CN104998557B - 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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- CN104998557B CN104998557B CN201410162723.1A CN201410162723A CN104998557B CN 104998557 B CN104998557 B CN 104998557B CN 201410162723 A CN201410162723 A CN 201410162723A CN 104998557 B CN104998557 B CN 104998557B
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 95
- 229940058401 polytetrafluoroethylene Drugs 0.000 title claims abstract description 83
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 83
- -1 poly tetrafluoroethylene Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003075 superhydrophobic effect Effects 0.000 title description 5
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 238000010792 warming Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 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 7
- 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 16
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 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
- 239000012528 membrane Substances 0.000 abstract description 26
- 239000000853 adhesive Substances 0.000 abstract description 2
- 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
- 230000004907 flux Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000004804 winding Methods 0.000 description 5
- 239000003570 air Substances 0.000 description 3
- 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
- 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
- 230000015572 biosynthetic process 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
- 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
- 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
- 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, sinter, it is characterised in that：It is configured to after solution add ptfe emulsion into fine carrier and solvent, is polyacrylic acid into fine carrier, solvent is water；The sintering under flowing atmosphere, is incubated 30~120min at 90 DEG C~120 DEG C, 260 DEG C~300 DEG C is 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 using temperature programmed control zonal cooling sintering；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 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
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 not good.
Prepared by current polytetrafluoroethylporous porous membrane uses bidirectional extending method more.This method will expect higher porosity
Film when, it is necessary to film carry out vast scale stretching, it is impossible to Surface Structures are 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.The shape for being often difficult to control to film is stretched 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 the important method for preparing polytetrafluoroethylene fibre, the patent 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, 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 obtains the polytetrafluoroethylene fibre pad precursor 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, controls sintering condition to obtain fiber shape by the method precision of temperature programmed control
State remains intact and has the superfine fibre reticular membrane of beading structure, special construction and the superfine fibre one of this nanoscale
Hydrophobic surface of the road formation with multistage coarse structure.Thus with 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, sinter, it is characterised in that：Into fibre load
Body is configured to after solution add ptfe emulsion with solvent, is polyacrylic acid into fine carrier, solvent is water；The sintering is adopted
Sintered with temperature programmed control zonal cooling, under 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.Pass through control
The post processing sintering condition containing the polytetrafluoroethylene (PTFE) precursor film into fine carrier is made, under stress, under carrier protective effect,
Polytetrafluoroethylgranule granule starts reorientation arrangement, is then decomposed in appropriate opportunity carrier, and polytetrafluoroethylgranule granule further takes
To rearrangement, catenate superfine fibre network structure is formed.Tool can be made by carrying out preparation using described programme-control condition
There is the super-hydrophobic polytetrafluoroethylfiber fiber film of special construction.If not under the conditions of the programme-control of the present invention, such as
CN101994161A is set forth at 280-350 DEG C and sintered 30-90 minutes, then can not obtain with multilevel roughness, water contact
The super-hydrophobic polytetrafluoroethylfiber fiber film that more than 150 ° of angle, and film is without flexibility.If not using programme-control (such as in addition
CN102282301A obtains polytetrafluoroethylene fibre pad in sintering at 400 DEG C, and the ash content of carrier (fibre-forming polymer) is less than 5%.)
Original form of fiber can not be then kept, causes fiber to collapse to flat.
Preferably, above-mentioned sintering using temperature programmed control zonal cooling sinter, flowing atmosphere under, 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 is wrapped on branch hold mode, big by winding layer numerical control polytetrafluoroethylene (PTFE) film thickness and average pore size
It is small.The winding of fiber is superimposed with the stress orientation beneficial to sintering process.
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；It is the uniform molten of 0.5%~30% mass concentration that polyacrylic acid, which is dissolved in water to be made into concentration,
Liquid, then stirring adds ptfe emulsion, obtains uniform mixed liquor；Polyacrylic acid is with polytetrafluoroethylene (PTFE) dry weight ratio 1:
1~50；
(2) make 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
Cross winding layer numerical control film thick；
(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 using temperature programmed control zonal cooling sintering, in 90 DEG C~120 DEG C insulations
30~120min, 260 DEG C~300 DEG C are warming up to 3~10 DEG C/min speed from 90 DEG C~120 DEG C, 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, with being 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
Have between beading superfine fibre reticular membrane, fiber and to be changed into inter-adhesive from unordered stacking, fibre morphology is homogeneous, surface is complete
Getting well, intensity and toughness also improve a lot, and can bear certain vacuum pressure (can still stablize under 0.7kPa vacuums and grasp
Make).
3. the polytetrafluoroethylporous porous membrane obtained by the present invention, with special super-hydrophobicity structure, obtained PTFE fiber
Surface forms a large amount of rough surfaces, and surface water contact angle >=150 °, porosity is up to more than 80%.
4th, the polytetrafluoroethylporous porous membrane obtained by the present invention is without support, and thickness is controllable, applied to membrane distillation process, leads to
Amount >=26L/m2H, rejection is more than 99%.
5th, the winding process progress of the invention proposed before sintering is preforming, and shape and thickness to final products film can
It is controlled, there is provided the thickness needed for film and intensity while high porosity (more than 80%) is ensured.In contrast to obtain
High porosity and poly tetrafluoroethylene obtained by the stretch processes stretched at high proportion, the inventive method are without support, shape
Formula is various, and thickness is controllable.
6th, the polytetrafluoroethylene (PTFE) super-hydrophobic film preparation method that the present invention is provided, 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 for planting nanoscale forms the hydrophobic surface with multistage coarse structure together with superfine fibre.Thus with super thin
Aqueous energy.
7th, present invention, avoiding the use of lubricant in biaxial tension etc., in the absence of the removing problem of lubricant, technique letter
Single, without extrusion, the Complicated Flow such as press mold pollutes small.
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 connection, 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 uniform, 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 are warming up to 290 DEG C from 110 DEG C, 290 DEG C are incubated 100min 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, is 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 of average pore size, tensile strength 490psi, 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 are warming up to 260 DEG C, 260 DEG C of insulation 120min, from 260 DEG C from 90 DEG C with 10 DEG C/min programming rates
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 of average pore size, tensile strength 460psi, 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 are warming up to 275 DEG C, 275 DEG C of insulation 110min, from 275 from 100 DEG C with 10 DEG C/min programming rates
380 DEG C 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 of average pore size, tensile strength 477psi, 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 are warming up to 280 DEG C, 280 DEG C of insulation 120min, from 280 from 100 DEG C with 8 DEG C/min programming rates
385 DEG C 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 of average pore size, tensile strength 470psi, 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 uniform, 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 are warming up to 295 DEG C from 120 DEG C, 295 DEG C are incubated 120min 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, is 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 are warming up to 300 DEG C, 300 DEG C of insulation 60min, from 300 from 115 DEG C with 5 DEG C/min programming rates
390 DEG C 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 of average pore size, tensile strength 478psi,
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 are warming up to 285 DEG C, 285 DEG C of insulation 70min, from 285 from 110 DEG C with 6 DEG C/min programming rates
380 DEG C 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
Spend the hollow-fibre membrane for 203um.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 (6)
1. a kind of preparation method of poly tetrafluoroethylene, including spinning solution is with liquid, system is fine, sinter, it is characterised in that：Into fine carrier
It is configured to after solution add ptfe emulsion with solvent, is polyacrylic acid into fine carrier, solvent is water；The sintering is used
Temperature programmed control zonal cooling is sintered, and under 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.
2. the preparation method of the poly tetrafluoroethylene as described in claim 1, the sintering is burnt using temperature programmed control zonal cooling
Knot, flowing atmosphere under, 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, 280 DEG C~300 DEG C are warming up to 5~8 DEG C/min speed from 100 DEG C~120 DEG C, 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 the poly tetrafluoroethylene as described in claim 1, includes preforming step before being sintered after the system is fine
Suddenly, it is described it is preforming be that polytetrafluoroethylene (PTFE) precursor film is wrapped on branch hold mode.
4. the preparation method of the poly tetrafluoroethylene as described in claim 1,2 or 3, 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.
5. the preparation method of the poly tetrafluoroethylene as described 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（1）The spinning solution progress spinning of middle preparation prepares fiber and obtained before polytetrafluoroethylene (PTFE)
Drive 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 and continuously leading to together with branch hold mode
Become a mandarin to take offence and be sintered under conditions of atmosphere；Sintering is incubated 30 using temperature programmed control zonal cooling sintering at 90 DEG C~120 DEG C
~120min, 260 DEG C~300 DEG C are warming up to 3~10 DEG C/min speed from 90 DEG C~120 DEG C, in 260 DEG C~300 DEG C guarantors
30~120min of temperature；370 DEG C~390 DEG C are warming up to from 260 DEG C~300 DEG C with 2~8 DEG C/min speed, 370 DEG C~390
DEG C insulation 5~120min.
6. the preparation method of the poly tetrafluoroethylene as described in claim 1,2,3 or 5, the flowing atmosphere is air, nitrogen
At least one of or inert gas.
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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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| JP7290209B2 (en) * | 2018-10-24 | 2023-06-13 | 住友電工ファインポリマー株式会社 | Hollow fiber membrane and hollow fiber membrane module |
| 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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| 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 |
| 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 |
| 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 |
| 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 |
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