CN109395605A - 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 PDF

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Publication number
CN109395605A
CN109395605A CN201710712503.5A CN201710712503A CN109395605A CN 109395605 A CN109395605 A CN 109395605A CN 201710712503 A CN201710712503 A CN 201710712503A CN 109395605 A CN109395605 A CN 109395605A
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CN
China
Prior art keywords
stem
transforaminal
ptfe
polytetrafluoroethylene
hole
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Application number
CN201710712503.5A
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Chinese (zh)
Inventor
周涛
孙琦
叶雷
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Chongqing Runze Pharmaceutical Co Ltd
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Chongqing Runze Pharmaceutical Co Ltd
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Priority to CN201710712503.5A priority Critical patent/CN109395605A/en
Publication of CN109395605A publication Critical patent/CN109395605A/en
Withdrawn legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/364Membrane distillation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D63/00Apparatus in general for separation processes using semi-permeable membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • B01D67/0004Organic membrane manufacture by agglomeration of particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/36Polytetrafluoroethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2323/00Details relating to membrane preparation
    • B01D2323/39Electrospinning
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/02Details relating to pores or porosity of the membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/38Hydrophobic 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, 300nm < hole aperture < 600nm, 200nm < stem diameter < 400nm, 70nm < transforaminal aperture < 150nm on the stem of hole;The porosity of hole is 80 ± 10%, and the porosity of transforaminal is 30 ± 15%;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

A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof
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, 300nm < hole on the stem of hole Lyriform pore diameter < 600nm, 200nm < stem diameter < 400nm, 70nm < transforaminal aperture < 150nm;The porosity of hole is 80 ± 10%, stem The porosity in hole is 30 ± 15%;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 480- 580nm, stem diameter 210-260nm, transforaminal aperture 75-90nm;Wherein the porosity of hole is 80-85%, the porosity of transforaminal For 25-30%;The total surface area of the stem, stem area: transforaminal area=5-8:1.
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: polytetrafluoroethylene (PTFE) is added in the sodium alginate homogeneous solution soluble in water for obtaining 14-15% concentration (PTFE) lotion (55-60%), so that PTFE and sodium alginate 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 to pressure value in 120-180s is greater than 70kpa no more than 75kpa, while with 4-5 DEG C/min It is warming up to 375-380 DEG C of temperature value, and keeps 10- in the case where pressure value is greater than 70kpa no more than 75kpa, 375-380 DEG C 12min;3. after heating, keeping vacuum to cooling to 50-100Pa.
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, 300nm < hole on the stem of hole Lyriform pore diameter < 600nm, 200nm < stem diameter < 400nm, 70nm < transforaminal aperture < 150nm;The porosity of hole is 80 ± 10%, stem The porosity in hole is 30 ± 15%;The total surface area of the stem, stem area: transforaminal area=1-15:1.100-200 μm of film thickness.Directly Diameter is 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: polytetrafluoroethylene (PTFE) is added in the sodium alginate homogeneous solution soluble in water for obtaining 14-15% concentration (PTFE) lotion (55-60%), so that PTFE and sodium alginate 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 to pressure value in 120-180s is greater than 70kpa no more than 75kpa, while with 4-5 DEG C/min It is warming up to 375-380 DEG C of temperature value, and keeps 10- in the case where pressure value is greater than 70kpa no more than 75kpa, 375-380 DEG C 12min;3. after heating, keeping vacuum to cooling to 50-100Pa.
(5) components such as film, water inlet grid, production network of rivers lattice, central tube are assembled.
158-171 ° of resulting materials hydrophobic angle.Gained PTFE material is carried out membrane distillation: the processing for oily waste water has Be adapted to industrial excellent properties and effect.Far super discharge standard after processing.Flux of membrane distillation > 20L/m2H, retention Rate is stablized 99.5% or more, is carried out continuously membrane distillation 3-4 months, flux drops to former flux 65-72%, material color after cleaning For pure white, for flux recovery before 95% or more, service phase is 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 480-580nm, stem diameter 210-260nm, transforaminal aperture 75-90nm;Wherein the porosity of hole is 80-85%, transforaminal Porosity is 25-30%;The total surface area of the stem, stem area: transforaminal area=5-8:1.
160-172 ° of resulting materials hydrophobic angle.Gained PTFE material is carried out membrane distillation: the processing for oily waste water has Be adapted to industrial excellent properties and effect.Far super discharge standard after processing.Flux of membrane distillation > 20L/m2H, retention Rate is stablized 99.5% or more, is carried out continuously membrane distillation 3-4 months, flux drops to former flux 65-72%, material color after cleaning For pure white, for flux recovery before 95% or more, service phase is 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 500nm, stem diameter 220nm, transforaminal aperture 80nm;Wherein the porosity of hole is 84%, and the porosity of transforaminal is 26%;Institute The total surface area of stem is stated, stem area: transforaminal area=6:1.
165 ° of resulting materials hydrophobic angle.Gained PTFE material is carried out membrane distillation: the processing for oily waste water has suitable It should be in industrial excellent properties and effect.Far super discharge standard after processing.Flux of membrane distillation > 20L/m2H, rejection are steady It is scheduled on 99.5% or more, is carried out continuously membrane distillation 3-4 months, flux drops to former flux 65-72%, and material color is pure after cleaning White, for flux recovery before 95% or more, service phase is 3-5.

Claims (6)

1. a kind of polytetrafluoroethylene (PTFE) rolled film, there is the pore structure of three-dimensional perforation, there is transforaminal on the stem of hole, 300nm < Hole aperture < 600nm, 200nm < stem diameter < 400nm, 70nm < transforaminal aperture < 150nm;The porosity of hole is 80 ± 10%, The porosity of transforaminal is 30 ± 15%;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 480-580nm, stem diameter 210-260nm, Transforaminal aperture 75-90nm;Wherein the porosity of hole is 80-85%, and the porosity of transforaminal is 25-30%;The total surface of the stem Product, stem area: transforaminal area=5-8:1.
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.
CN201710712503.5A 2017-08-18 2017-08-18 A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof Withdrawn CN109395605A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710712503.5A CN109395605A (en) 2017-08-18 2017-08-18 A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710712503.5A CN109395605A (en) 2017-08-18 2017-08-18 A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof

Publications (1)

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CN109395605A true CN109395605A (en) 2019-03-01

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