CN103857462A - Hydrophilic polyvinylidene fluoride-based hollow-fiber separation membrane, and method for manufacturing same - Google Patents
Hydrophilic polyvinylidene fluoride-based hollow-fiber separation membrane, and method for manufacturing same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 76
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 53
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 26
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 26
- 239000012528 membrane Substances 0.000 title claims abstract description 22
- 238000000926 separation method Methods 0.000 title claims abstract description 10
- 238000009987 spinning Methods 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 238000012805 post-processing Methods 0.000 claims abstract description 13
- 238000002145 thermally induced phase separation Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
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- 239000011347 resin Substances 0.000 claims description 38
- 230000004888 barrier function Effects 0.000 claims description 25
- 238000009792 diffusion process Methods 0.000 claims description 25
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- 239000004642 Polyimide Substances 0.000 claims description 20
- 229920002647 polyamide Polymers 0.000 claims description 20
- 229920001721 polyimide Polymers 0.000 claims description 20
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 17
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 16
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 12
- 229920002301 cellulose acetate Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005191 phase separation Methods 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000011109 contamination Methods 0.000 abstract 1
- 229920001477 hydrophilic polymer Polymers 0.000 abstract 1
- 208000012886 Vertigo Diseases 0.000 description 31
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- 230000000052 comparative effect Effects 0.000 description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- UBNPTJSGEYBDCQ-UHFFFAOYSA-N 1-phenylethanone Chemical compound CC(=O)C1=CC=CC=C1.CC(=O)C1=CC=CC=C1 UBNPTJSGEYBDCQ-UHFFFAOYSA-N 0.000 description 2
- 229920006060 Grivory® Polymers 0.000 description 2
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- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 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 1
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920004748 ULTEM® 1010 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 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
- 150000001875 compounds Chemical class 0.000 description 1
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- 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
- 230000010148 water-pollination Effects 0.000 description 1
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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
In general, a process manufacturing for polyvinylidene fluoride-based separation membrane and a membrane manufactured using same employ a non-solvent induced phase separation method and a thermally induced phase separation method. However, the hydrophilic polyvinylidene fluoride-based hollow-fiber separation membrane according to the present invention is manufactured using a spinning solution that contains a predetermined hydrophilic polymer and a poor solvent for excellent mechanical strength, and has small pores, a high permeation flow rate, and high membrane contamination resistance. Also, when a separation membrane for water treatment is manufactured, predetermined post-processing processes for providing porosity and hydrophilicity are eliminated, such that the separation membrane may be manufactured economically and efficiently.
Description
Technical field
The present invention relates to the manufacture method that a kind of hydrophilicity kynoar is (PVDF) hollow fiber separating film, more particularly, relate to one and prepare the spinning solution that comprises Kynoar (PVDF), hydrophilic macromolecule, specific Weak solvent, this spinning solution of spinning also makes it to carry out thermic phase transfer and PVDF hollow fiber separating film and the manufacture method thereof manufactured.
Background technology
In recent years, as water purification and the operation of disposing of sewage, the membrane separation technique of utilizing diffusion barrier in extensive use.Conventionally, be used in the diffusion barrier of water treatment in the process of former water of filtering pollution, pollution sources are adsorbed on film surface and grow, thereby pollute on film surface, if this type of diffusion barrier is seriously polluted, can make to filter time, the permeable pressure of effect raises, and reduces gradually output, finally can cause the reduction of diffusion barrier filtering function.In order to suppress the pollution of this type of diffusion barrier, use chlorine system and acid, alkali to wash, but these methods can cause the diffusion barrier shortening in service life, therefore, just using in recent years the material that chemical resistance is high is that Kynoar is the research of resin,
Being that resin is in the diffusion barrier manufacture method of raw material using Kynoar, conventionally adopt following phase separation method (NIPS, Nonsolvent-Induced Phase Separation): the method will comprise the Polymer Solution that Kynoar is resin, good solvent and pore-foaming agent, at the temperature that lower than Kynoar is melting point resin, cast and extruding spinning, and freeze solidly in non-solvent (non-solvent), thereby form cellular structure.Described phase separation method has advantages of can free adjusting hole size, but exists the mechanical strength of diffusion barrier weak and film is polluted to the shortcoming of weak surface characteristic aspect because of hydrophobicity.
In addition, thermally induced phase separation (TIPS, Thermally induced phase separation) for following method: using Kynoar is resin and Weak solvent, rise at the temperature that Kynoar is melting point resin, carry out spinning after cooling curing and manufacture diffusion barrier.For described thermally induced phase separation, company of Asahi Chemical Industry (Asahi KASEI) adds inorganic fine particles and manufactured micro-filtration membrane (secondary filter film) as pore-foaming agent, needs but exist the troublesome operation extracting inorganic fine particles and need carry out hydrophiling operation after spinning.On the contrary, east beautiful (TORAY) company is in the manufacture of milipore filter at double-deck Kynoar, utilize thermally induced phase separation to form inner supporting course, the Kynoar that comprises hydrophilic macromolecule by the utilization of phase separation method is that resin solution is manufactured outside diffusion barrier active layer.The milipore filter of described east beautiful (TORAY) company has formed double-decker, therefore, can obtain the diffusion barrier of high strength, high flow capacity, but because used thermally induced phase separation and phase separation method in manufacture method simultaneously, therefore have the shortcoming that manufacturing expense is high.On the contrary, Korean Chemistry Inst (publication 10-2009-0011655) is in the manufacture method of polyvinylidene fluoride hollow fiber membrane, be that resin-coating is upper in tubular type macromolecule supporting course (polyester) using comprising as the Kynoar of the polyacrylonitrile of hydrophilic macromolecule, utilize phase separation method to manufacture.For the coat film of described Korean Chemistry Inst, owing to having used interior support layer, therefore can produce high-intensity diffusion barrier, but in the time using diffusion barrier, there is coat peeling, and, if when not having the mode of supporting course to manufacture, there is fracture strength and become very weak shortcoming.
Recently, industrial little and to see through the demand of method of the diffusion barrier that flow stain resistance high, film is high more and more higher for low cost fabrication mechanical strength excellence, hole dimension.
This specification is with reference to many sections of papers and patent documentation, and indicated it and quote.This description with reference to and quoted the entirety of the paper of quoting and patent documentation disclosure, more clearly stating technical merit and the content of the present invention of this area.
Summary of the invention
The problem that invention will solve
The inventor is for developing low-cost manufacturing machine excellent strength, hole dimension (size) is little, see through the method for the high and diffusion barrier that film stain resistance is high of flow, study intensively, it found that: by add specific hydrophilic macromolecule in the spinning solution that comprises Kynoar (PVDF) and Weak solvent, and its spinning is carried out to thermic phase transfer method, even if can produce surface modification treatment and surperficial coating processing after not carrying out, in mechanical strength, hole size, see through also very excellent PVDF hollow fiber separating film of all aspects such as flow and film stain resistance, thereby complete the present invention.
Therefore, the object of the invention is to, a kind of mechanical strength, hole size are provided, are the manufacture method of hollow fiber separating film through flow and the equal excellent hydrophilic PVDF of film stain resistance.
Another object of the present invention is to, it is hollow fiber separating film that mechanical strength, the hole size of manufacturing by said method, the hydrophilic PVDF that sees through flow and the equal excellence of film stain resistance are provided.
Another object of the present invention is, a kind of composition is provided, and it is hollow fiber separating film for the manufacture of described hydrophilicity kynoar.
Other object of the present invention and advantage can be clearer and more definite by following detailed description of the invention, claims and accompanying drawing.
Solve problem method used
According to an embodiment of the present invention, it is the manufacture method of hollow fiber separating film that a kind of hydrophilicity kynoar is provided, the method comprise the steps (i) with step (ii):
(i) obtain the step of spinning solution, the Kynoar that this spinning solution comprises 10～60 % by weight is resin (PVDF), the hydrophilic resin of more than one that select in the group being formed by PEI (PEI), polyimides (PI), polyamide (PA) and cellulose acetate (CA) of 5～30 % by weight, and the Weak solvent of 20～85 % by weight (poor-solvent);
(ii) described spinning solution carried out to spinning and manufacture the step of hollow fiber separating film.
With respect to macromolecule resin gross weight, the use amount of described PVDF is preferably 10～50 % by weight, more preferably 20～40 % by weight.If described PVDF use amount is less than 10 % by weight, the weakened of hollow-fibre membrane, if be greater than 50 % by weight, the viscosity of Polymer Solution is too high, thereby has the problem that is difficult to moulding hollow fiber separating film by spinning.
With respect to macromolecule resin gross weight, the use amount of described hydrophilic macromolecule is preferably 5～30 % by weight, more preferably 10～25 % by weight.Now, if the use amount of described hydrophilic macromolecule is less than 5 % by weight, the film stain resistance deficiency of the diffusion barrier of manufacturing, if exceed 30 % by weight, the ratio shared due to hydrophilic macromolecule in macromolecule gross weight is high, therefore, the particle of hydrophilic macromolecule becomes large and the hole of diffusion barrier diminishes, therefore not preferred.
Preferred described hydrophilic macromolecule use by PEI (PEI), polyimides (PI), polyamide (PA) and cellulose acetate (CA), select any one more than.Further preferably use more than one that select in the group being formed by PEI (PEI), polyimides (PI) and polyamide (PA).
In addition, preferably to use weight average molecular weight be 100000～500000 hydrophilic macromolecule to described hydrophilic macromolecule.
With respect to macromolecule resin gross weight, the use amount of described Weak solvent is preferably 20～85 % by weight, more preferably 35～70 % by weight.Here, as Weak solvent, as long as dissolving resins more than 5 % by weight under the low temperature below 60 DEG C, but the solvent of the above resin of solubilized 5 % by weight in the high-temperature area more than 60 DEG C and below melting point resin, have no particular limits, but preferably use by gamma-butyrolacton (lactone), cyclohexanone (cyclohexanone), acetophenone (Acetophenone), isophorone (isophorone), select any one more than.
Below, describe for the manufacture method of utilizing described PVDF diffusion barrier manufacture macromolecule resin to manufacture PVDF hollow fiber separating film.
(i) step is to obtain the step of spinning solution, for example, and can be by by Kynoar being resin (PVDF) 10～60 % by weight; More than one hydrophilic resin 5～30 % by weight of selecting in the group being formed by PEI (PEI), polyimides (PI), polyamide (PA) and cellulose acetate (CA); And Weak solvent (poor-solvent) 20～85 % by weight are mixed, by the manufacture of described PVDF diffusion barrier with macromolecule resin with 120～180 DEG C of temperature heating and make its even melting, thereby the method for manufacturing spinning solution is implemented.
Be not particularly limited by the method for macromolecule resin for PVDF diffusion barrier manufacture described in even melting, can exemplify: devote in the continuous resin kneading device of screw-type extruder etc. and manufacture the method for uniform spinning solution; Or in the spinning solution manufacturing installation of mixer that is provided with prescribed level, manufacture the method for uniform spinning solution.Now, preferably the temperature of each device remains 120～180 DEG C.
Preferred described spinning solution quantitatively moves to nozzle by gear pump and carries out spinning, and carries out cooling curing in phase transfer groove.Now, in order to reduce heat loss, preferably the feed-line from macromolecule resin manufacturing installation to gear pump, feed-line from gear pump to nozzle are heated.
Step is afterwards (ii) spinning solution as above to be carried out to spinning and the step of manufacturing hollow fiber separating film.
In concrete example, described step (ii) can be undertaken by thermally induced phase separation.For example, can by utilize identical nozzle by described spinning solution and solidified inside bathe carry out spinning and in phase transfer groove cooling curing spinning solution, thereby the method for manufacturing hollow fiber separating film is implemented.
Described solidified inside is bathed and phase transfer groove can use the mixture of Weak solvent or water and Weak solvent or the mixture of water and good solvent.Now, be not particularly limited as described Weak solvent, but more than preferably using any one that select from gamma-butyrolacton (lactone), cyclohexanone (cyclohexanone), acetophenone (Acetophenone), isophorone (isophorone); More than preferably using as good solvent any one that select from dimethyl formamide, METHYLPYRROLIDONE, dimethylacetylamide and dimethyl sulfoxide (DMSO).
In addition, described solidified inside is bathed and the temperature of phase transfer groove is 0～80 DEG C, more preferably 10～50 DEG C.Now, cooling rapidly if the temperature of the bath of described solidified inside and phase transfer groove, lower than 0 DEG C, can cause, therefore there is too fast curing phenomenon on hollow fiber separating film surface, thus the porosity that is difficult to give hollow fiber separating film; If exceed 80 DEG C, solidify slowly owing to crossing, cause polymer crystallization to become large, the size in hole also becomes greatly thereupon, can cause the problem that mechanical strength dies down.
Preferably, in concrete example, method of the present invention also comprises the step that the diffusion barrier to (ii) being manufactured by described step stretches.
Described stretching step can be stretched and be produced final hollow fiber separating film and implement by stretching-machine.
Described stretching is can improve the mechanicalness intensity of hollow fiber separating film and increase pure water the method that sees through flow, and it is not particularly limited.For example, damp and hot stretching can be undertaken by rotating roller in stretching-machine front-end and back-end, and the rotary speed of each roller can be controlled.In addition, stretching-machine can make water or steam, preferably temperature is remained on to 80～90 DEG C.In addition, more than stretching ratio is preferably 1 times and below 5 times.
Described stretching step can be undertaken by local elongation method, also can be undertaken by cyclic tension method after being separated, wherein, described local elongation method is that external stress is concentrated on the privileged site of diffusion barrier, and repeatedly carry out this stress and concentrate, thereby based on the stretch method of operation of hysteresis; After described being separated, cyclic tension method is to move back the method that circulates and stretch to positive direction with against direction continuously between bobbin and mound bobbins of separating.After use is separated when cyclic tension method, if external stress vertically acts on the direction of growth of platelet (lamellae) on the not stretching hollow-fibre membrane that does not apply external stress completely, in macromolecule thin area, there is microfibrillar structure, if while applying its above external stress, fento length increases, the lengthening distance between platelet region.In addition, when applying external stress with the angled mode of the direction of growth of platelet, can be at the macromolecular chain end generation microfibrillar structure of platelet inside.
In concrete example, the inventive method is characterised in that, described step does not comprise that operation, surface hydrophilic treatment process, porous that the separation membrane surface of manufacturing is applied give postprocessing working procedures after (ii).
Due to the intensity of hollow fiber polymer membrane and the permeable amount relation that is inversely proportional to, be therefore difficult to improve this two kinds of performances simultaneously.In the past in order to obtain high permeability rate or high strength, by carrying out surface modification treatment or post processing, or after first manufacturing the macromolecular fibre supporting course of braiding (braid) shape, the method that applies hydrophilic macromolecule has thereon been implemented surface treatment or coating.But these methods need to be carried out two hollow-fibre membrane manufacture processes more than step, therefore there is the shortcoming that manufacturing expense is high, the time is long.
The hollow-fibre membrane of manufacturing by method of the present invention, to utilize the spinning solution that comprises specific hydrophilic macromolecule and Weak solvent to manufacture, need to be for hydrophiling, give porous, give the objects such as intensity and to the separation membrane surface of manufacturing apply, surface treatment and post processing, and, even if do not carry out these processing, hollow-fibre membrane of the present invention itself is little, high through flow with regard to mechanical strength excellence, hole dimension (size), and film stain resistance is very outstanding simultaneously.
Therefore, as a concrete example of the present invention, the manufacture method that a kind of hollow fiber separating film is provided, is characterized in that, does not comprise that operation, surface hydrophilic treatment process, porous that the separation membrane surface of manufacturing is applied give postprocessing working procedures in described step after (ii).According to the method, owing to having got rid of specific working procedure of coating, surface treatment procedure and postprocessing working procedures, therefore there is economy and efficiency.
According to another embodiment of the present invention, it is hollow fiber separating film that a kind of hydrophilicity kynoar of manufacturing by method as above is provided.
For the PVDF hollow fiber separating film of manufacturing by manufacture method as above, give post processing, surface treatment, coating processing etc. even if do not carry out specific porous, its film itself is little, high through flow with regard to mechanical strength excellence, hole dimension, and film stain resistance is very outstanding simultaneously.
For the hydrophilic PVDF hollow fiber separating film of manufacturing by method of the present invention, as the cross-section structure of film formed and do not there is macroporous zincblende (
sphalerite) structure, therefore mechanical strength excellence, the external diameter of hollow fiber separating film is 1～5mm scope, and internal diameter is 0.6～4.8mm scope, and average pore size is 0.1～0.02 μ m, and it is 200～1200L/m that pure water sees through flow
2hr(-500mmHg), there is more than 60% porosity, show outstanding film stain resistance.
According to another embodiment of the invention, it is hollow fiber separating film manufacture composition that a kind of hydrophilicity kynoar is provided, and said composition comprises: Kynoar is resin (PVDF) 10～60 % by weight; Hydrophilic resin 5～30 % by weight of more than one that select in the group being formed by PEI (PEI), polyimides (PI), polyamide (PA) and cellulose acetate (CA); And Weak solvent (poor-solvent) 20～85 % by weight.
Hollow fiber separating film manufacture of the present invention is characterised in that with composition, do not use taking surface modification treatment or post processing as object, but has the purposes of manufacturing hollow fiber separating film supporting structure self.
Composition of the present invention obtains by the method for mixing following compound: Kynoar is resin (PVDF) 10～60 % by weight; Hydrophilic resin 5～30 % by weight of more than one that select in the group being formed by PEI (PEI), polyimides (PI), polyamide (PA) and cellulose acetate (CA); And Weak solvent (poor-solvent) 20～85 % by weight.By mixture described in even melting and carry out spinning, even if can obtain and not carry out specific porous and give post processing, surface treatment, coating processing etc., itself is little with regard to mechanical strength excellence, hole dimension, see through flow hydrophilicity kynoar high and that film stain resistance is very outstanding is hollow membrane.
In concrete example, more than one for selecting in the group being formed by PEI (PEI), polyimides (PI) and polyamide (PA) of described hydrophilic resin.In addition, preferably to use weight average molecular weight be 100000～500000 macromolecule to described hydrophilic resin.
In addition, described Weak solvent can be more than one the solvent of selecting in the group being made up of gamma-butyrolacton (lactone), cyclohexanone (cyclohexanone), acetophenone (Acetophenone) and isophorone (isophorone).
Invention effect
According to the present invention, it is hollow fiber separating film that a kind of hydrophilicity kynoar is provided, the spinning solution manufacture that its utilization comprises specific hydrophilic macromolecule and Weak solvent, the mechanical strength excellence of this diffusion barrier, hole dimension be little, see through that flow is high and film stain resistance is high, the shortcoming that in the manufacturing process that the perfect Kynoar carrying out according to phase separation method and thermally induced phase separation in prior art is diffusion barrier and the aspect such as the characteristic of the film of manufacturing exists.
In addition, the hydrophilicity kynoar of manufacturing by method of the present invention is hollow fiber separating film, even if do not carry out other postprocessing working procedures, also at hole size, see through aspect flow, hydrophily and intensity all and there is excellent characteristic, can get rid of thus that specific porous is given post processing and postprocessing working procedures is given in hydrophiling, therefore can bring economy and efficiency.
Brief description of the drawings
Fig. 1 is by the figure of thickness, pore size and the section of the hollow fiber separating film made according to the method for the present invention of SEM (Scanning Electron Microscope, SEM) observation.
Fig. 2 is by the figure of the surface state of the hollow fiber separating film made according to the method for the present invention of SEM (Scanning Electron Microscope, SEM) observation.
Detailed description of the invention
Illustrate in greater detail the present invention by embodiment below.These embodiment are only for further illustrating the present invention, and to those skilled in the art, it is self-evident that protection scope of the present invention is not limited to these embodiment.
Embodiment
< embodiment 1>
Be resin (PVDF by Kynoar, Su Wei (Solvay) company, solef6010) 35 % by weight, gamma-butyrolacton (GBL) 55 % by weight, PEI (PEI, sand bit (SABIC innovation plasitics) company, ULTEM1010) 10 % by weight are mixed, and stir 12 hours in 170 DEG C of reactors that are filled with nitrogen after, be transferred in the gutter under equal state and stablize 12 hours, thereby prepared spinning component.Then, spray spinning component and solidified inside by nozzle simultaneously and bathe (GBL80 % by weight, water 20 % by weight) and be shaped to doughnut form, and impregnated in the non-solvent being contained in outside coagulating bath (phase transfer groove), thereby formed hollow-fibre membrane.Described non-solvent has used pure water, and the constant displacement pump speed that solidified inside is bathed is 4.5ml/min, and carries out at 25 DEG C of temperature.In order to transfer described spinning solution, the nitrogen pressure in reactor is decided to be to 5kgf/cm to discharge to be installed with
2above, the shifting pump of manufacturing solution remains on 30rpm, and distance between nozzle and the non-solvent of phase transfer groove is fixed as to 10cm.
By SEM (Scanning Electron Microscope, SEM) after measuring thickness, pore size, section and the surface state of the hollow fiber separating film of manufacturing according to said method, be shown in Fig. 1 and Fig. 2, can confirm spherical zincblende (
sphalerite) the connected shape of structure.In addition, the method by < experimental example > measure manufacturing hollow fiber separating film basic physical properties and be shown in Table 1.
< embodiment 2>
Except replacing outside the PEI of embodiment 1 with polyimides (PI, vapour bar polymer (Ciba polymer) company, Matrimid5218), adopt the method identical with embodiment 1 to manufacture hollow fiber separating film.
< embodiment 3>
Except replacing outside the PEI of embodiment 1 with polyamide (PA, Ames chemistry (EMS-Grivory) company, Grivory G16), adopt the method identical with embodiment 1 to manufacture hollow fiber separating film.
< embodiment 4>
Except replacing outside the PEI of embodiment 1 with Triafol T (CTA, Yi Shiman (EASTMAN) company, CA-436-80S), adopt the method identical with embodiment 1 to manufacture hollow fiber separating film.
< embodiment 5>
Except replacing with acetophenone (Acetophenone) the gamma-butyrolacton (GBL) of embodiment 1, adopt the method identical with embodiment 1 to manufacture hollow fiber separating film.
< embodiment 6>
Except replacing with isophorone (isophorone) the gamma-butyrolacton (GBL) of embodiment 1, adopt the method identical with embodiment 1 to manufacture hollow fiber separating film.
< comparative example 1>
Except replacing outside the PEI of embodiment 1 with polyacrylonitrile (PAN, aldrich (Aldrich) company), adopt the method identical with embodiment 1 to manufacture hollow fiber separating film.
< comparative example 2>
Adopt the method identical with embodiment 1 to manufacture hollow fiber separating film, but do not use hydrophilic macromolecule in composition, but be that resin 40 % by weight, gamma-butyrolacton (GBL) 60 % by weight are mixed and manufacture by Kynoar.
< comparative example 3>
While comparing with comparative example 2, except replacing gamma-butyrolacton (GBL) with METHYLPYRROLIDONE (NMP) and stirring at 150 DEG C, adopt the method identical with comparative example 1 to manufacture hollow fiber separating film.
< comparative example 4>
While comparing with comparative example 2, except replacing gamma-butyrolacton (GBL) with dimethylacetylamide (DMAc), adopt the method identical with comparative example 2 to manufacture hollow fiber separating film.
< experimental example >
1. pure water sees through flow measurement
The hollow fiber separating film self obtaining in above-described embodiment 1～6 and comparative example 1～3 is manufactured to the module with certain length and number, uses at normal temperatures TMP(Trans Membrane Pressure) 1kgf/cm
2pressure to go out-to enter (Out-In) mode force (forcing) pump pure water that pressurizes, thus measure.
2. the mensuration of average pore size
Measure the hollow fiber separating film of manufacturing in described embodiment 1～6 and comparative example 1～3 by Capillary Flow pore analysis instrument (Capillary Flow Porometer).
3. contact angle determination
Measure the hollow fiber separating film of manufacturing in described embodiment 1～6 and comparative example 1～3 in the mode of dynamic contact angle (dynamiccontact angle) by KRSS K100 surface tension instrument (Tensiometers).
4. stretching strength determination
Measure the hot strength of the hollow fiber separating film of manufacturing in described embodiment 1～6 and comparative example 1～3 with micro-stretching strength determination instrument (Micro-Forcing Tester).
As above-mentioned experimental example, the basic physical properties of the hollow fiber separating film to manufacturing is measured, and the results are shown in following table 1.
Table 1
Experimental result shows, embodiment 1～6 at hole size, see through flow, contact angle and fracture strength etc. and guaranteed excellent specific property aspect all, and the characteristic of embodiment 1～3 and 5～6 is excellent especially.
Claims (12)
1. hydrophilicity kynoar is a manufacture method for hollow fiber separating film, comprising:
(i) obtain the step of spinning solution, the Kynoar that this spinning solution contains 10～60 % by weight is resin PVDF, the hydrophilic resin of more than one that select in the group being formed by PEI PEI, polyimides PI, polyamide PA and cellulose acetate CA of 5～30 % by weight, and the Weak solvent of 20～85 % by weight; And
(ii) described spinning solution carried out to spinning and manufacture the step of hollow fiber separating film.
2. the method for claim 1, is characterized in that, carries out described step (ii) by thermally induced phase separation.
3. the method for claim 1, is characterized in that, also comprises: by the described step step that (ii) the middle diffusion barrier of manufacturing stretches.
4. the method for claim 1, is characterized in that, does not comprise that operation, surface hydrophilic treatment process, porous that the separation membrane surface of manufacturing is applied give postprocessing working procedures in described step after (ii).
5. the method for claim 1, is characterized in that, more than one for selecting in the group being made up of PEI PEI, polyimides PI and polyamide PA of described hydrophilic resin.
6. the method for claim 1, is characterized in that, the weight average molecular weight of described hydrophilic resin is 100000～500000.
7. the method for claim 1, is characterized in that, more than one for selecting in the group being made up of gamma-butyrolacton, cyclohexanone, acetophenone and isophorone of described Weak solvent.
8. hydrophilicity kynoar is a hollow fiber separating film, and it is by the method manufacture described in any one in claim 1～7.
9. hydrophilicity kynoar is a hollow fiber separating film manufacture composition, comprises:
The Kynoar of 10～60 % by weight is resin PVDF;
The hydrophilic resin of more than one that select in the group being formed by PEI PEI, polyimides PI, polyamide PA and cellulose acetate CA of 5～30 % by weight; And
The Weak solvent of 20～85 % by weight.
10. composition as claimed in claim 9, is characterized in that, more than one for selecting in the group being made up of PEI PEI, polyimides PI and polyamide PA of described hydrophilic resin.
11. compositions as claimed in claim 9, is characterized in that, the weight average molecular weight of described hydrophilic resin is 100000～500000.
12. compositions as claimed in claim 9, is characterized in that, more than one for selecting in the group being made up of gamma-butyrolacton, cyclohexanone, acetophenone and isophorone of described Weak solvent.
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| KR1020110119649A KR101462939B1 (en) | 2011-11-16 | 2011-11-16 | Hydrophilic Polyvinylidene Fluoride Based Hollow Fiber Membrane and Preparing Method Thereof |
| KR10-2011-0119649 | 2011-11-16 | ||
| 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 (en) | 2016-08-24 |
| KR101462939B1 (en) | 2014-11-19 |
| KR20130053933A (en) | 2013-05-24 |
| WO2013073828A1 (en) | 2013-05-23 |
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