/m2H, rejection 99.5%.
Embodiment 4
The ptfe emulsion of solid content 60% is added drop-wise in the aqueous gelatin solution that mass fraction is 7% and stirred, is made into
Spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.
It is wound on diameter 5cm cylinder branch hold modes, winds 6 layers, and is sent to blowing air in tube furnace, sintering process program control
Temperature, from room temperature to 120 DEG C of programming rates, 10 DEG C/min, 120 DEG C of insulation 120min, 388 DEG C are warming up to from 120 DEG C, programming rate
For 4 DEG C/min, after reaching sintering temperature, i.e. 388 DEG C of sintering stage temperature is incubated 26min.
Cooling：Under the flowing atmosphere of argon gas, 150 DEG C are cooled to from 388 DEG C with 15 DEG C/min speed, in 150 DEG C of guarantors
Warm 120min, then natural cooling.
Extract cylinder branch hold mode after being taken out after cooling out, obtain the cylindric poly tetrafluoroethylene that thickness is 198um, cut off
It can obtain flat porous membrane.158 ° of the film hydrophobic contact angle, porosity 85%, 0.45 μm of average pore size, tensile strength
460psi, elongation 320%, when being operated for membrane distillation, flux 30L/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 stirred,
It is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.
It is wound on diameter 0.5cm cylinder branch hold modes, winds 5 layers, and is sent in Muffle furnace and leads to nitrogen, sintering process program
Temperature control, from room temperature to 130 DEG C of programming rates, 8 DEG C/min, 130 DEG C of insulation 100min, 385 DEG C are warming up to from 130 DEG C, heating speed
Spend for 7 DEG C/min, after reaching sintering temperature, i.e. 385 DEG C of sintering stage temperature is incubated 35min.
Cooling：Under the flowing atmosphere of nitrogen, 160 DEG C are cooled to from 385 DEG C with 12 DEG C/min speed, in 160 DEG C of guarantors
Warm 100min, then natural cooling.
Extract cylinder branch hold mode after being taken out after cooling out, obtain the tubular membrane that thickness is 165um.The film hydrophobic contact angle
172 °, porosity 84%, 0.15 μm, tensile strength 480psi of average pore size, elongation 325%, 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 sodium alginate aqueous solution that mass fraction is 8% and stirred,
It is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.
It is wound on diameter 0.5cm cylinder branch hold modes, winds 5 layers, and is sent in tube furnace and leads to argon gas, sintering process program
Temperature control, from room temperature to 160 DEG C of programming rates, 5 DEG C/min, 160 DEG C of insulation 100min, 380 DEG C are warming up to from 160 DEG C, heating speed
Spend for 5 DEG C/min, after reaching sintering temperature, i.e. 380 DEG C of sintering stage temperature is incubated 60min.
Cooling：Under the flowing atmosphere of argon gas, 170 DEG C are cooled to from 380 DEG C with 10 DEG C/min speed, in 170 DEG C of guarantors
Warm 90min, then natural cooling.
Extract cylinder branch hold mode after being taken out after cooling out, obtain the tubular membrane that thickness is 188um.The film hydrophobic contact angle
164 °, porosity 84%, 0.35 μm, tensile strength 480psi of average pore size, elongation 320%, operated for tubular membrane membrane distillation
When, flux 37L/m2H, rejection 99.6%.
Embodiment 7
The ptfe emulsion of solid content 60% is added drop-wise in the aqueous gelatin solution that mass fraction is 4% and stirred, is made into
Spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.
It is wound on diameter 0.1cm cylinder branch hold modes, winds 6 layers, and is sent to blowing air in tube furnace, sintering process program
Temperature control, from room temperature to 200 DEG C of programming rates, 3 DEG C/min, 200 DEG C of insulation 30min, 385 DEG C are warming up to from 200 DEG C, programming rate
For 2 DEG C/min, after reaching sintering temperature, i.e., at 370 DEG C of sintering stage temperature, 120min is incubated.
Cooling：Under the flowing atmosphere of nitrogen, 185 DEG C are cooled to from 370 DEG C with 9 DEG C/min speed, in 185 DEG C of insulations
70min, then natural cooling.
Extract cylinder branch hold mode after being taken out after cooling out, obtain the hollow-fibre membrane that thickness is 198um.The film hydrophobic contact angle
174 °, porosity 85%, 0.45 μm, tensile strength 450psi of average pore size, elongation 365%, for hollow-fibre membrane membrane distillation
During operation, flux 40L/m2H, rejection 99.9%.
Claims (5)
1. a kind of preparation method of poly tetrafluoroethylene, including sintered into fine carrier system is fine, it is characterised in that：Sintering uses
Temperature programmed control zonal cooling sinter, in the case where flowing atmosphere, with 3~10 DEG C/min speed from room temperature to 120 DEG C~
200 DEG C, 30~120min is incubated at 120 DEG C~200 DEG C；With 2~8 DEG C/min speed 360 are warming up to from 120 DEG C~200 DEG C
DEG C~400 DEG C, it is incubated 5~120min at 360 DEG C~400 DEG C；Cooling treatment is carried out after sintering, it is described to be cooled in flowing atmosphere
Under, be cooled to 150~200 DEG C from 360 DEG C~400 DEG C with 3~15 DEG C/min speed, 150~200 DEG C be incubated 30~
120min, then natural cooling；The polytetrafluoroethylene (PTFE) thickness is 165-201 μm.
2. the preparation method of the poly tetrafluoroethylene as described in claim 1, include preforming step, institute before being sintered after system is fine
It is to enclose polytetrafluoroethylene (PTFE) precursor film winding 5-6 on branch hold mode to state preforming.
3. the preparation method of poly tetrafluoroethylene as claimed in claim 2, the support membrane is cylindric, a diameter of 0.1-
5cm。
4. the preparation method of the poly tetrafluoroethylene as described in claim 1-3 is any, comprises the following steps：
（1）Preparation of spinning solution：Water-soluble polymer is dissolved in water and is made into the homogeneous solution that concentration is 0.5%~30% mass concentration,
Then stirring adds ptfe emulsion, obtains uniform mixed liquor；Into fine carrier and polytetrafluoroethylene (PTFE) dry weight ratio 1:1~
50；
（2）System is fine：Using the method pair of spinning（1）The spinning solution progress spinning of middle preparation prepares fiber and obtains poly- four
PVF precursor film；
（3）It is preforming：It is anticipated that use specification, will（2）In obtained by the polytetrafluoroethylene (PTFE) precursor film that obtains be wrapped in phase
Answer on the branch hold mode of shape, form the film of flat, tubular type, hollow fiber form or rolling, be film-made by winding layer numerical control thick；
（4）Sintering：Will（3）In obtained preforming polytetrafluoroethylene (PTFE) precursor film be put into high temperature furnace together with branch hold mode and continuously leading to
Become a mandarin to take offence and be sintered under conditions of atmosphere；Sintering using temperature programmed control zonal cooling sinter, with 3~10 DEG C/min speed from
Room temperature is incubated 30~120min to 120 DEG C~200 DEG C, at 120 DEG C~200 DEG C；With 2~8 DEG C/min speed from 120 DEG C
~200 DEG C are warming up to 360 DEG C~400 DEG C, and 5~120min is incubated at 360 DEG C~400 DEG C；
（5）Cooling：In the case where flowing atmosphere, it is cooled to from 360 DEG C~400 DEG C 150 with 3~15 DEG C/min speed~
200 DEG C, 30~120min is incubated at 150~200 DEG C, then natural cooling.
5. the preparation method of the poly tetrafluoroethylene as described in claim 1-4 is any, the flowing atmosphere be nitrogen, air or
At least one of inert gas.
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| CN105013345A (en) | 2015-11-04 |
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