CN103857462B - Hydrophilicity kynoar system hollow fiber separating film and manufacture method thereof - Google Patents
Hydrophilicity kynoar system hollow fiber separating film and manufacture method thereof Download PDFInfo
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- CN103857462B CN103857462B CN201280048355.7A CN201280048355A CN103857462B CN 103857462 B CN103857462 B CN 103857462B CN 201280048355 A CN201280048355 A CN 201280048355A CN 103857462 B CN103857462 B CN 103857462B
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- 238000000034 method Methods 0.000 title claims abstract description 91
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 50
- 238000009987 spinning Methods 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000012805 post-processing Methods 0.000 claims abstract description 13
- 238000002145 thermally induced phase separation Methods 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 239000004697 Polyetherimide Substances 0.000 claims description 24
- 229920001601 polyetherimide Polymers 0.000 claims description 24
- 239000002033 PVDF binder Substances 0.000 claims description 23
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 23
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 20
- 239000004642 Polyimide Substances 0.000 claims description 18
- 229920001721 polyimide Polymers 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 17
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 11
- 238000012546 transfer Methods 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 4
- 229920002873 Polyethylenimine Polymers 0.000 claims 2
- 229920002521 macromolecule Polymers 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005191 phase separation Methods 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 229920002301 cellulose acetate Polymers 0.000 description 10
- 235000012489 doughnuts Nutrition 0.000 description 5
- 230000006355 external stress Effects 0.000 description 5
- SYTQFBVTZCYXOV-UHFFFAOYSA-N 3,5,5-trimethylcyclohex-2-en-1-one Chemical compound CC1=CC(=O)CC(C)(C)C1.CC1=CC(=O)CC(C)(C)C1 SYTQFBVTZCYXOV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052950 sphalerite Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920006060 Grivory® Polymers 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 108700005457 microfibrillar Proteins 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 229920004748 ULTEM® 1010 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
- B01D69/04—Tubular 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
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
-
- 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
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The present invention provides a kind of hydrophilicity kynoar system hollow fiber separating film, it utilizes the spinning solution manufacture comprising specific hydrophilic macromolecule and Weak solvent, the mechanical strength of this separation film, hole dimension be little, high through flow and film stain resistance is high, and the Kynoar system carried out with thermally induced phase separation according to phase separation method in perfect prior art separates in film manufacturing process and the shortcoming of the aspect existence such as characteristic of manufactured film.Additionally, present invention also offers a kind of manufacture method separating film, it eliminates specific porous and gives postprocessing working procedures and hydrophiling imparting postprocessing working procedures when manufacturing water and processing and separate film, thus provides economical and efficiency separation film manufacturing method.
Description
Technical field
The present invention relates to the manufacturer of a kind of hydrophilicity kynoar system (PVDF) hollow fiber separating film
Method, more particularly, it relates to one prepare comprise Kynoar (PVDF), hydrophilic macromolecule,
The spinning solution of specific Weak solvent, this spinning solution of spinning also is allowed to carry out thermic phase transfer and manufacture
PVDF hollow fiber separating film and manufacture method thereof.
Background technology
In recent years, as water purification and the operation of process sewage, it is widely applied and utilizes the film separating film to divide
From technology.Generally, be used in water process separate film filter pollute former water during, polluter
Absorption is on film surface and grows, thus pollutes on film surface, if this type of separation fouling membrane is tight
Weight, can make the permeable pressure of effect during filtration raise, and gradually decrease volume of production, eventually result in separation
The reduction of membrane filtration function.In order to suppress this type of to separate the pollution of film, chlorine system and acid, alkali is used to carry out
Washing, but these methods can cause the shortening that separates film service life, therefore, the most just uses
The material i.e. research of Kynoar system resin that chemical resistance is high,
In using Kynoar system resin as the separation film manufacturing method of raw material, generally use the most non-
Solvent causes phase separation method (NIPS, Nonsolvent-Induced Phase Separation): the method will comprise poly-
The macromolecular solution of vinylidene fluoride resin, good solvent and porogen, less than Kynoar system resin
Carry out at a temperature of fusing point casting and extruding spinning, and freeze solidly in non-solvent (non-solvent), from
And form cellular structure.Described phase separation method have can the advantage of free adjusting hole size,
But lacking in terms of the surface characteristic that the mechanical strength that there is separation film is weak and weak to fouling membrane because of hydrophobicity
Point.
It addition, thermally induced phase separation (TIPS, Thermally induced phase separation) is such as lower section
Method: use Kynoar system resin and Weak solvent, in the temperature rising to Kynoar system melting point resin
Cool and solidify after carrying out spinning under degree and manufacture separation film.For described thermally induced phase separation, Asahi Chemical Industry
(Asahi KASEI) company adds inorganic fine particles as porogen and has manufactured micro-filtration membrane (secondary filter
Film), but need after there is spinning extract inorganic fine particles and the troublesome operation of hydrophiling operation need to be carried out.
On the contrary, east beautiful (TORAY) company is in the manufacture of double-deck Kynoar system ultrafilter membrane, sharp
Form the supporting course of inside with thermally induced phase separation, utilized by phase separation method and comprise hydrophilic
Separation film activity layer outside the resin solution manufacture of high molecular Kynoar system.Described east is beautiful
(TORAY) ultrafilter membrane of company constitutes double-decker, accordingly, it is capable to access high intensity, high flow capacity
Separation film, but be because in manufacture method being simultaneously used thermally induced phase separation and phase separation
, therefore there is the shortcoming that manufacturing expense is high in method.On the contrary, Korean Chemistry Inst's (publication
10-2009-0011655) in the manufacture method of polyvinylidene fluoride hollow fiber membrane, will comprise as parent
The Kynoar system resin of the polyacrylonitrile of aqueous high molecular is coated on tubular type macromolecule supporting course (polyester)
On, utilize phase separation method to manufacture.To the coat film of described Korean Chemistry Inst and
Speech, owing to employing interior support layer, therefore, it is possible to produce the separation film of high intensity, but is using
When separating film, coat peeling occurs, and, if in time not having to manufacture in the way of supporting course, having
Fracture strength becomes very weak shortcoming.
Recently, industrial for low cost manufacture mechanical strength, hole dimension little and high through flow,
The demand of the method separating film that the stain resistance of film is high is more and more higher.
This specification with reference to many papers and patent documentation, and indicated it and quote.This explanation
Book reference has also quoted cited paper and the entirety of patent documentation disclosure, definitely to illustrate
The technical merit of this area and present disclosure.
Summary of the invention
The problem that invention is to be solved
The present inventor in order to developing low-cost manufacture mechanical strength, hole dimension (size) is little, pass through
The method separating film that flow is high and film stain resistance is high, is studied intensively, itself found that: logical
Cross in comprising Kynoar (PVDF) and the spinning solution of Weak solvent, add specific hydrophilic height
Molecule, and its spinning is carried out thermic phase transfer method, it is possible to even if producing the table after not carrying out
Face modification and surface-coated process, mechanical strength, hole size, through flow and film resistant
The PVDF hollow fiber separating film that all aspects such as metachromia are the most excellent, thus complete the present invention.
Therefore, it is an object of the invention to, it is provided that a kind of mechanical strength, hole size, through flow and
The manufacture method of the hydrophilic PVDF system hollow fiber separating film that film stain resistance is all excellent.
Another object of the present invention is to, it is provided that the mechanical strength that manufactured by said method, hole size,
Through the hydrophilic PVDF system hollow fiber separating film that flow and film stain resistance are all excellent.
It is a further object of the present invention to provide a kind of compositions, it is poly-partially that it is used for manufacturing described hydrophilic
Fluorothene system hollow fiber separating film.
Other purpose of the present invention and advantage by following detailed description of the invention, claims with
And accompanying drawing can be definitely.
Solve the method used by problem
According to an embodiment of the present invention, it is provided that a kind of hydrophilicity kynoar system doughnut separates
The manufacture method of film, the method comprises the steps (i) with step (ii):
(i) obtaining the step of spinning solution, this spinning solution comprises the Kynoar of 10～60 weight %
Be resin (PVDF), 5～30 weight % by Polyetherimide (PEI), polyimides (PI),
More than one the hydrophilic resin selected in the group that polyamide (PA) and cellulose acetate (CA) are formed
Fat, and the Weak solvent (poor-solvent) of 20～85 weight %；
(ii) described spinning solution is carried out spinning and manufacture the step of hollow fiber separating film.
Relative to macromolecule resin gross weight, the usage amount of described PVDF is preferably 10～50 weight %,
More preferably 20～40 weight %.If described PVDF usage amount is less than 10 weight %, doughnut
Film strength dies down, if more than 50 weight %, the viscosity of macromolecular solution is too high, thus exists by spinning
The problem that silk is difficult to molding hollow fiber separating film.
Relative to macromolecule resin gross weight, the usage amount of described hydrophilic macromolecule is preferably 5～30 weights
Amount %, more preferably 10～25 weight %.Now, if the usage amount of described hydrophilic macromolecule is little
In 5 weight %, then the manufactured film stain resistance separating film is not enough, if more than 30 weight %, due to
In macromolecule gross weight, the ratio shared by hydrophilic macromolecule is high, therefore, and the particle of hydrophilic macromolecule
Change separates greatly the hole of film and diminishes, the most preferred.
The most described hydrophilic macromolecule uses by Polyetherimide (PEI), polyimides (PI), gathers
Amide (PA) and cellulose acetate (CA) are selected any one more than.Further preferably use
The group being made up of Polyetherimide (PEI), polyimides (PI) and polyamide (PA) is selected
More than one.
It addition, described hydrophilic macromolecule be preferably used weight average molecular weight be 100000～500000 hydrophilic
Property macromolecule.
Relative to macromolecule resin gross weight, the usage amount of described Weak solvent is preferably 20～85 weight %,
More preferably 35～70 weight %.Here, as Weak solvent, as long as low below 60 DEG C
The lower resin that can dissolve more than 5 weight % of temperature, but the high-temperature region more than 60 DEG C and below melting point resin
In territory, the solvent of the above resin of solubilized 5 weight %, has no particular limits, but be preferably used by
Gamma-butyrolacton (lactone), Ketohexamethylene (cyclohexanone), 1-Phenylethanone. (Acetophenone),
Isophorone (isophorone) is selected any one more than.
Hereinafter, for utilizing described PVDF to separate film manufacture macromolecule resin to manufacture PVDF hollow
The manufacture method of fiber separating film illustrates.
(i) step is the step obtaining spinning solution, such as, and can be by by Kynoar system resin
(PVDF) 10～60 weight %；By Polyetherimide (PEI), polyimides (PI), polyamide
(PA) more than one hydrophilic resins 5～30 and selected in the group that formed of cellulose acetate (CA)
Weight %；And Weak solvent (poor-solvent) 20～85 weight % is mixed, by described PVDF
Separate film manufacture macromolecule resin and make its molten homogeneous with 120～180 DEG C of temperature heating, thus manufacture
The method of spinning solution is implemented.
The method of film manufacture macromolecule resin is separated the most particularly for PVDF described in molten homogeneous
Limit, can enumerate: devote in the continuous resin kneading device of screw-type extruder etc. and manufacture all
The method of even spinning solution；Or manufacture in device being provided with the spinning solution of blender of prescribed level
The method manufacturing uniform spinning solution.Now, the temperature of the most each device remains 120～180 DEG C.
The most described spinning solution is quantitatively moved by gear pump to nozzle and carries out spinning, and in phase transfer
Groove cools and solidifies.Now, in order to reduce heat loss, preferably manufacture device to from macromolecule resin
Feed-line to gear pump, the feed-line from gear pump to nozzle heat.
Step afterwards is (ii) spinning solution as above to be carried out spinning and manufactures doughnut and separate
The step of film.
In concrete example, described step (ii) can be carried out by thermally induced phase separation.Such as, can be by profit
With identical nozzle described spinning solution and solidified inside bathed carry out spinning and in phase transfer groove cooling solid
Change spinning solution, thus the method manufacturing hollow fiber separating film is implemented.
Described solidified inside bath and phase transfer groove can use Weak solvent or water and the mixture of Weak solvent or
Water and the mixture of good solvent.Now, it is not particularly limited as described Weak solvent, but preferably makes
With from gamma-butyrolacton (lactone), Ketohexamethylene (cyclohexanone), 1-Phenylethanone. (Acetophenone),
Isophorone (isophorone) is selected any one more than；It is preferably used from diformazan as good solvent
That selects in base Methanamide, METHYLPYRROLIDONE, dimethyl acetylamide and dimethyl sulfoxide is any
More than one.
It addition, the bath of described solidified inside and the temperature of phase transfer groove are 0～80 DEG C, more preferably 10
～50 DEG C.Now, if the temperature of the bath of described solidified inside and phase transfer groove is less than 0 DEG C, then can cause rapidly
, therefore there is too fast solidification phenomenon on hollow fiber separating film surface, thus be difficult to give hollow in cooling
The porosity of fiber separating film；If more than 80 DEG C, owing to too slowly solidifying, causing polymer crystallization
Becoming big, the size in hole also becomes big therewith, can cause the problem that mechanical strength dies down.
Preferably in concrete example, the method for the present invention also includes that the separation film to (ii) being manufactured by described step enters
The step of row stretching.
Described stretching step can carry out stretching by stretching-machine and produce final hollow fiber separating film
Implement.
Described stretching is can to improve the mechanical strength of hollow fiber separating film and increase pure water through flow
Method, it is not particularly limited.Such as, damp and hot stretching can be in stretching-machine front-end and back-end
In carried out by rotating roller, the rotary speed of each roller can control.It addition, stretching-machine can use water
Or steam, preferably keeps the temperature at 80～90 DEG C.It addition, stretching ratio be preferably more than 1 times and
Less than 5 times.
Described stretching step can be carried out by local elongation method, it is possible to is entered by separated Posterior circle pulling method
OK, wherein, described local elongation method is to make external stress concentrate on the specific part separating film, and instead
Carry out this stress concentration again, thus the method carrying out stretching operation based on hysteresis；Described be separated after
Cyclic tension method is to circulate to positive direction and reverse direction continuously between solution bobbin and mound bobbins and carry out moving back
The method of stretching.When using separated Posterior circle pulling method, if entirely without applying external stress
On non-stretched hollow-fibre membrane, external stress acts perpendicularly to the direction of growth of platelet (lamellae), then exist
There is microfibrillar structure in macromolecule thin area, increasing if applying fento length during the external stress more than it,
Lengthening distance between platelet region.It addition, execute in the way of angled with the direction of growth of platelet
When adding external stress, can be at the macromolecular chain end generation microfibrillar structure within platelet.
In concrete example, the method is characterized in that, described step does not (ii) include manufactured afterwards
Separation membrane surface be coated operation, surface hydrophilic treatment process, porous give post processing work
Sequence.
Due to the intensity of hollow fiber polymer membrane and permeable amount inversely, therefore, it is difficult to improve simultaneously
Both performances.In the past in order to obtain high permeability rate or high intensity, by carry out surface modification treatment or after
Process, or after first manufacturing the macromolecular fibre supporting course of braiding (braid) shape, apply thereon
The method of hydrophilic macromolecule implements surface and processes or coating.But, these methods need to carry out two
, therefore there is manufacturing expense height, the shortcoming of time length in hollow-fibre membrane manufacture process more than individual step.
The hollow-fibre membrane manufactured by the method for the present invention, is to utilize to comprise specific hydrophilic macromolecule
Manufacture with the spinning solution of Weak solvent, it is not necessary to for hydrophiling, give porous, imparting intensity etc.
Purpose and manufactured separation membrane surface is coated, surface process and post processing, and, even if
Do not carry out these to process, the hollow-fibre membrane of the present invention inherently mechanical strength, hole dimension (size)
Little, high through flow, film stain resistance is the most outstanding simultaneously.
A concrete example accordingly, as the present invention, it is provided that the manufacture method of a kind of hollow fiber separating film,
It is characterized in that, do not include manufactured separation membrane surface is coated after described step is (ii)
Operation, surface hydrophilic treatment process, porous give postprocessing working procedures.According to the method, due to row
Except specific working procedure of coating, surface treatment procedure and postprocessing working procedures, the most economical and effect
Forthright.
According to another embodiment of the present invention, it is provided that a kind of by method as above manufacture hydrophilic
Property Kynoar system hollow fiber separating film.
For the PVDF hollow fiber separating film manufactured by manufacture method as above, even if not
Carrying out specific porous and give post processing, surface process, coating process etc., its film inherently machinery is strong
Degree excellence, hole dimension are little, high through flow, and film stain resistance is the most outstanding simultaneously.
For the hydrophilic PVDF hollow fiber separating film manufactured by the method for the present invention, as film
Cross-section structure define do not have macroporous sphalerite (Sphalerite) structure, because of
This mechanical strength, the external diameter of hollow fiber separating film is 1～5mm scope, and internal diameter is 0.6～4.8mm
Scope, average pore size is 0.1～0.02 μm, and pure water is 200～1200L/m through flow2hr
(-500mmHg), has the porosity of more than 60%, shows outstanding film stain resistance.
According to another embodiment of the invention, it is provided that a kind of hydrophilicity kynoar system doughnut divides
From film manufacture compositions, said composition comprises: Kynoar system resin (PVDF) 10～60 weight
Amount %；By Polyetherimide (PEI), polyimides (PI), polyamide (PA) and cellulose acetate
(CA) more than one hydrophilic resin 5～30 weight % selected in the group formed；And it is weak molten
Agent (poor-solvent) 20～85 weight %.
The hollow fiber separating film manufacture compositions of the present invention is characterised by, not with surface modification at
Use for the purpose of reason or post processing, but there is the use manufacturing hollow fiber separating film supporting structure self
On the way.
The compositions of the present invention is obtained by the method mixing following compound: Kynoar system resin
(PVDF) 10～60 weight %；By Polyetherimide (PEI), polyimides (PI), polyamide
(PA) more than one the hydrophilic resin 5 and selected in the group that formed of cellulose acetate (CA)～
30 weight %；And Weak solvent (poor-solvent) 20～85 weight %.By mixed described in molten homogeneous
Compound also carries out spinning, it is possible to even if acquisition is not carried out, specific porous gives post processing, surface processes,
Coating process etc., itself is little, through flow height and film stain resistance with regard to mechanical strength, hole dimension
The most outstanding hydrophilicity kynoar system hollow membrane.
In concrete example, described hydrophilic resin is by Polyetherimide (PEI), polyimides (PI)
The group formed with polyamide (PA) is selected more than one.It addition, described hydrophilic resin is preferred
The macromolecule using weight average molecular weight to be 100000～500000.
It addition, described Weak solvent can be by gamma-butyrolacton (lactone), Ketohexamethylene (cyclohexanone),
The one selected in the group that 1-Phenylethanone. (Acetophenone) and isophorone (isophorone) are formed
Above solvent.
Invention effect
According to the present invention, it is provided that a kind of hydrophilicity kynoar system hollow fiber separating film, it utilizes bag
Spinning solution manufacture containing specific hydrophilic macromolecule and Weak solvent, the mechanical strength of this separation film,
Hole dimension is little, high through flow and film stain resistance is high, causes phase according to non-solvent in perfect prior art
The Kynoar system that partition method is carried out with thermally induced phase separation separates in the manufacturing process of film and manufactured
The shortcoming that exists of the aspect such as characteristic of film.
It addition, the hydrophilicity kynoar system hollow fiber separating film manufactured by the method for the present invention,
Even if not carrying out other postprocessing working procedures, also at hole size, through flow, hydrophilic and intensity
All aspects have the characteristic of excellence, it is possible to get rid of specific porous and give post processing and hydrophilic
Change and give postprocessing working procedures, therefore, it is possible to bring economy and efficiency.
Accompanying drawing explanation
Fig. 1 is to be observed by scanning electron microscope (Scanning Electron Microscope, SEM)
The figure of the thickness of hollow fiber separating film made according to the method for the present invention, pore size and section.
Fig. 2 is to be observed by scanning electron microscope (Scanning Electron Microscope, SEM)
The figure of apparent condition of hollow fiber separating film made according to the method for the present invention.
Detailed description of the invention
Below, the present invention is illustrated in greater detail by embodiment.These embodiments are only used for the most concrete
The present invention is described, to those skilled in the art, it is real that protection scope of the present invention is not limited to these
It is self-evident for executing example.
Embodiment
<embodiment 1>
By Kynoar system resin (PVDF, Su Wei (Solvay) company, solef6010) 35 weights
Amount %, gamma-butyrolacton (GBL) 55 weight %, Polyetherimide (PEI, husky bit (SABIC innovation
Plasitics) company, ULTEM1010) 10 weight % mix, and are being filled with the 170 of nitrogen
After DEG C reactor stirs 12 hours, it is transferred in the gutter under equal state stablize 12 hours,
Thus prepared spinning component.Then, sprayed spinning component and solidified inside bath by nozzle simultaneously
(GBL80 weight %, water 20 weight %) is shaped to doughnut form, and impregnated in and be contained in outside
In non-solvent in coagulating bath (phase transfer groove), thus define hollow-fibre membrane.Described non-solvent makes
With pure water, the dosing pump speed of solidified inside bath is 4.5ml/min, and carries out at a temperature of 25 DEG C.For
Transfer described spinning solution, is set as 5kgf/cm by the nitrogen pressure in reactor to discharge pressure2Above,
The shifting pump manufacturing solution is maintained at 30rpm, the spacing of nozzle with the non-solvent of phase transfer groove is fixed
For 10cm.
Measured according to upper by scanning electron microscope (Scanning Electron Microscope, SEM)
After stating the thickness of hollow fiber separating film, pore size, section and the apparent condition that method manufactures,
Be shown in Fig. 1 and Fig. 2, can confirm that spherical sphalerite (Sphalerite) structure
The shape being connected.It addition, by the base of the hollow fiber separating film manufactured by the method mensuration of<experimental example>
This physical property is also shown in Table 1.
<embodiment 2>
Except with polyimides (PI, vapour bar polymer (Ciba polymer) company, Matrimid5218)
Replace outside the Polyetherimide of embodiment 1, use method same as in Example 1 to manufacture hollow
Fiber separating film.
<embodiment 3>
Except with polyamide (PA, chemical (EMS-Grivory) company of Ames, Grivory G16)
Replace outside the Polyetherimide of embodiment 1, use method same as in Example 1 to manufacture hollow
Fiber separating film.
<embodiment 4>
Except with Triafol T (CTA, Yi Shiman (EASTMAN) company, CA-436-80S)
Replace outside the Polyetherimide of embodiment 1, use method same as in Example 1 to manufacture hollow
Fiber separating film.
<embodiment 5>
Except replace with 1-Phenylethanone. (Acetophenone) embodiment 1 gamma-butyrolacton (GBL) it
Outward, method same as in Example 1 is used to manufacture hollow fiber separating film.
<embodiment 6>
Except replace with isophorone (isophorone) embodiment 1 gamma-butyrolacton (GBL) it
Outward, method same as in Example 1 is used to manufacture hollow fiber separating film.
<comparative example 1>
Except replacing embodiment 1 with polyacrylonitrile (PAN, aldrich (Aldrich) company)
Outside Polyetherimide, method same as in Example 1 is used to manufacture hollow fiber separating film.
<comparative example 2>
Use method same as in Example 1 to manufacture hollow fiber separating film, but composition does not use parent
Aqueous high molecular, but by Kynoar system resin 40 weight %, gamma-butyrolacton (GBL) 60 weight
Amount % is mixed and is manufactured.
<comparative example 3>
When comparing with comparative example 2, except with METHYLPYRROLIDONE (NMP) replace γ-
Butyrolactone (GBL) and at 150 DEG C stirring outside, in using the method identical with comparative example 1 to manufacture
Hollow fiber separation film.
<comparative example 4>
When comparing with comparative example 2, except replacing γ-Ding Nei with dimethyl acetylamide (DMAc)
Outside ester (GBL), the method identical with comparative example 2 is used to manufacture hollow fiber separating film.
<experimental example>
1. pure water passes through flow measurement
The hollow fiber separating film self obtained in above-described embodiment 1～6 and comparative example 1～3 is manufactured
Become and there is certain length and the module of bar number, at normal temperatures with TMP(Trans Membrane Pressure)
1kgf/cm2Pressure also uses force (forcing) pump to carry out pressurized pure water to go out-to enter (Out-In) mode, thus surveys
Fixed.
2. the mensuration of average pore size
Described embodiment is measured by Capillary Flow Porosimetry (Capillary Flow Porometer)
1～6 and comparative example 1～3 in manufacture hollow fiber separating film.
3. contact angle determination
By KRSS K100 surface tension instrument (Tensiometers) with dynamic contact angle (dynamic
Contact angle) mode measure described embodiment 1～6 and comparative example 1～3 in the hollow that manufactures fine
Dimension separates film.
4. stretching strength determination
With micro-stretching strength determination instrument (Micro-Forcing Tester) measure described embodiment 1～6 and
The hot strength of the hollow fiber separating film manufactured in comparative example 1～3.
Such as above-mentioned experimental example, the basic physical properties of manufactured hollow fiber separating film is determined, and
The results are shown in table 1 below.
Table 1
Test result indicate that, embodiment 1～6 is at hole size, through flow, contact angle and fracture strength
Ensure that excellent specific property etc. all aspects, and the characteristic of embodiment 1～3 and 5～6 is the most excellent.
Claims (7)
1. a manufacture method for hydrophilicity kynoar system hollow fiber separating film, including:
I () obtains the step of spinning solution, this spinning solution contains the Kynoar of 10～60 weight %
Be resin PVDF, 5～30 weight % by Polyetherimide PEI, polyimides PI and polyamide PA institute
More than one and the hydrophilic resin that weight average molecular weight is 100000～500000 selected in the group of composition,
And 20～85 Weak solvents of weight %；And
(ii) described spinning solution is carried out spinning in the phase transfer groove of 10～50 DEG C and manufacture hollow fibre
Dimension separates the step of film,
Wherein, after described step (ii), do not include the work that manufactured separation membrane surface is coated
Sequence, surface hydrophilic treatment process, porous give postprocessing working procedures.
2. the manufacturer of hydrophilicity kynoar system as claimed in claim 1 hollow fiber separating film
Method, it is characterised in that carry out described step (ii) by thermally induced phase separation.
3. the manufacturer of hydrophilicity kynoar system as claimed in claim 1 hollow fiber separating film
Method, it is characterised in that also include: separate the step that film carries out stretching by manufacture in described step (ii).
4. the manufacturer of hydrophilicity kynoar system as claimed in claim 1 hollow fiber separating film
Method, it is characterised in that described Weak solvent is for by gamma-butyrolacton, Ketohexamethylene, 1-Phenylethanone. and isophorone institute
Composition group in select more than one.
5. a hydrophilicity kynoar system hollow fiber separating film, it is to pass through Claims 1 to 4
According to any one of method manufacture.
6. a hydrophilicity kynoar system hollow fiber separating film manufacture compositions, comprises:
The Kynoar system resin PVDF of 10～60 weight %；
The group being made up of Polyetherimide PEI, polyimides PI and polyamide PA of 5～30 weight %
In more than one and the hydrophilic resin that weight average molecular weight is 100000～500000 selected；And
The Weak solvent of 20～85 weight %.
7. hydrophilicity kynoar system as claimed in claim 6 hollow fiber separating film manufacture combination
Thing, it is characterised in that described Weak solvent is for by gamma-butyrolacton, Ketohexamethylene, 1-Phenylethanone. and isophorone institute
Composition group in select more than one.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| KR10-2011-0119649 | 2011-11-16 | ||
| KR1020110119649A KR101462939B1 (en) | 2011-11-16 | 2011-11-16 | Hydrophilic Polyvinylidene Fluoride Based Hollow Fiber Membrane and Preparing Method Thereof |
| PCT/KR2012/009591 WO2013073828A1 (en) | 2011-11-16 | 2012-11-14 | Hydrophilic polyvinylidene fluoride-based hollow-fiber separation membrane, and method for manufacturing same |
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| CN103857462B true CN103857462B (en) | 2016-08-24 |
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| KR101661671B1 (en) * | 2013-06-28 | 2016-09-30 | 제일모직 주식회사 | A method for manufacturing porous separators for use of secondary cell using nano steam, separators made by the method, and secondary cell |
| CN103495347B (en) * | 2013-10-15 | 2016-05-25 | 山东招金膜天有限责任公司 | A kind of continuous thermally induced phase separation film formation device and film-forming process |
| JP6203393B2 (en) | 2013-12-16 | 2017-09-27 | サビック グローバル テクノロジーズ ビー．ブイ． | Treated mixed matrix polymer membrane |
| EP3057689A4 (en) | 2013-12-16 | 2016-08-31 | Sabic Global Technologies Bv | Uv and thermally treated polymeric membranes |
| CN103861481B (en) * | 2014-04-03 | 2015-11-04 | 陕西科技大学 | A kind of method preparing polyvinylidene fluoride porous film |
| CN104209016B (en) * | 2014-07-30 | 2017-02-08 | 昆明理工大学 | Magnetic electric filtering membrane and preparation method thereof |
| CN104857866B (en) * | 2015-05-18 | 2017-06-16 | 上海交通大学 | A kind of method for preparing hydrophilic modifying polyvinylidene fluoride film |
| JP6791945B2 (en) * | 2016-03-09 | 2020-11-25 | 旭化成株式会社 | Porous hollow fiber membrane, its manufacturing method, and filtration method |
| CN109414658B (en) * | 2016-06-24 | 2021-08-03 | 东丽株式会社 | Composite porous hollow fiber membrane, preparation method thereof, membrane module and operation method |
| CN106637493B (en) * | 2016-09-23 | 2018-11-09 | 江西师范大学 | Nylon66 fiber/PVDF/PEO/ boric acid composite nano fibers and preparation method thereof |
| CN111013400A (en) * | 2019-12-30 | 2020-04-17 | 安徽普朗膜技术有限公司 | Method for preparing polyvinylidene fluoride tubular membrane by low-temperature thermal induced phase method |
| TWI740635B (en) | 2020-09-09 | 2021-09-21 | 財團法人工業技術研究院 | Polyvinylidene fluoride film composition, and polyvinylidene fluoride isolation film |
| CN112316756A (en) * | 2020-11-12 | 2021-02-05 | 艾克飞膜材(嘉兴)有限公司 | High-strength and high-retention TIPS hollow fiber membrane and preparation method thereof |
| CN114849500B (en) * | 2022-05-17 | 2023-02-10 | 江苏艾乐膜科技有限公司 | Preparation method of hydrophilized modified hollow fiber ultrafiltration membrane based on TIPS method |
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| KR101462939B1 (en) | 2014-11-19 |
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