CN107441962A - A kind of preparation method of super-hydrophobic poly tetrafluoroethylene - Google Patents
A kind of preparation method of super-hydrophobic poly tetrafluoroethylene Download PDFInfo
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- CN107441962A CN107441962A CN201710790475.9A CN201710790475A CN107441962A CN 107441962 A CN107441962 A CN 107441962A CN 201710790475 A CN201710790475 A CN 201710790475A CN 107441962 A CN107441962 A CN 107441962A
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- ptfe
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- warming
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 99
- 229940058401 polytetrafluoroethylene Drugs 0.000 title claims abstract description 85
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 85
- -1 poly tetrafluoroethylene Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000003075 superhydrophobic effect Effects 0.000 title description 5
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 238000010792 warming Methods 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 18
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 34
- 238000009413 insulation Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000004804 winding Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003570 air 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
- 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
- 241001672694 Citrus reticulata Species 0.000 claims 1
- 239000012456 homogeneous solution Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000000463 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
- 238000010276 construction Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 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
- 239000002245 particle 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
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- 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
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a kind of preparation method of poly tetrafluoroethylene, including spinning solution is with liquid, system is fine, sinters, it is characterised in that：Ptfe emulsion is added after being configured to solution into fine carrier and solvent, is polyacrylic acid into fine carrier, solvent is water；The sintering is sintered using temperature programmed control zonal cooling, in the case where flowing atmosphere, is incubated 30~120min at 90 DEG C~120 DEG C, 260 DEG C~300 DEG C are warming up to from 90 DEG C~120 DEG C with 3~10 DEG C/min speed, 30~120min is incubated at 260 DEG C~300 DEG C；370 DEG C~390 DEG C are warming up to from 260 DEG C~300 DEG C with 2~8 DEG C/min speed, 5~120min is incubated at 370 DEG C~390 DEG C；The polytetrafluoroethylene (PTFE) film thickness is 160 210 μm.The present invention is fabulous to solve the givey problem of fiber in polytetrafluoroethylene (PTFE) precursor film sintering, and obtain that there is beading superfine fibre reticular membrane, it is changed into inter-adhesive from unordered stacking between fiber, fibre morphology is homogeneous, surface is intact, intensity and toughness also improve a lot, and can bear certain vacuum pressure.
Description
The present patent application is application number 201410162723.1, the applying date 2014 year 04 month 22 days, and " one kind is super for denomination of invention
The divisional application of the preparation method of hydrophobic poly tetrafluoroethylene ".
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 the critical nature of polytetrafluoroethylene (PTFE) (PTFE) material, 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 (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. 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, sintering condition is controlled to obtain fiber shape by the way that the method for temperature programmed control is accurate
State remains intact and has the superfine fibre reticular membrane of beading structure, special construction and the superfine fibre one of this nanoscale
Road forms the hydrophobic surface with multistage coarse structure.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 spinning solution is with liquid, system is fine, sinters, it is characterised in that：Carried into fibre
Body adds ptfe emulsion after being configured to solution with solvent, is polyacrylic acid into fine carrier, solvent is water；The sintering is adopted
Sintered with temperature programmed control zonal cooling, in the case where flowing atmosphere, 30~120min is incubated at 90 DEG C~120 DEG C, with 3~10 DEG C/min
Speed be warming up to 260 DEG C~300 DEG C from 90 DEG C~120 DEG C, 260 DEG C~300 DEG C be incubated 30~120min；With 2~8 DEG C/
Min speed is warming up to 370 DEG C~390 DEG C from 260 DEG C~300 DEG C, and 5~120min is incubated at 370 DEG C~390 DEG C；It is described poly-
Tetrafluoroethene film thickness is 160-210 μm.By controlling the post processing sintered bar containing the polytetrafluoroethylene (PTFE) precursor film into fine carrier
Part, under stress, under carrier protective effect, polytetrafluoroethylgranule granule starts reorientation arrangement, then when appropriate
Airborne body decomposes, and polytetrafluoroethylgranule granule is further orientated rearrangement, forms catenate superfine fibre network structure.Using described
Programme-control condition carry out prepare the super-hydrophobic polytetrafluoroethylfiber fiber film with special construction can be made.If not in this hair
Under the conditions of bright programme-control, 30-90 minutes are sintered as CN101994161A is set forth at 280-350 DEG C, then can not be had
There is multilevel roughness, more than 150 ° of water contact angle super-hydrophobic polytetrafluoroethylfiber fiber film, and film is without flexibility.If in addition not
Using programme-control, (such as CN102282301A is sintered at 400 DEG C and is obtained polytetrafluoroethylene fibre pad, carrier (fibre-forming polymer)
Ash content be less than 5%.) original form of fiber can not be then kept, cause fiber to collapse to flat.
Preferably, above-mentioned sintering using temperature programmed control zonal cooling sinter, in the case where flowing atmosphere, with 2~15 DEG C/min from
Room temperature to 90 DEG C~120 DEG C, 90 DEG C~120 DEG C be incubated 50~100min, with 5~8 DEG C/min speed from 100 DEG C~
120 DEG C are warming up to 280 DEG C~300 DEG C, and 60~120min is incubated at 280 DEG C~300 DEG C；With 4~7 DEG C/min speed from 280
DEG C~300 DEG C be warming up to 380 DEG C~390 DEG C, 380 DEG C~390 DEG C be incubated 30~80min.
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。
The mass concentration of the polyacrylic acid aqueous solution is 0.5%~30%, and polyacrylic acid is 1: 1 with polytetrafluoroethylene (PTFE) dry weight ratio
~50.
Specifically, a kind of preparation method of poly tetrafluoroethylene, comprises the following steps：
(1) preparation of spinning solution；Polyacrylic acid is dissolved in water and is made into concentration as the uniform molten of 0.5%~30% mass concentration
Liquid, then stirring add ptfe emulsion, obtain uniform mixed liquor；Polyacrylic acid is with polytetrafluoroethylene (PTFE) dry weight ratio 1:
1~50；
(2) system is fine；Fiber is prepared using the method for spinning or stretching to the spinning solution progress spinning prepared in (1) to be gathered
Tetrafluoroethene precursor film；
(3) it is preforming：It is anticipated that use specification, the winding of polytetrafluoroethylene (PTFE) precursor film will be obtained obtained by (2)
On the branch hold mode of respective shapes, the film of the different shapes such as flat, tubular type, hollow fiber form or rolling and specification is formed, is led to
It is thick to cross winding layer numerical control film；
(4) sinter；The preforming polytetrafluoroethylene (PTFE) precursor film obtained in (3) is put into high temperature furnace even together with branch hold mode
Continuous be passed through under conditions of flowing atmosphere is sintered；Sintering is sintered using temperature programmed control zonal cooling, in 90 DEG C~120 DEG C insulations
30~120min, 260 DEG C~300 DEG C are warming up to from 90 DEG C~120 DEG C with 3~10 DEG C/min speed, at 260 DEG C~300 DEG C
It is incubated 30~120min；Be warming up to 370 DEG C~390 DEG C from 260 DEG C~300 DEG C with 2~8 DEG C/min speed, 370 DEG C~
390 DEG C of 5~120min of insulation.
Above-mentioned flowing atmosphere is that air, nitrogen or inert gas are at least one.
Beneficial effect
1. the poly tetrafluoroethylene of unique structure has been made in the present invention, has and to be formed by beading filament is crisscross
Hole three-dimensional communication structure, is the hydrophobic surface that one of formation has multistage coarse structure, and beading filament refers to polytetrafluoro
Mutually the filament to be formed is cohered in point and/or face between ethene particle；Hole is in labyrinth hole, and maximum diameter of hole is 1.0 μm, minimum aperture
Footpath is 0.01 μm, and average pore size is 0.1 μm~0.5 μm；Filament is nanofiber, and average diameter is 500 ± 50nm.
2. the present invention is fabulous to solve the givey problem of fiber in polytetrafluoroethylene (PTFE) precursor film sintering, and obtains
There is beading superfine fibre reticular membrane, be changed into inter-adhesive from unordered stacking between fiber, fibre morphology is homogeneous, surface is complete
Good, intensity and toughness also improve a lot, and can bear certain vacuum pressure and (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 >=26L/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, while high porosity (more than 80%) is ensured, 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.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of poly tetrafluoroethylene made from preparation method of the present invention；It can be seen from accompanying drawing
Observe：The poly tetrafluoroethylene of the present invention has by the crisscross hole three-dimensional communication structure formed of beading filament, hole
Gap is in labyrinth hole, and even pore distribution connects, and nanofiber form is homogeneous intact.
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 polyacrylic acid aqueous solution that mass fraction is 15% and stirred
Mix uniformly, be made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 5cm cylinders
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 insulation 90min, 290 DEG C, 290 DEG C of insulation 100min are warming up to from 110 DEG C with 7 DEG C/min programming rates, from
290 DEG C are warming up to 380 DEG C, and programming rate is 6 DEG C/min, are incubated 60min.Extract cylinder branch hold mode after being taken out after cooling out, obtain
Thickness is 165 μm of cylindric poly tetrafluoroethylene, cuts off and can obtain flat porous membrane.171 ° of the film hydrophobic contact angle,
Porosity 87%, 0.35 μm, tensile strength 490psi of average pore size, elongation 385%, when being operated for membrane distillation, flux
38L/m2H, rejection 99.7%.
Embodiment 2
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 8% and 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 insulation 120min, 260 DEG C are warming up to from 90 DEG C with 10 DEG C/min programming rates, 260 DEG C of insulation 120min, from 260 DEG C
375 DEG C are warming up to, programming rate is 8 DEG C/min, is incubated 115min.Extract cylinder branch hold mode after being taken out after cooling out, obtain thickness
For 160um cylindric poly tetrafluoroethylene, cut off and can obtain flat porous membrane.156 ° of the film hydrophobic contact angle, hole
Rate 83%, 0.40 μm, tensile strength 460psi of average pore size, elongation 312%, when being operated for membrane distillation, flux 27L/
m2H, rejection 99.3%.
Embodiment 3
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 6% and 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 insulation 110min, 275 DEG C are warming up to from 100 DEG C with 10 DEG C/min programming rates, 275 DEG C of insulation 110min, from 275
DEG C 380 DEG C are warming up to, programming rate is 3 DEG C/min, is incubated 90min.Extract cylinder branch hold mode after being taken out after cooling out, obtain thickness
For 166um cylindric poly tetrafluoroethylene, cut off and can obtain flat porous membrane.163 ° of the film hydrophobic contact angle, hole
Rate 82%, 0.25 μm, tensile strength 477psi of average pore size, elongation 322%, when being operated for membrane distillation, flux 29L/
m2H, rejection 99.6%.
Embodiment 4
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 5% and 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 insulation 100min, 280 DEG C are warming up to from 100 DEG C with 8 DEG C/min programming rates, 280 DEG C of insulation 120min, from 280
DEG C 385 DEG C are warming up to, programming rate is 4 DEG C/min, is incubated 80min.Extract cylinder branch hold mode after being taken out after cooling out, obtain thickness
For 210um cylindric poly tetrafluoroethylene, cut off and can obtain flat porous membrane.169 ° of the film hydrophobic contact angle, hole
Gap rate 84%, 0.40 μm, tensile strength 470psi of average pore size, elongation 330%, when being operated for membrane distillation, flux 32L/
m2H, rejection 99.3%.
Embodiment 5
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 10% and stirred
Mix uniformly, be made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 0.5cm circles
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 insulation 30min, 295 DEG C, 295 DEG C of insulation 120min are warming up to from 120 DEG C with 3 DEG C/min programming rates, from
295 DEG C are warming up to 390 DEG C, and programming rate is 2 DEG C/min, are incubated 10min.Extract cylinder branch hold mode after being taken out after cooling out, obtain
Thickness is 170um tubular membrane.170 ° of the film hydrophobic contact angle, porosity 85%, 0.5 μm of average pore size, tensile strength
472psi, elongation 350%, when being operated for tubular membrane membrane distillation, flux 36L/m2H, rejection 99.6%.
Embodiment 6
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 6% and 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 cylinders
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 insulation 50min, 300 DEG C are warming up to from 115 DEG C with 5 DEG C/min programming rates, 300 DEG C of insulation 60min, from 300
DEG C 390 DEG C are warming up to, programming rate is 6 DEG C/min, is incubated 30min.Extract cylinder branch hold mode after being taken out after cooling out, obtain thickness
For 188um tubular membrane.173 ° of the film hydrophobic contact angle, porosity 88%, 0.35 μm, tensile strength 478psi of average pore size,
Elongation 359%, when being operated for tubular membrane membrane distillation, flux 38L/m2H, rejection 99.6%.
Embodiment 7
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 3% and 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 cylinders
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 insulation 80min, 285 DEG C are warming up to from 110 DEG C with 6 DEG C/min programming rates, 285 DEG C of insulation 70min, from 285
DEG C 380 DEG C are warming up to, programming rate is 5 DEG C/min, is incubated 60min.Extract cylinder branch hold mode after being taken out after cooling out, obtain thickness
For 203um hollow-fibre membrane.175 ° of the film hydrophobic contact angle, porosity 85%, 0.38 μm of average pore size, tensile strength
490psi, elongation 370%, during for hollow-fibre membrane distillation procedure, flux 43L/m2H, rejection 99.7%.
Claims (7)
1. a kind of preparation method of poly tetrafluoroethylene, including spinning solution is with liquid, system is fine, sinters, it is characterised in that：Into fine carrier
Ptfe emulsion is added after being configured to solution with solvent, is polyacrylic acid into fine carrier, solvent is water；The sintering uses
Temperature programmed control zonal cooling sinters, and in the case where flowing atmosphere, 30~120min is incubated at 90 DEG C~120 DEG C, with 3~10 DEG C/min's
Speed is warming up to 260 DEG C~300 DEG C from 90 DEG C~120 DEG C, and 30~120min is incubated at 260 DEG C~300 DEG C；With 2~8 DEG C/min
Speed be warming up to 370 DEG C~390 DEG C from 260 DEG C~300 DEG C, 370 DEG C~390 DEG C be incubated 5~120min；The polytetrafluoro
Ethene film thickness is 160-210 μm.
2. the preparation method of poly tetrafluoroethylene as claimed 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, 90 DEG C~120 DEG C insulations 50~
100min, 280 DEG C~300 DEG C are warming up to from 100 DEG C~120 DEG C with 5~8 DEG C/min speed, in 280 DEG C~300 DEG C insulations
60~120min；380 DEG C~390 DEG C are warming up to from 280 DEG C~300 DEG C with 4~7 DEG C/min speed, at 380 DEG C~390 DEG C
It is incubated 30~80min.
3. the preparation method of poly tetrafluoroethylene as claimed in claim 1 or 2, include preforming step before being sintered after the system is fine
Suddenly, it is described it is preforming be by polytetrafluoroethylene (PTFE) precursor film winding 5-6 circle on branch hold mode.
4. the preparation method of the poly tetrafluoroethylene as described in claim 1,2 or 3, the support membrane is cylindrical shape, a diameter of
0.1-5cm。
5. the preparation method of the poly tetrafluoroethylene as described in claim 1-4 is any, the mass concentration of the polyacrylic acid aqueous solution
For 0.5%~30%, polyacrylic acid is 1 with polytetrafluoroethylene (PTFE) dry weight ratio:1~50.
6. the preparation method of poly tetrafluoroethylene as claimed in claim 1, comprises the following steps：
（1）Preparation of spinning solution；Polyacrylic acid 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；Polyacrylic acid is with 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, form flat, tubular type, hollow fiber form or rolling shape；
（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, 90 DEG C~120 DEG C be incubated 30~
120min, 260 DEG C~300 DEG C are warming up to from 90 DEG C~120 DEG C with 3~10 DEG C/min speed, in 260 DEG C~300 DEG C insulations
30~120min；370 DEG C~390 DEG C are warming up to from 260 DEG C~300 DEG C with 2~8 DEG C/min speed, at 370 DEG C~390 DEG C
It is incubated 5~120min.
7. the preparation method of the poly tetrafluoroethylene as described in claim 1-6 is any, the flowing atmosphere be air, nitrogen or
Inert gas is at least one.
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| CN201710790475.9A CN107441962B (en) | 2014-04-22 | 2014-04-22 | Preparation method of super-hydrophobic polytetrafluoroethylene membrane |
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| CN201710790475.9A CN107441962B (en) | 2014-04-22 | 2014-04-22 | Preparation method of super-hydrophobic polytetrafluoroethylene membrane |
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| CN112210838A (en) * | 2020-08-19 | 2021-01-12 | 浙江理工大学 | Preparation method of polytetrafluoroethylene fiber with surface microsphere structure |
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| CN109395604A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethylhollow hollow fiber membrane and preparation method thereof |
| CN109395615A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethylene film and preparation method thereof |
| CN109395599A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof |
| CN109395595A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethylhollow hollow fiber membrane and preparation method thereof |
| CN109395600A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof |
| CN109395598A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof |
| CN109395596A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethylhollow hollow fiber membrane and preparation method thereof |
| CN109395606A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof |
| CN109395607A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of polytetrafluoroethylene film and preparation method thereof |
| US11801480B2 (en) * | 2018-10-24 | 2023-10-31 | Sumitomo Electric Fine Polymer, Inc. | Hollow-fiber membrane and hollow-fiber membrane module |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5037457A (en) * | 1988-12-15 | 1991-08-06 | Millipore Corporation | Sterile hydrophobic polytetrafluoroethylene membrane laminate |
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN102908911A (en) * | 2012-10-31 | 2013-02-06 | 辽宁省电力有限公司电力科学研究院 | Processing method of polytetrafluoroethylene microporous filtering material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5585727B2 (en) * | 2012-03-12 | 2014-09-10 | 三菱レイヨン株式会社 | Porous membrane manufacturing method and porous membrane drying apparatus |
| CN103882541B (en) * | 2012-12-19 | 2016-03-23 | 中国科学院大连化学物理研究所 | A kind of polytetrafluoroethylene fibre and hollow-fibre membrane and Synthesis and applications thereof |
| CN103285739B (en) * | 2013-05-16 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of preparation method of hydrophobic porous diffusion barrier |
-
2014
- 2014-04-22 CN CN201410162723.1A patent/CN104998557B/en not_active Expired - Fee Related
- 2014-04-22 CN CN201710790475.9A patent/CN107441962B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5037457A (en) * | 1988-12-15 | 1991-08-06 | Millipore Corporation | Sterile hydrophobic polytetrafluoroethylene membrane laminate |
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN102908911A (en) * | 2012-10-31 | 2013-02-06 | 辽宁省电力有限公司电力科学研究院 | Processing method of polytetrafluoroethylene microporous filtering material |
Non-Patent Citations (1)
| Title |
|---|
| 郭占军等: ""热处理对PTFE牵伸性能的影响"", 《纺织学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210838A (en) * | 2020-08-19 | 2021-01-12 | 浙江理工大学 | Preparation method of polytetrafluoroethylene fiber with surface microsphere structure |
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