CN104998556B - A kind of preparation method of super-hydrophobic polytetrafluoroethylfiber fiber film - Google Patents
A kind of preparation method of super-hydrophobic polytetrafluoroethylfiber fiber film Download PDFInfo
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- CN104998556B CN104998556B CN201410161928.8A CN201410161928A CN104998556B CN 104998556 B CN104998556 B CN 104998556B CN 201410161928 A CN201410161928 A CN 201410161928A CN 104998556 B CN104998556 B CN 104998556B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000835 fiber Substances 0.000 title claims description 35
- 230000003075 superhydrophobic effect Effects 0.000 title description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 91
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims abstract description 79
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 79
- -1 poly tetrafluoroethylene Polymers 0.000 claims abstract description 51
- 238000001816 cooling Methods 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 29
- 238000010792 warming Methods 0.000 claims abstract description 26
- 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
- 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
- 239000002243 precursor Substances 0.000 claims description 20
- 238000009413 insulation Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 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
- 238000000034 method Methods 0.000 description 32
- 239000012528 membrane Substances 0.000 description 24
- 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 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
- 239000008187 granular material Substances 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
- 239000002245 particle 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
- 208000013201 Stress fracture Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 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
- 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Landscapes
- 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；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；Cooling treatment 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.
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 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, 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 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；Sintering uses journey
Sequence temperature 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 speed
Rate 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's
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；Cooling after sintering
Processing, 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,
30~120min is incubated at 150~200 DEG C, then natural cooling.
By controlling the post processing sintering condition containing the polytetrafluoroethylene (PTFE) precursor film into fine carrier, under stress,
Under carrier protective effect, polytetrafluoroethylgranule granule starts reorientation arrangement, is then decomposed in appropriate opportunity carrier, polytetrafluoroethyl-ne
Alkene particle is further orientated rearrangement, forms catenate superfine fibre network structure.Carried out using described programme-control condition
The super-hydrophobic polytetrafluoroethylfiber fiber film with special construction can be made in preparation.If not in the programme-control condition of the present invention
Under, 30-90 minutes are sintered as CN101994161A is set forth at 280-350 DEG C, then can not obtain with multilevel roughness, water
The super-hydrophobic polytetrafluoroethylfiber fiber film that more than 150 ° of contact angle, and film is without flexibility.If programme-control is not used (such as in addition
CN102282301A is sintered at 400 DEG C and is obtained polytetrafluoroethylene fibre pad, 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.By controlling the cooling condition after sintering, further
Reduce the micro-fractures on fiber, form seamless fiber surface, the intensity and toughness of reinforcing fiber.
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 is incubated 50~100min to 90 DEG C~120 DEG C, at 100 DEG C~120 DEG C, 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 are warming up to 380 DEG C~390 DEG C, and 30~80min is incubated at 380 DEG C~390 DEG C.
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：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, with 3~10 DEG C/min speed
Rate is incubated 30~120min from room temperature 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) cool down：In the case where flowing atmosphere, 150~200 are cooled to from 360 DEG C~400 DEG C with 3~15 DEG C/min speed
DEG C, 30~120min is incubated at 150~200 DEG C, then natural cooling.
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 and surface are intact,
Intensity and toughness also improve a lot, and can bear certain vacuum pressure (can under 0.8kPa vacuums still stably operable).
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
Measure ＞ 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, 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 12% 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.
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 221 μm, cutting off can
Obtain flat porous membrane.175 ° of the film hydrophobic contact angle, porosity 87%, 0.35 μm of average pore size, tensile strength
580psi, elongation 382%, when being operated for membrane distillation, flux 43L/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 9% 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.
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 198um, cutting off can
Obtain flat porous membrane.163 ° of the film hydrophobic contact angle, porosity 82%, 0.45 μm of average pore size, tensile strength
480psi, elongation 330%, when being operated for membrane distillation, flux 26L/m2H, rejection 99.5%.
Embodiment 3
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, 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.
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 200um, cutting off can
Obtain flat porous membrane.166 ° of the film hydrophobic contact angle, porosity 84%, 0.25 μm of average pore size, tensile strength
489psi, elongation 340%, when being operated for membrane distillation, flux 30L/m2H, rejection 99.5%.
Embodiment 4
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 7% 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.
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 188um, cut off
It can obtain flat porous membrane.169 ° of the film hydrophobic contact angle, porosity 84%, 0.45 μm of average pore size, tensile strength
495psi, elongation 340%, when being operated for membrane distillation, flux 32L/m2H, rejection 99.2%.
Embodiment 5
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 13% 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.
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 195um.The film hydrophobic contact angle
170 °, porosity 84%, 0.5 μm, tensile strength 510psi of average pore size, elongation 345%, 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 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 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.
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 172um.The film hydrophobic contact angle
175 °, porosity 89%, 0.35 μm, tensile strength 565psi of average pore size, elongation 355%, grasped for tubular membrane membrane distillation
When making, flux 37L/m2H, rejection 99.6%.
Embodiment 7
The ptfe emulsion of solid content 60% is added drop-wise in the polyacrylic acid aqueous solution that mass fraction is 4% 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.
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 210um.The film hydrophobic contact angle
175 °, porosity 85%, 0.4 μm, tensile strength 650psi of average pore size, elongation 365%, for hollow-fibre membrane membrane distillation
During operation, flux 41L/m2H, rejection 99.9%.
Claims (6)
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；Sintering uses program
Temperature 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 speed
260 DEG C~300 DEG C are warming up to from 90 DEG C~120 DEG C, 30~120min is incubated at 260 DEG C~300 DEG C；With 2~8 DEG C/min's
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 cold after sintering
But handle, it is described to be cooled under flowing atmosphere, it is cooled to 150~200 from 360 DEG C~400 DEG C with 3~15 DEG C/min speed
DEG C, 30~120min is incubated at 150~200 DEG C, then natural cooling.
2. the preparation method of the poly tetrafluoroethylene as described in claim 1, the sintering is burnt using temperature programmed control zonal cooling
Knot, in the case where flow atmosphere, with 2~15 DEG C/min from room temperature to 90 DEG C~120 DEG C, 100 DEG C~120 DEG C 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 the poly tetrafluoroethylene as described in claim 1 or 2, include preforming step before being sintered after 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 poly tetrafluoroethylene as claimed in claim 1 or 2, the mass concentration of the polyacrylic acid aqueous solution are
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 spinning process pair（1）The spinning solution progress spinning of middle preparation prepares fiber and obtains polytetrafluoroethylene (PTFE) forerunner
Film；
（3）It is preforming：Will（2）In obtained by the polytetrafluoroethylene (PTFE) precursor film that obtains be wrapped on the branch hold mode of respective shapes, shape
Into 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 is sintered using temperature programmed control zonal cooling, 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 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,
30~120min is incubated at 150~200 DEG C, then natural cooling.
6. the preparation method of the poly tetrafluoroethylene as described in claim 1,2 or 5, the flowing atmosphere be air, nitrogen or
At least one of inert gas.
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| CN105664733B (en) * | 2016-01-21 | 2019-08-02 | 巨化集团技术中心 | A kind of preparation method of perfluor hollow fiber composite membrane |
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| 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 |
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| 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 |
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