CN105013341A - Preparation method of super-hydrophobic polytetrafluoroethylene film - Google Patents
Preparation method of super-hydrophobic polytetrafluoroethylene film Download PDFInfo
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- CN105013341A CN105013341A CN201410161715.5A CN201410161715A CN105013341A CN 105013341 A CN105013341 A CN 105013341A CN 201410161715 A CN201410161715 A CN 201410161715A CN 105013341 A CN105013341 A CN 105013341A
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 95
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 84
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000003075 superhydrophobic effect Effects 0.000 title description 5
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 239000000835 fiber Substances 0.000 claims abstract description 39
- 238000001816 cooling Methods 0.000 claims abstract description 32
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- 238000009987 spinning Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 81
- 238000000034 method Methods 0.000 claims description 34
- 238000009413 insulation Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 9
- 210000002950 fibroblast Anatomy 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003570 air Substances 0.000 claims description 6
- 239000012510 hollow fiber Substances 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 description 24
- 208000027418 Wounds and injury Diseases 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000001523 electrospinning Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 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
- 239000002121 nanofiber Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 208000013201 Stress fracture Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a preparation method of a polytetrafluoroethylene film. The preparation method comprises the steps of preparing a spinning solution, preparing fibers and sintering and is characterized by adding polytetrafluoroethylene emulsion after preparing a solution with a fiber forming carrier and a solvent, wherein the fiber forming carrier is polyvinyl alcohol, and the solvent is water; adopting multistep continuous sintering through program temperature control, and in flowing atmospheres, increasing the temperature from a room temperature to 120-200 DEG C at a rate of 3-10 DEG C/min and insulating at 120-200 DEG C for 30-120 minutes; increasing the temperature from 120-200 DEG C to 360-400 DEG C at a rate of 2-8 DEG C/min and insulating at 360-400 DEG C for 5-120 minutes; carrying out cooling treatment after sintering: in the flowing atmospheres, reducing the temperature from 360-400 DEG C to 150-200 DEG C at a rate of 3-15 DEG C/min, insulating at 150-200 DEG C for 30-120 minutes and then carrying out natural cooling.
Description
Technical field
The present invention relates to a kind of preparation method of the diffusion barrier material for separating of field, be specifically related to a kind of preparation method of hydrophobic membrane material.
Technical background
Hydrophobicity is the critical nature of polytetrafluoroethylene (PTFE) (PTFE) material, is the main performance that polytetrafluoroethylporous porous membrane is applied to membrane material.Although polytetrafluoroethylmaterial material has low-surface-energy, the water contact angle of smooth polytetrafluoroethylene (PTFE) plane is between 98 to 112 °, and hydrophobic performance is not good.
Current polytetrafluoroethylporous porous membrane preparation adopts bidirectional extending method more.When this method will expect the film of higher porosity, need to carry out vast scale stretching to film, cannot control by Surface Structures, and thickness is only below tens microns, backing material is needed in using, and backing material itself often has certain limitation in heat resistance or chemical stability or hydrophobic performance, thus limit the application of this biaxial stretching film.Stretch at high proportion simultaneously and be often difficult to the shape of controlling diaphragm, therefore main based on Flat Membrane.The patents such as Chinese patent CN1775847A, CN102007242A, CN101543734B, CN102151494A all carry out polytetrafluoroethylporous porous membrane preparation based on above stretch processes.
The patents such as support methods prepares the important method of polytetrafluoroethylene fibre, CN101994161A and CN102282301A adopt the preparation of electrostatic spinning technique to polytetrafluoroethylsuperfine superfine fiber to report.All relate to the step of high temperature sintering removing fibroblast carrier in these reports, but these sintering processes only pay close attention to the removal of fibroblast template.Specifically: the object of CN101994161A is a kind of polytetrafluoroethylsuperfine superfine fiber of preparation, its preparation method adopts polyvinyl alcohol to make carrier, to be weaved out polytetrafluoroethylene fibre precursor by electrospinning process, post-processing approach is by polytetrafluoroethylene fibre precursor at 100 ~ 120 DEG C dry 5 ~ 15 minutes, then sinters 30 ~ 90 minutes at 280 ~ 350 DEG C; The object of sintering removes to make polyvinyl alcohol decompose.And CN102282301A improving one's methods of a kind of polytetrafluoroethylene (PTFE) pad is mainly provided, its objective is that the technological parameter (spinning fluid viscosity) in order to improve electrospinning obtains the polytetrafluoroethylene fibre pad precursor of uniform diameter, at 400 DEG C, sintering obtains polytetrafluoroethylene fibre pad again, and the ash content of carrier (fibre-forming polymer) is less than 5%.The patents such as CN101994161A and CN102282301A adopt electrostatic spinning technique to polytetrafluoroethylsuperfine superfine fiber (pad), only consider and how to obtain polytetrafluoroethylsuperfine superfine fiber (pad), have to conventional polytetrafluoroethylsuperfine superfine fiber (pad).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of poly tetrafluoroethylene, by controlling the post processing sintering condition of the polytetrafluoroethylene (PTFE) precursor film containing fibroblast carrier, by the method precise hard_drawn tuhes sintering condition of temperature programmed control and cooling condition to obtain fibre morphology and remain intact and to have the superfine fibre reticular membrane of beading structure, the special construction of this nanoscale forms the hydrophobic surface with multistage coarse structure together with superfine fibre.Thus there is ultra-hydrophobicity.
Object of the present invention is realized by following technical measures:
A preparation method for poly tetrafluoroethylene, comprise spinning solution dosing, system fibre, sintering, it is characterized in that: fibroblast carrier and solvent add ptfe emulsion after being mixed with solution, fibroblast carrier is polyvinyl alcohol, and solvent is water; Sintering adopts temperature programmed control zonal cooling sintering, under flowing atmosphere, with the speed of 3 ~ institute, 0 DEG C/min from room temperature to institute flat 0 DEG C ~ flat 00 DEG C, is incubated a 30 ~ flat 0min flat 0 DEG C of institute ~ flat 00 DEG C; 360 DEG C ~ 400 DEG C are warmed up to from institute flat 0 DEG C ~ flat 00 DEG C, at 360 DEG C ~ 400 DEG C insulation 5 ~ flat 0min with the speed of flat ~ 8 DEG C/min; Carry out cooling processing after sintering, described cooling under flowing atmosphere, with 3 ~ speed of institute 5 DEG C/min is cooled to institute 50 ~ flat 00 DEG C from 360 DEG C ~ 400 DEG C, at institute 50 ~ flat 00 DEG C of insulation 30 ~ flat 0min, then cooling naturally.By controlling the post processing sintering condition of the polytetrafluoroethylene (PTFE) precursor film containing fibroblast carrier; under effect of stress; under carrier protective effect; polytetrafluoroethylgranule granule starts reorientation arrangement; subsequently in appropriate carrier decomposition on opportunity; the further orientation of polytetrafluoroethylgranule granule is reset, and forms catenate superfine fibre network structure.Programme-control condition described in employing is prepared the super-hydrophobic polytetrafluoroethylfiber fiber film that can obtain and have special construction.If not under programme-control condition of the present invention, as CN101994161A be set forth in 280-350 DEG C at sinter 30-90 minute, then cannot obtain have multilevel roughness, the super-hydrophobic polytetrafluoroethylfiber fiber film of water contact angle more than 150 °, and film does not have flexibility.If (obtain polytetrafluoroethylene fibre pad as CN102282301A sinters at 400 DEG C, the ash content of carrier (fibre-forming polymer) is less than 5% not adopt programme-control in addition.) then cannot keep original form of fiber, cause fiber to collapse to flat.By controlling the cooling condition after sintering, further reducing the micro-fractures on fiber, forming seamless fiber surface, the intensity of fortifying fibre and toughness.
The preparation method of above-mentioned poly tetrafluoroethylene, comprise preforming step before sintering after system is fine, described preformed is wrapped on supporting die by polytetrafluoroethylene (PTFE) precursor film, by winding layer numerical control polytetrafluoroethylene (PTFE) film thickness and mean pore size.The winding of fiber is superimposed with the stress orientation being beneficial to sintering process.
The mass concentration of polyvinyl alcohol water solution is 0.5% ~ 30%, and polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight are than being 1:1 ~ 50.
Particularly, a kind of preparation method of poly tetrafluoroethylene, comprises the following steps:
(1) preparation of spinning solution; Be made into water-soluble for polyvinyl alcohol the homogeneous solution that concentration is 0.5% ~ 30% mass concentration, then stir and add ptfe emulsion, obtain uniform mixed liquor; Polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight ratio are in 1:1 ~ 50;
(2) system is fine; Adopt the method for spinning or stretching spinning solution to preparation in (1) to carry out spinning to prepare fiber and obtain polytetrafluoroethylene (PTFE) precursor film;
(3) preformed: according to the use specification of expection, the polytetrafluoroethylene (PTFE) precursor film that obtains obtained in (2) is wrapped on the supporting die of respective shapes, form the film of flat, the difformity such as tubular type, hollow fiber form or rolling and specification, thick by winding layer numerical control masking;
(4) sinter; The preformed polytetrafluoroethylene (PTFE) precursor film obtained in (3) is put into high temperature furnace together with supporting die sinter under the condition passing into flowing atmosphere continuously; Sintering adopts temperature programmed control zonal cooling sintering, with the speed of 3 ~ institute, 0 DEG C/min from room temperature to institute flat 0 DEG C ~ flat 00 DEG C, is incubated a 30 ~ flat 0min flat 0 DEG C of institute ~ flat 00 DEG C; 360 DEG C ~ 400 DEG C are warmed up to from institute flat 0 DEG C ~ flat 00 DEG C, at 360 DEG C ~ 400 DEG C insulation 5 ~ flat 0min with the speed of flat ~ 8 DEG C/min;
(5) cool: under flowing atmosphere, with 3 ~ speed of institute 5 DEG C/min is cooled to institute 50 ~ flat 00 DEG C from 360 DEG C ~ 400 DEG C, at institute 50 ~ flat 00 DEG C of insulation 30 ~ flat 0min, and then cooling naturally.
Above-mentioned flowing atmosphere is nitrogen, air or inert gas at least one.
Beneficial effect
Institute. the present invention has obtained the poly tetrafluoroethylene of structure uniqueness, have by the crisscross hole three-dimensional communication structure formed of beading filament, be the hydrophobic surface that one formation has multistage coarse structure, beading filament refers to that between polytetrafluoroethylgranule granule, the filament of formation is cohered in point and/or face mutually; Hole is hole, labyrinth, and maximum diameter of hole is 1.0 μm, and minimum-value aperture 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. what the present invention was fabulous solves the givey problem of fiber in polytetrafluoroethylene (PTFE) precursor film sintering, and obtain and there is beading superfine fibre reticular membrane, between fiber from unordered stacking become inter-adhesive, fibre morphology and surface intact, intensity and toughness also improve a lot, and can bear certain vacuum pressure (can under 0.7kPa vacuum still stably operable).
3. the polytetrafluoroethylporous porous membrane obtained by the present invention, has special super-hydrophobicity structure, and the PTFE fiber surface obtained forms a large amount of rough surface, surface water contact angle >=150 °, and porosity is up to more than 80%.
4, the polytetrafluoroethylporous porous membrane obtained by the present invention is without the need to supporting, and thickness is controlled, is applied to Membrane Materials process, flux >20L/m
2h, rejection is more than 99%.
5, the present invention proposes the winding process before sintering and carry out preformed, can control the shape of final products film and thickness, while guarantee high porosity (more than 80%), provide the thickness needed for film and intensity.In contrast to the stretch processes stretched at high proportion for obtaining high porosity, the poly tetrafluoroethylene that the inventive method obtains is without the need to supporting, and various informative, thickness is controlled.
6, polytetrafluoroethylene (PTFE) super-hydrophobic film preparation method provided by the invention, adopt sintering condition rate-determining steps, carrier was decomposed on appropriate opportunity, and polytetrafluoroethylgranule granule melting orientation is reset, obtain and have beading superfine fibre reticular membrane, the special construction of this nanoscale forms the hydrophobic surface with multistage coarse structure together with superfine fibre.Thus there is ultra-hydrophobicity.
7, present invention, avoiding the use of lubricant in biaxial tension etc., there is not the removing problem of lubricant, technique is simple, and without the need to extruding, the Complicated Flows such as press mold, pollute little.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the poly tetrafluoroethylene that preparation method of the present invention obtains; Can observe from accompanying drawing: poly tetrafluoroethylene of the present invention has by the crisscross hole three-dimensional communication structure formed of beading filament, and hole is hole, labyrinth, even pore distribution is communicated with, and nanofiber form is homogeneous intact.
Detailed description of the invention
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment can only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 15%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 5cm cylinder supporting die, be wound around 5 layers, and deliver to logical nitrogen in tube furnace, sintering process temperature programmed control, from room temperature to 140 DEG C of programming rates, 7 DEG C/min, 140 DEG C of insulation 80min, be warmed up to 373 DEG C from 140 DEG C, programming rate is 8 DEG C/min, after arriving sintering temperature, i.e. sintering stage temperature 373 DEG C, insulation 100min.
Cooling: under the flowing atmosphere of nitrogen, is cooled to institute 80 DEG C with the speed of 8 DEG C/min from 373 DEG C, at institute 80 DEG C of insulation 80min, then naturally cools.
Extract cylinder supporting die out after taking out after cooling, obtain the cylindric poly tetrafluoroethylene that thickness is 190 μm, cut off and can obtain flat porous membrane.This film hydrophobic contact angle 173 °, porosity 87%, average pore size 0.5 μm, hot strength 490psi, percentage elongation 370%, when operating for Membrane Materials, flux 26L/m
2h, rejection 99.4%.
Embodiment 2
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 8%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 5cm cylinder supporting die, be wound around 5 layers, and deliver to blowing air in tube furnace, sintering process temperature programmed control, from room temperature to 150 DEG C of programming rates, 6 DEG C/min, 70min is incubated at 150 DEG C, be warmed up to 390 DEG C from 150 DEG C, programming rate is 6 DEG C/min, after arriving sintering temperature, i.e. sintering stage temperature 392 DEG C, insulation 10min.
Cooling: under the flowing atmosphere of air, with institute 5 DEG C/min speed be cooled to flat 00 DEG C from 390 DEG C, flat 00 DEG C insulation 30min, then naturally cooling.
Extract cylinder supporting die out after taking out after cooling, obtain the cylindric poly tetrafluoroethylene that thickness is 211um, cut off and can obtain flat porous membrane.This film hydrophobic contact angle 169 °, porosity 84%, average pore size 0.42 μm, hot strength 446psi, percentage elongation 304%, when operating for Membrane Materials, flux 22L/m
2h, rejection 99.6%.
Embodiment 3
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 6%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 5cm cylinder supporting die, be wound around 5 layers, and deliver to logical nitrogen in tube furnace, sintering process temperature programmed control, from room temperature to 180 DEG C of programming rates, 4 DEG C/min, 180 DEG C of insulation 40min, be warmed up to 376 DEG C from 180 DEG C, programming rate is 3 DEG C/min, after arriving sintering temperature, i.e. sintering stage temperature 376 DEG C, insulation 80min.
Cooling: under the flowing atmosphere of nitrogen, is cooled to institute 90 DEG C with the speed of 5 DEG C/min from 376 DEG C, at institute 90 DEG C of insulation 40min, then naturally cools.
Extract cylinder supporting die out after taking out after cooling, obtain the cylindric poly tetrafluoroethylene that thickness is 199um, cut off and can obtain flat porous membrane.This film hydrophobic contact angle 163 °, porosity 83%, average pore size 0.25 μm, hot strength 478psi, percentage elongation 315%, when operating for Membrane Materials, flux 25L/m
2h, rejection 99.5%.
Embodiment 4
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 5%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 5cm cylinder supporting die, be wound around 6 layers, and deliver to logical argon gas in tube furnace, sintering process temperature programmed control, from room temperature to 120 DEG C of programming rates, 10 DEG C/min, 120 DEG C of insulation 120min, be warmed up to 388 DEG C from 120 DEG C, programming rate is 4 DEG C/min, after arriving sintering temperature, i.e. sintering stage temperature 388 DEG C, insulation 26min.
Cooling: under the flowing atmosphere of argon gas, with institute 5 DEG C/min speed from 388 DEG C be cooled to institute 50 DEG C, institute 50 DEG C insulation flat 0min, then naturally cooling.
Extract cylinder supporting die out after taking out after cooling, obtain thickness be 206um cylindric poly tetrafluoroethylene, cut off and can obtain flat porous membrane.This film hydrophobic contact angle 157 °, porosity 86%, average pore size 0.48 μm, hot strength 474psi, percentage elongation 322%, when operating for Membrane Materials, flux 29L/m
2h, rejection 99.2%.
Embodiment 5
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 10%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 0.5cm cylinder supporting die, be wound around 5 layers, and deliver to logical nitrogen in Muffle furnace, sintering process temperature programmed control, from room temperature to 130 DEG C of programming rates, 8 DEG C/min, 130 DEG C of insulation 100min, be warmed up to 385 DEG C from 130 DEG C, programming rate is 7 DEG C/min, after arriving sintering temperature, i.e. sintering stage temperature 385 DEG C, insulation 35min.
Cooling: under the flowing atmosphere of nitrogen, with institute flat DEG C/min speed from 385 DEG C be cooled to institute 60 DEG C, institute 60 DEG C insulation institute 00min, then naturally cooling.
Extract cylinder supporting die out after taking out after cooling, obtain the tubular membrane that thickness is 178um.This film hydrophobic contact angle 171 °, porosity 85%, average pore size 0.15 μm, hot strength 455psi, percentage elongation 329%, when operating for tubular membrane Membrane Materials, flux 34L/m
2h, rejection 99.6%.
Embodiment 6
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 6%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 0.5cm cylinder supporting die, be wound around 5 layers, and deliver to logical argon gas in tube furnace, sintering process temperature programmed control, from room temperature to 160 DEG C of programming rates, 5 DEG C/min, 160 DEG C of insulation 100min, be warmed up to 380 DEG C from 160 DEG C, programming rate is 5 DEG C/min, after arriving sintering temperature, i.e. sintering stage temperature 380 DEG C, insulation 60min.
Cooling: under the flowing atmosphere of argon gas, with institute 0 DEG C/min speed from 380 DEG C be cooled to institute 70 DEG C, institute 70 DEG C insulation 90min, then naturally cooling.
Extract cylinder supporting die out after taking out after cooling, obtain the tubular membrane that thickness is 190um.This film hydrophobic contact angle 164 °, porosity 84%, average pore size 0.35 μm, hot strength 468psi, percentage elongation 325%, when operating for tubular membrane Membrane Materials, flux 38L/m
2h, rejection 99.6%.
Embodiment 7
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 3%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 0.1cm cylinder supporting die, be wound around 6 layers, and deliver to blowing air in tube furnace, sintering process temperature programmed control, from room temperature to 200 DEG C of programming rates, 3 DEG C/min, 200 DEG C of insulation 30min, be warmed up to 385 DEG C from 200 DEG C, programming rate is 2 DEG C/min, after arriving sintering temperature, namely at sintering stage temperature 370 DEG C, insulation 120min.
Cooling: under the flowing atmosphere of air, is cooled to institute 85 DEG C with the speed of 9 DEG C/min from 370 DEG C, at institute 85 DEG C of insulation 70min, then naturally cools.
Extract cylinder supporting die out after taking out after cooling, obtain the hollow-fibre membrane that thickness is 188um.This film hydrophobic contact angle 175 °, porosity 84%, average pore size 0.45 μm, hot strength 460psi, percentage elongation 358%, during for hollow-fibre membrane distillation procedure, flux 40L/m
2h, rejection 99.9%.
Claims (5)
1. a preparation method for poly tetrafluoroethylene, comprise spinning solution dosing, system fibre, sintering, it is characterized in that: fibroblast carrier and solvent add ptfe emulsion after being mixed with solution, fibroblast carrier is polyvinyl alcohol, and solvent is water; Sintering adopts temperature programmed control zonal cooling sintering, under flowing atmosphere, with the speed of 3 ~ 10 DEG C/min from room temperature to 120 DEG C ~ 200 DEG C, at 120 DEG C ~ 200 DEG C insulation 30 ~ 120min; 360 DEG C ~ 400 DEG C are warmed up to from 120 DEG C ~ 200 DEG C, at 360 DEG C ~ 400 DEG C insulation 5 ~ 120min with the speed of 2 ~ 8 DEG C/min; Carry out cooling processing after sintering, described cooling, under flowing atmosphere, is cooled to 150 ~ 200 DEG C with the speed of 3 ~ 15 DEG C/min from 360 DEG C ~ 400 DEG C, at 150 ~ 200 DEG C of insulation 30 ~ 120min, then naturally cools.
2. the preparation method of poly tetrafluoroethylene as claimed in claim 1, comprise preforming step before sintering after system is fine, described preformed is wrapped on supporting die by polytetrafluoroethylene (PTFE) precursor film.
3. the preparation method of poly tetrafluoroethylene as claimed in claim 1 or 2, the mass concentration of described polyvinyl alcohol water solution is 0.5% ~ 30%, and polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight are than being 1:1 ~ 50.
4. the preparation method of poly tetrafluoroethylene as claimed in claim 1, comprises the following steps:
(1) preparation of spinning solution: be made into the homogeneous solution that concentration is 0.5% ~ 30% mass concentration by water-soluble for polyvinyl alcohol, then stirs and adds ptfe emulsion, obtain uniform mixed liquor; Polyvinyl alcohol and polytetrafluoroethylene (PTFE) dry weight ratio are in 1:1 ~ 50;
(2) system is fine: adopt the method for spinning or stretching spinning solution to preparation in (1) to carry out spinning and prepare fiber and obtain polytetrafluoroethylene (PTFE) precursor film;
(3) preformed: according to the use specification of expection, be wrapped on the supporting die of respective shapes by the polytetrafluoroethylene (PTFE) precursor film that obtains obtained in (2), forms flat, tubular type, hollow fiber form or rolling shape;
(4) sinter: the preformed polytetrafluoroethylene (PTFE) precursor film obtained in (3) is put into high temperature furnace together with supporting die and sinters under the condition passing into flowing atmosphere continuously; Sintering adopts temperature programmed control zonal cooling sintering, with the speed of 3 ~ 10 DEG C/min from room temperature to 120 DEG C ~ 200 DEG C, at 120 DEG C ~ 200 DEG C insulation 30 ~ 120min; 360 DEG C ~ 400 DEG C are warmed up to from 120 DEG C ~ 200 DEG C, at 360 DEG C ~ 400 DEG C insulation 5 ~ 120min with the speed of 2 ~ 8 DEG C/min;
(5) cool: under flowing atmosphere, be cooled to 150 ~ 200 DEG C with the speed of 3 ~ 15 DEG C/min from 360 DEG C ~ 400 DEG C, at 150 ~ 200 DEG C of insulation 30 ~ 120min, then naturally cool.
5. the preparation method of the poly tetrafluoroethylene as described in claim 1,2,3 or 4, described flowing atmosphere is nitrogen, air or inert gas at least one.
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| CN201410161715.5A CN105013341B (en) | 2014-04-22 | 2014-04-22 | A kind of preparation method of polytetrafluoroethylene (PTFE) super-hydrophobic film |
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| CN201410161715.5A CN105013341B (en) | 2014-04-22 | 2014-04-22 | A kind of preparation method of polytetrafluoroethylene (PTFE) super-hydrophobic film |
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| CN105013341B CN105013341B (en) | 2018-02-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669451A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine fiber membrane |
| WO2017080478A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN102389720A (en) * | 2011-09-29 | 2012-03-28 | 浙江开创环保科技有限公司 | Polytetrafluoroethylene membrane with supporting materials and preparation method thereof |
| 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 |
| CN103272497A (en) * | 2013-04-22 | 2013-09-04 | 浙江国泰密封材料股份有限公司 | Preparation method for multifunctional PTFE composite film |
-
2014
- 2014-04-22 CN CN201410161715.5A patent/CN105013341B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN102389720A (en) * | 2011-09-29 | 2012-03-28 | 浙江开创环保科技有限公司 | Polytetrafluoroethylene membrane with supporting materials and preparation method thereof |
| 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 |
| CN103272497A (en) * | 2013-04-22 | 2013-09-04 | 浙江国泰密封材料股份有限公司 | Preparation method for multifunctional PTFE composite film |
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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669451A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine fiber membrane |
| WO2017080474A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultra-fine fiber membrane |
| WO2017080478A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber membrane |
| CN106669451B (en) * | 2015-11-11 | 2022-02-08 | 重庆润泽医药有限公司 | Polytetrafluoroethylene superfine fiber membrane |
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