CN109395606A - A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof - Google Patents
A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof Download PDFInfo
- Publication number
- CN109395606A CN109395606A CN201710712504.XA CN201710712504A CN109395606A CN 109395606 A CN109395606 A CN 109395606A CN 201710712504 A CN201710712504 A CN 201710712504A CN 109395606 A CN109395606 A CN 109395606A
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- Prior art keywords
- stem
- transforaminal
- ptfe
- polytetrafluoroethylene
- hole
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- 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
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
-
- 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
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- 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
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- 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)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of polytetrafluoroethylene (PTFE) rolled films, have the pore structure of three-dimensional perforation, there is transforaminal on the stem of hole, and hole aperture is 800 ± 200nm, and stem diameter is 500 ± 100nm, 175 ± 25nm of transforaminal aperture；The porosity of hole is 60 ± 10%, and the porosity of transforaminal is 55 ± 10%；The total surface area of the stem, stem area: transforaminal area=1-15:1.The polytetrafluoroethylene (PTFE) rolled film that the present invention provides a kind of service phases is long, separating effect is excellent.
Description
Technical field
The present invention relates to polytetrafluoroethylene (PTFE) rolled films and preparation method thereof to be particularly suitable for membrane distillation for separating.
Technical background
Polytetrafluoroethylene (PTFE) since its use temperature range is wide, while have excellent chemical stability, low frictional properties and absolutely
Edge thermal insulation not only has excellent chemical stability, thermal stability, electricity using the separation membrane material that polytetrafluoroethylene (PTFE) is prepared as raw material
Insulating properties also has the characteristics such as outstanding waterproof, radix saposhnikoviae, moisture-inhibiting, ventilative and charge stable storing.It is in manufacture protective garment, bag
Formula deduster, architectural lighting etc. have shown excellent performance.National Palaestra " Bird Nest ", dome in thousand of Britain etc.
A large amount of PTFE microporous barriers are used.However that there are still flux in the application is small, filtering essence for current microporous teflon membran
The disadvantages of low, fenestra is easy to pollute, at high cost is spent, the application of industrialized production is had not been achievable.
Inventor has been devoted to the research to the structure of high molecular material, and the control and modification to material structure can get
The high molecular material of different characteristics and function.However polytetrafluoroethylene film relation be- tween structure and properties are not made clear of at present
It is thorough, as separation accuracy is difficult to take into account with treatment effeciency；With accurate microstructure, it is easy to impaired, service phase is short, use cost
It is high；Polytetrafluoroethylene (PTFE) physical and chemical performance is stablized, and structure control, performance improvement realize difficulty is big, and difficulty of processing is big etc.；Polytetrafluoroethyl-ne
Alkene material is in separation in application, how to cooperate with matching to obtain better performance etc. between microstructure and macroscopic form.
Summary of the invention
The polytetrafluoroethylene (PTFE) rolled film that the purpose of the present invention is to provide a kind of service phases is long, separating effect is excellent.
The purpose of the present invention is what is realized by following measures:
A kind of polytetrafluoroethylene (PTFE) rolled film has the pore structure of three-dimensional perforation, there is transforaminal, hole aperture on the stem of hole
For 800 ± 200nm, stem diameter is 500 ± 100nm, 175 ± 25nm of transforaminal aperture；The porosity of hole is 60 ± 10%, transforaminal
Porosity be 55 ± 10%；The total surface area of the stem, stem area: transforaminal area=1-15:1.
The film is during the Selective Separation for substance, when one such or different kinds of molecules is passing through material table
When face and/or inside, the microstructure of molecule will receive itself and the effect of material and the influence of bond structure, to affect object
The percent of pass and throughput of matter, the microstructure of another aspect material also will receive influence, to influence material separation tower, clothes
Labour phase etc..So both ensure that separate substance by efficiency and throughput, combine the utilization rate of material.Transforaminal is on stem
Distribution situation be one of key factor.
Preferably, in order to further increase correlated performance, the polytetrafluoroethylene (PTFE) rolled film, hole aperture is 750-
900nm, stem diameter 500-600nm, transforaminal aperture 155-185nm；Wherein the porosity of hole is 55-70%, the hole of transforaminal
Rate is 50-60%；The total surface area of the stem, stem area: transforaminal area=3-6:1.
Above-mentioned polytetrafluoroethylene (PTFE) rolled film, 100-200 μm of film thickness.
A kind of wound membrane element, including blade, blade are made of two above-mentioned polytetrafluoroethylene (PTFE) rolled films, production network of rivers lattice,
The production network of rivers case is between two films；Setting water inlet grid between blade.Producing network of rivers lattice can be polyester textile, net of intaking
Lattice are plastic wire.Blade one end is glued to get up to form a bag, the other end (polyester textile stretched) and central tube with holes
(generally PVC material) bonding.Have between blade into water grid, they are in wound configuration on central tube together.Produce water
As product water collection channel, grid of intaking is used as grid to aquaporin, while reinforcing giving aquaporin flow turbulence.Multiple membrane elements
Part connects, and in columnar pressure vessel, that is, constitutes rolled membrane module.
Preferably, above-mentioned wound membrane element, diameter 80-250mm.
Polytetrafluoroethylene (PTFE) has stable inert physical and chemical performance, and processing is not easy, especially for its microstructure
Control and holding are even more industry problem.The present invention provides the preparation method of the polytetrafluoroethylene (PTFE) rolled film of above-mentioned special construction,
Using method of electrostatic spinning, including the preparation of spinning lotion, spinning, preforming, sintering, temperature-control pressure-control continuous sintering in the sintering；
It is described it is preforming be that the precursor film for obtaining spinning is wrapped on cylinder branch hold mode.
The present invention provides the preparation method with the PTFE high molecular material of above structure, comprising the following steps:
(1) spinning solution prepares: the gelatin homogeneous solution soluble in water for obtaining 14-15% concentration, and polytetrafluoroethylene (PTFE) cream is added
Liquid (55-60%), so that PTFE and gelatin mass ratio are 2-3:1；
(2) spinning: electrostatic spinning is carried out using high-voltage electrostatic spinning apparatus, obtains even fiber precursor film；Spinning voltage
15 ~ 20kV, 12 ~ 30cm of distance；
(3) preforming: the precursor film that spinning is obtained is wrapped on cylinder branch hold mode；Winding circle number can control film thickness；
(4) be sintered: 1. under a high vacuum (3-5Pa) with 5-6 DEG C/min from room temperature to 98-103 DEG C, and keep temperature and
Pressure 25-30min；2. being filled with nitrogen in 60-150s to pressure 65-70kpa, while temperature value is warming up to 4-5 DEG C/min
375-380 DEG C, and 10-12min is kept at 65-70kpa, 375-380 DEG C；3. making vacuum in 5-10min extremely after heating
50-100Pa is kept to cooling.
Above-mentioned spinning lotion is prepared as preparing high molecular polymerization composition granule, the high molecular polymer using emulsion polymerization
Grain average grain diameter is 15-80nm.This makes material have better stem, pore size, optimizes the property such as impact flexibility, ageing resistance
Energy.
Membrane component, membrane module routinely assemble the components such as film, water inlet grid, production network of rivers lattice, central tube.
Porosity=hole porosity of material+(porosity of 1- hole) * transforaminal porosity.
Beneficial effect
1. the present invention improves the treating capacity that material carries out substance selection by the improvement to polytetrafluoroethylene (PTFE) semi-permeable material structure
With the persistence of separation, selection performance, the efficiency of selection and selection effect of material are preferable, and the service phase of material is long.
2. the super-hydrophobic polytetrafluoroethylfiber fiber film that the present invention is coupled hardness with softness has stable and firm fibre morphology
With transforaminal structure, collapsing for bone skeleton is prevented.
3. present invention filling density is big, easy to use.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment can only be used
In invention is further explained, it should not be understood 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 aforementioned present invention.
Embodiment 1
A kind of polytetrafluoroethylene (PTFE) rolled film has the pore structure of three-dimensional perforation, there is transforaminal, hole aperture on the stem of hole
For 800 ± 200nm, stem diameter is 500 ± 100nm, 175 ± 25nm of transforaminal aperture；The porosity of hole is 60 ± 10%, transforaminal
Porosity be 55 ± 10%；The total surface area of the stem, stem area: transforaminal area=1-15:1.100-200 μm of film thickness.Diameter
For 80-250mm.
Stem surface area graphical analysis: with scanning electron microscope (SEM photograph amplifies 10000-50000 times) shooting material
Photo.The photo (the TV image processor TVIP- of Japanese Avionics company production is scanned with image processing facility
The TV image processor that 4100II, Latock system engineering company provide) stem and transforaminal are separated to obtain stem and transforaminal figure
As handling image by software, obtaining respective area, stem area and transforaminal area-graph can be calculated as the ratio between gross area.
Aperture, stem diameter, porosity are detected using nanometer CT.
The preparation method of this polytetrafluoroethylene (PTFE) rolled film, according to the following steps:
(1) spinning solution prepares: the gelatin homogeneous solution soluble in water for obtaining 14-15% concentration, and polytetrafluoroethylene (PTFE) cream is added
Liquid (55-60%), so that PTFE and gelatin mass ratio are 2-3:1；
(2) spinning: electrostatic spinning is carried out using high-voltage electrostatic spinning apparatus, obtains even fiber precursor film；Spinning voltage
15 ~ 20kV, 12 ~ 30cm of distance；
(3) preforming: the precursor film that spinning is obtained is wrapped on cylinder branch hold mode；
(4) be sintered: 1. under a high vacuum (3-5Pa) with 5-6 DEG C/min from room temperature to 98-103 DEG C, and keep temperature and
Pressure 25-30min；2. being filled with nitrogen in 60-150s to pressure 65-70kpa, while temperature value is warming up to 4-5 DEG C/min
375-380 DEG C, and 10-12min is kept at 65-70kpa, 375-380 DEG C；3. making vacuum in 5-10min extremely after heating
50-100Pa is kept to cooling.
(5) components such as film, water inlet grid, production network of rivers lattice, central tube are assembled.
154-175 ° of resulting materials hydrophobic angle.Gained PTFE material is subjected to membrane distillation: for the processing of lemon juice, being had
It is adapted to industrial excellent properties and effect.Can not damage nutriment (such as vitamin C, total acid, TSS) obtain it is highly concentrated
Contracting fruit juice.Flux of membrane distillation > 20L/m2H, rejection are stablized 99.5% or more, are carried out continuously membrane distillation 3-5 months, flux
Former flux 68-75% is dropped to, material color is pure white after cleaning, and before 95% or more, service phase is flux recovery
3-5.
Embodiment 2
A kind of polytetrafluoroethylene (PTFE) rolled film has the pore structure of three-dimensional perforation, there is transforaminal, hole aperture on the stem of hole
For 750-900nm, stem diameter 500-600nm, transforaminal aperture 155-185nm；Wherein the porosity of hole is 55-70%, transforaminal
Porosity be 50-60%；The total surface area of the stem, stem area: transforaminal area=3-6:1.100-200 μm of film thickness.Diameter is
80-250mm。
155-175 ° of resulting materials hydrophobic angle.Gained PTFE material is subjected to membrane distillation: for the processing of lemon juice, being had
It is adapted to industrial excellent properties and effect.Can not damage nutriment (such as vitamin C, total acid, TSS) obtain it is highly concentrated
Contracting fruit juice.Flux of membrane distillation > 20L/m2H, rejection are stablized 99.5% or more, are carried out continuously membrane distillation 3-5 months, flux
Former flux 68-75% is dropped to, material color is pure white after cleaning, and before 95% or more, service phase is flux recovery
3-5.
Embodiment 3
A kind of polytetrafluoroethylene (PTFE) rolled film has the pore structure of three-dimensional perforation, there is transforaminal, hole aperture on the stem of hole
For 880nm, stem diameter 550nm, transforaminal aperture 160nm；Wherein the porosity of hole is 58%, and the porosity of transforaminal is 58%；
The total surface area of the stem, stem area: transforaminal area=5:1.150 μm of film thickness.Film diameter is 120mm.
160 ° of resulting materials hydrophobic angle.Gained PTFE material is subjected to membrane distillation: for the processing of lemon juice, there is adaptation
In industrial excellent properties and effect.Nutriment (such as vitamin C, total acid, TSS) can not be damaged and obtain highly enriched fruit
Juice.Flux of membrane distillation > 20L/m2H, rejection are stablized 99.5% or more, are carried out continuously membrane distillation 3-5 months, flux decline
To former flux 68-75%, material color is pure white after cleaning, and for flux recovery before 95% or more, service phase is 3-5
Year.
Claims (6)
1. a kind of polytetrafluoroethylene (PTFE) rolled film has the pore structure of three-dimensional perforation, there is transforaminal, hole lyriform pore on the stem of hole
Diameter is 800 ± 200nm, and stem diameter is 500 ± 100nm, 175 ± 25nm of transforaminal aperture；The porosity of hole is 60 ± 10%, stem
The porosity in hole is 55 ± 10%；The total surface area of the stem, stem area: transforaminal area=1-15:1.
2. polytetrafluoroethylene (PTFE) rolled film as described in claim 1, hole aperture is 750-900nm, stem diameter 500-600nm,
Transforaminal aperture 155-185nm；Wherein the porosity of hole is 55-70%, and the porosity of transforaminal is 50-60%；The summary table of the stem
Area, stem area: transforaminal area=3-6:1.
3. polytetrafluoroethylene (PTFE) rolled film as claimed in claim 1 or 2,100-200 μm of film thickness.
4. a kind of wound membrane element, including blade, blade as two polytetrafluoroethylene (PTFE) rolled films as described in claim 1,2 or 3,
Network of rivers lattice composition is produced, the production network of rivers case is between two films；Setting water inlet grid between blade.
5. wound membrane element as claimed in claim 4, diameter 80-250mm.
6. the preparation method of polytetrafluoroethylene (PTFE) rolled film as described in claim 1-3, using method of electrostatic spinning, including spinning lotion
Preparation, spinning, preforming, sintering, temperature-control pressure-control continuous sintering in the sintering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710712504.XA CN109395606A (en) | 2017-08-18 | 2017-08-18 | A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710712504.XA CN109395606A (en) | 2017-08-18 | 2017-08-18 | A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101918488A (en) * | 2007-12-20 | 2010-12-15 | 菲利普莫里斯生产公司 | Hollow/porous fibers and applications thereof |
| CN103894077A (en) * | 2014-04-10 | 2014-07-02 | 江南大学 | Composite filter membrane with multidimensional pore structure and preparation method thereof |
| KR20150079209A (en) * | 2013-12-31 | 2015-07-08 | 도레이케미칼 주식회사 | Controlled surface porosity PTFE hollow-fiber type membrane and method for manufacturing thereof |
| CN104998557A (en) * | 2014-04-22 | 2015-10-28 | 成都百途医药科技有限公司 | Production method of super-hydrophobic polytetrafluoroethylene membrane |
| CN106669443A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber tubular film |
| CN106669444A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber membrane |
| CN106948164A (en) * | 2017-03-08 | 2017-07-14 | 杭州安诺过滤器材有限公司 | Film being made up of the acid fiber by polylactic of the continuous poriferous structure of nanometer and preparation method thereof |
-
2017
- 2017-08-18 CN CN201710712504.XA patent/CN109395606A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101918488A (en) * | 2007-12-20 | 2010-12-15 | 菲利普莫里斯生产公司 | Hollow/porous fibers and applications thereof |
| KR20150079209A (en) * | 2013-12-31 | 2015-07-08 | 도레이케미칼 주식회사 | Controlled surface porosity PTFE hollow-fiber type membrane and method for manufacturing thereof |
| CN103894077A (en) * | 2014-04-10 | 2014-07-02 | 江南大学 | Composite filter membrane with multidimensional pore structure and preparation method thereof |
| CN104998557A (en) * | 2014-04-22 | 2015-10-28 | 成都百途医药科技有限公司 | Production method of super-hydrophobic polytetrafluoroethylene membrane |
| CN106669443A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber tubular film |
| CN106669444A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber membrane |
| CN106948164A (en) * | 2017-03-08 | 2017-07-14 | 杭州安诺过滤器材有限公司 | Film being made up of the acid fiber by polylactic of the continuous poriferous structure of nanometer and preparation method thereof |
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