TW572775B - Multi-component composite membrane and method for preparing the same - Google Patents
Multi-component composite membrane and method for preparing the same Download PDFInfo
- Publication number
- TW572775B TW572775B TW90126417A TW90126417A TW572775B TW 572775 B TW572775 B TW 572775B TW 90126417 A TW90126417 A TW 90126417A TW 90126417 A TW90126417 A TW 90126417A TW 572775 B TW572775 B TW 572775B
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- item
- patent application
- scope
- polymer
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 22
- 239000012528 membrane Substances 0.000 title description 14
- 239000002131 composite material Substances 0.000 title 1
- 239000010408 film Substances 0.000 claims description 147
- 229920000642 polymer Polymers 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 46
- 239000002243 precursor Substances 0.000 claims description 46
- -1 polyethylene Polymers 0.000 claims description 40
- 238000002360 preparation method Methods 0.000 claims description 25
- 238000010884 ion-beam technique Methods 0.000 claims description 21
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229920001155 polypropylene Polymers 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 16
- 239000000470 constituent Substances 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 230000035699 permeability Effects 0.000 claims description 13
- 230000005855 radiation Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- 238000009736 wetting Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 229920000554 ionomer Polymers 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005373 pervaporation Methods 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 238000001223 reverse osmosis Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000011282 treatment Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 3
- RFSDQDHHBKYQOD-UHFFFAOYSA-N 6-cyclohexylmethyloxy-2-(4'-hydroxyanilino)purine Chemical compound C1=CC(O)=CC=C1NC1=NC(OCC2CCCCC2)=C(N=CN2)C2=N1 RFSDQDHHBKYQOD-UHFFFAOYSA-N 0.000 claims 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- 229920001296 polysiloxane Polymers 0.000 claims 2
- UMNVUZRZKPVECS-UHFFFAOYSA-N 2-propanoyloxyethyl propanoate Chemical compound CCC(=O)OCCOC(=O)CC UMNVUZRZKPVECS-UHFFFAOYSA-N 0.000 claims 1
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 claims 1
- 102000004190 Enzymes Human genes 0.000 claims 1
- 108090000790 Enzymes Proteins 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims 1
- 229920002125 Sokalan® Polymers 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- 238000001631 haemodialysis Methods 0.000 claims 1
- 230000000322 hemodialysis Effects 0.000 claims 1
- 229920000092 linear low density polyethylene Polymers 0.000 claims 1
- 239000004707 linear low-density polyethylene Substances 0.000 claims 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 229920000768 polyamine Polymers 0.000 claims 1
- 229920002098 polyfluorene Polymers 0.000 claims 1
- 229920000306 polymethylpentene Polymers 0.000 claims 1
- 239000011116 polymethylpentene Substances 0.000 claims 1
- 239000005033 polyvinylidene chloride Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 230000000191 radiation effect Effects 0.000 claims 1
- 230000009466 transformation Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000000137 annealing Methods 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229920006370 Kynar Polymers 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 230000004660 morphological change Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- 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
- B01D71/26—Polyalkenes
- B01D71/261—Polyethylene
-
- 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
- B01D71/26—Polyalkenes
- B01D71/262—Polypropylene
-
- 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
- B29C55/026—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets of preformed plates or sheets coated with a solution, a dispersion or a melt of thermoplastic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
- B29C55/065—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed in several stretching steps
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/24998—Composite has more than two layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Secondary Cells (AREA)
- Laminated Bodies (AREA)
- External Artificial Organs (AREA)
Description
572775 玖、發明說明.: 【發明所屬之技術領域】 相關應用對應參考 此發明申請案係以在2000年6月23曰向韓國工業 財產局(Korean Industrial Property Office)提出的第 2000 34948 $虎申請案為基礎’其内容併入本文中以供參 考0 發明背景 (a)發明領域 10本發明係與多成分組成薄膜及其製備方法有關,且更特 別地’係與包含有支持層和活性層之多成分組成薄膜, 該活性層係具有如傳統活性層般密集的結構,其能夠在 其上面依照加工條件而形成細孔,並藉著可控制大小的 細孔而改良透氣性,該組成薄膜具有活性層的特殊性 15 質,並藉由離子束輻射作用來強化支持層和活性層之間 的界面黏附強度,以及製備相同物之方法。 t Hi (b)相關的技藝的描述 現今有許多的薄膜類型正在使用,例如微量過渡 20 膜、超濾膜、氣體分離膜、全蒸發膜與逆滲透膜。 本發明係與微量過濾膜有關,並特別係與應用於可 充電的裡離子電池之分隔器有關’其包含如聚乙稀和聚 丙稀的聚稀煙。 當聚烯烴之一的高結晶性聚丙烯(HCPP)用於本 6 572775 發明的分隔器中.時’分隔器的透氣性被預期將會增加。 一般的聚丙烯之結晶度係低於50。/〇,但是Hcpp結晶 度係大於50%,而且鳴高度全同立構的,因此其密度、 熔點、溶解熱與結晶溫度高,且例如剛性、耐熱性、衝 5擊強度、抗刮痕性與尺寸安定性的特性是優良的。 一組成薄膜通常係由界面聚合作用、膜改質作用與 次塗作用來加以製備。藉由使用例如微量過濾膜或超濾 膜的微孔薄膜來作為一支持層,浸塗作用係廣泛地應用 於製備組成薄膜中,將談微孔薄膜以一當做一活性層使 10用的材料的溶液加以塗佈,並將該塗佈的薄膜弄乾。藉 著浸塗作用製備的組成薄膜,具有一包含有規律大小的 孔洞之支持層與一具有密集結構之活性層。該組成薄膜 在應用上受到限制,因為該活性層具有較少的類似於微 量過渡膜或超濾膜之相同尺寸的孔洞,而且其容易因為 15 在支持層和活性層之間的弱界面黏附強度而脫層。 此組成薄膜可如美國專利第3,249,1〇9、4,388,189, 和5,102,552號中所述的,藉由在微孔薄膜上塗佈一個 聚合物而製備。除此之外,一種親水性單體,例如丙稀 酸’與例如聚乙烯氧化物之聚合物,係以電暈處理來 20進行接枝作用,因而該薄膜係具有一個經修飾的表面, 且其因而特別具有如美國專利第4,346,142、5,085,775, 和5,294,346中所揭露的親水性。然而,雖然該膜具有 一經修飾的表面和親水性,由於該過程係為複雜的且膜 的透氣性並不理想,接枝聚合作用的方法並不常被應 7 572775 用。 一用於一般的電池之具有規則-大小的孔洞之分隔 器,其係以一聚合物電解質溶液一塗布,且其係在如美 國專利第5,716,421號和歐洲專利第0933824 A2號中 5所揭露之可充電的鋰離子電池中作為一分隔器。然而, 當分隔器係以前述的方法製備的時候,該薄膜係具有密 集的結構,也就是說,在膜的表面上沒有形成孔洞,且 通透性(例如透氣性)降低,且在支持層和活性的層之間 的界面黏附強度不足。 10 【發明内容】 發明摘要 本發明的一個目的是提供一包含有支持層和活性層 之多成分組成薄膜,該活性層係具有如傳統活性層般密 集的結構,其能夠在其上面依照加工條件而形成細孔, 15並藉著可控制大小的細孔而具有改良的透氣性,該組成 薄膜具有活性層的特殊性f,並藉由離子束輻射作用來 強化支持層和活性層之間的界面黏附強度,以及製備該 組成薄膜之方法。 為了要達成這個目的,本發明提供一種包含一支持 2〇層和二個活性層之多成分組成薄膜。 此外,本發明提供一多成分組成薄膜的製備方法, 其包含下列步驟: a)藉由將一作為一支持層之聚合物喷射入一擠 壓機内來製備一前驅物薄膜; 25 b)在低於該聚合物熔點的溫度下將該前驅物薄 8 膜退火·; C)在反應氣體的輔助下以離子束輻射照射在該 退火的前驅物薄膜的二表面或其中之一表面 上; d) 在該被離子束輻射照射之前驅物薄膜的二表 面上塗布以一聚合物溶液,其係用來作為一活 性層; e) 乾燥該塗佈的前驅物薄膜; f) 在低於室溫的溫度下’低溫延展該乾的前驅物 薄膜; δ)在低於聚合物熔點的溫度下,高溫延展該經低 溫延展的前驅物薄膜;以及 h)在低於聚合物熔點之溫度下,利用一張力熱固 化高溫度·延展的前驅物薄膜。 囷式簡要說明 、田隨附的圖式一起思考時,藉由參考下列的詳細描 述本發明及其許多伴隨的優點將更明白且更容易了解, 其中: 第1圖係表示根據本發明之實施例丨的組成薄膜的 表面之掃瞒式電子顯微鏡(SEM)相片;以及 第2圖係為表示依據比較例1的一習知組成薄膜表 面的SEM相片。 【實式】 發明的詳細說明 在下述的詳細描述中,僅僅藉著例示本發明之發明 572775 人所預想的最佳實施態樣來顯示並描述本發明之較佳具 體例。如同所將被了解的,本發明可以在各種明顯不同 的態樣中加以改良,而全部都不背離本發明。因此,圖 式和描述在本質上,係要被視為用於例示說明而不是用 5 於限制的。 本發明係在下述中加以詳細地描述。 本發明提供一種組成薄膜及其之製備方法,其包含 以一活性材料塗布一沒有孔洞之一般薄膜,而不是如傳 統方法的以一活性材料塗布一微孔薄膜。 10 本發明的組成薄膜係藉著結合運用傳統乾燥過程和 使用一溶液的相轉化作用而製備的,其中該等孔係藉由 延展作用而在該乾燥過程中形成。除此之外,當增加一 離子束輻射照射步驟至製備步驟中以製備本發明的薄膜 時,將改善在支持層和活性層之間的一界面鍵結。 15 使用一傳統乾燥過程的製備方法,係為在將聚合物 的結晶區域以一特定方向來定向之後,將一非結晶區域 經由冷的延伸作用來打破,同時結晶區域的方向的一致 性對於薄膜的特性是具有決定性的。 使用相轉化作用的方法,係為一種在調控的溫度下 20藉由聚合物和溶液的溶劑之相_分離或是在製備一聚合物 /合液之後使用無溶劑的方式來形成孔洞的方法。 為了要改良該表面’其運用了一離子束輻射照射過 程其中例如氫、氫、氧、氮和二氧化碳的氣想,係被 離子化並在具有反應氣體㈣境之下照射至該表面,該 10 572775 反應氣體係在該離子化氣體與該薄膜表面碰撞的時候要 與該離子以及該表面反應者。 在本發明中,為了要製備一作為一支持層之材料, 一前驅物薄膜係在該乾燥過程的一步驟中製備,其係被 5塗布以一用來作為一活性層的聚合物溶液,其係在適當 的情況下從聚合物溶液中相分離的,並且其係被延展, 而藉此該製備膜而在膜上形成孔洞。在該膜製備的時 候,為了要在支持層和活性層之間增加界面黏附強度, 離子束輻射照射過程係在塗布過程之前施行,因而改良 10 了膜之表面。本發明的組成薄膜包有孔含材料,其係分 別地用作支持層和活性層。在前驅物薄膜製備期間將聚 合物的結晶區域以某一方向來定向之後,藉由一延伸過 程來形成支持層的孔洞時,支持層與活性層的孔洞大小 和分布係彼此不同的。另一方面,活性層的孔洞係在經 15由相-轉化作用形成一緻密結構之聚合物薄膜之後,藉由 一延伸過程而形成。聚合物薄膜的微-裂縫和微-孔洞可以 在薄膜變延展之前依據相-轉化作用的條件而加以形成, 因此孔洞形成的程度是可依據相-轉化作用的條件而加以 控制的。 20 本發明的支持層與傳統的乾燥過程所製備的薄膜具 有相同的特性,同時該活性層會依據該加工條件而具有 各種不同大小的孔洞。除此之外,在支持層與活性層之 間的聚合物鏈中之相互-擴散作用以及在支持層和活性 層之間的表面化學鍵結的強度,係經由高溫延展作用與 25熱-固化作用而改善。當離子束照射到該等層次的時候, 11 572775 該表面的化學鍵可以進一步地加強。 用於本發明的支持層之材料並未限制於某些材料, 且其通常包含一或更多由下述材料組成之組群中所選出 之材料:高密度聚乙烯、低密度聚乙烯、線性低密度聚 5 乙烯、聚丙烯、高結晶性聚丙烯、聚乙烯-丙稀共聚物、 聚乙烯-丁烯共聚物、聚乙烯-己烯共聚物、聚乙烯-辛烯 共聚物、聚苯乙烯-乙烯-丁烯-苯乙烯共聚物、聚苯乙稀、 聚苯醚、聚楓、聚碳酸酯、聚酯、聚醯胺、聚胺基曱酸 脂、聚丙烯酸酯、聚偏二氣乙烯、聚偏氟乙烯、聚石夕氧 10 烷、聚烯烴、離聚物、聚曱基戊烯與氫化寡環戊二稀 (HOCP),以及其混合物,且較佳係僅使用為選自上述群 組的材料、摻合-材料或層合材料。 作為活性層的聚合物溶液的聚合物,係被依照該組 成薄膜的最後用途來選擇,其係較佳地包含至少一選自 15下列群組的材料,該群組包含有聚乙烯、聚丙烯、聚偏 氟乙烯、聚偏氟乙烯-六氟丙烯共聚物、聚環氧乙烷、聚 環氧丙烧、聚環氧丁烧,聚胺基甲酸醋,聚丙烯腈,聚 丙烯酸酯,聚丙烯酸,聚醯胺,聚丙烯醯胺、聚乙酸乙 烯酯、聚乙烯咄咯啶酮、聚三縮四乙二醇二丙烯酸酯、 20聚礙、聚苯醚、聚碳酸醋、聚酯、聚偏二氣乙烯、聚石夕 氧烷和聚烯烴離聚物,以及其之衍生物。 聚口物溶液的溶劑係依聚所使用的聚合物而選擇 的’且其係較佳包含至少一選自下列群組的溶劑:i•甲美 •2吡咯啶輞(NMP)、丙酮、乙醇、正_丙醇、正·丁醇二 己烧、環己醇、乙酸、乙酸乙醋、乙鍵、二甲基甲酿 胺(DMF)、一甲基乙醯胺(DMAc)、二噚烷、四氫呋 12 25 572775 喃(THF)、二甲亞颯(DMSO)、環己烷、苯、甲苯、二 甲苯與水,以及其之混合物。 該聚合物溶液係較佳地在下列的條件下使用。在該 聚合物溶液的塗布過程期間,一般沒有孔洞的薄膜係在 5 聚合物溶液中加以浸塗,該聚合物溶液的濃度係較佳地 在0.01 wt%或更多的。除此之外,該被塗布的聚合物之 乾燥係較佳的於選自由氮、氧、二氧化碳和空氣所構成 的群組之氣體環境下,在小於該溶劑的飽和蒸汽壓力之 飽和蒸汽壓力的氣體環境中,於相對濕度為1到100% 10 的條件下進行。活性層在塗層與乾燥之後,其厚度係較 佳地介於〇· 1到20/zm之間。 離子束輕射照射係在1 〇-1到1 〇-6 torr之間的真空 下進行,以活化電子、氫、氦、氧、氮、二氧化碳、空 氣、氟、氖、氫、氪和Νβ,以及其之混合物,上述的 15離子粒子具有從0·01到106千電子伏特的能量。較佳 地’該離子粒子的數量係介於105到個離子/cm2 之間。該反應氣體係i佳地包含氦、氫、氧、氮、氨、 一氧化碳、二氧化碳、氣氟碳化合物、甲烷、和Ν2〇 , 以及其之混合物,而且該反應氣體的流速係較佳地在0.5 20 到20毫升/分鐘之間。 依照本發明之組成薄蹲的製備方法包含以下的步 驟。 a)製備支持層的前驅物薄膜:前驅物薄膜係以一 具有T形鑄模或管狀鑄模之擠壓機,擠壓出一 13 572775 用來作為一支持層的聚合物而加以製備。 b) 退火·該刖驅物薄膜係在一乾燥爐中以一個低 於聚合物之熔點的溫度退火,因此該前驅物薄 膜具有增加的結晶性與彈性回復比例。 c) 在反應氣體的辅助下以離子束輻射照射:在前 驅物薄膜被置於在一真空室内且離子化氣體 係被注入離子搶之内而具有一能量後,該具有 一能量之離子粒子係依據電流的的不同,而被 輻射照射在該前驅物薄膜之一上或兩側上。調 控一能量源以使該等離子的能量係介於〇〇1 到106千電子伏排特之間。在輻射照射該離子 束時,一流速在〇·5到20毫升/分鐘間改變 之反應氣體係被注入該真空室内以修飾該前 驅物薄膜的表面。依據該多成分組成薄膜所需 要的物理性質,該前驅物薄膜之表面的修飾作 用可以在退火作用之前或之後進行。 d) 以一用來作為活性層的聚合物溶液來塗布該 前驅物薄膜:在一聚合物溶液藉由將一用來作 為活性層的聚合物溶解在一所欲的溶劑中而 製備之後,該前驅物薄膜係以該聚合物溶液加 以塗布的。該前驅物薄膜可以在退火作用之前 或之後使用。除此之外,在塗布之前,離子 束的輻射照射作用可以依據該多成分組成薄 膜所需要的物理性質,而在反應氣體的輔助 14 572775 下進行.。濃縮和塗布條件會依據所使用的材料 和δ亥組成薄膜的最終用同之不同而改變。· e) 藉由相-轉化·作用形成聚合物薄膜:在塗布作用 之後,該溶劑係在適當條件下被蒸發。該活性 5 層之聚合物薄膜的結構係有賴於乾燥作用的 狀況。 f) 低溫延展作用:微裂縫係在一低於室溫之溫度 下’使用一滾筒或其他不同的延展機具,被單 軸向地延展一經退火的薄膜而形成。 10 g)尚溫延展作用··藉由離子束輻射照射作用,並 在一個低於支持層和活性層之聚合物的熔點 之溫度下,經由使用滾筒或其他的機具來單軸 向地或雙軸向地延展該經低溫延展的薄膜,而 形成具有所欲尺寸的微孔洞並將機械特性提 15 供至薄膜。 h)熱固化作用·在鬲溫延展作用之後,該薄膜在 一低於支持與活性層之聚合物的熔點之溫 度,於張力下熱固化一段特定時間。 該多成分組成薄膜的製備步驟,描述了用來製備具 20有最適當之物理特性之薄膜的所有過程,其中依據這謝 物理特性該薄膜可以省略某些步驟或加入一些處理,而 也可藉由改變每個該等步驟的次序來加以製備。 下列各項實施例和比較例進一步的詳細說明本發 明,但是本發明並不侷限於這些例子。 25 藉著下列各項實施例和比較例所製備之微孔薄膜, 15 572775 係依照下列各項特性加以評估: a) 厚度; b) 透氣性:JIS<PSI17日本工業規格磅17; c) 孔洞大小:掃瞄式電子顥微鏡(SEM),穿隧式 5 電子顯微鏡(TEM); d) 界面黏附強度:JIS Z0237 ;且 e) 電解質的浸濕速率(所使用之電解質:碳酸乙 二醇(EC):二甲基碳酸鹽(dc) = 4:6) 實施例1:從高結晶性聚丙烯和Kynar461製備組 1〇 成薄膜 高結晶性聚丙烯係被用來作為一支持層,而聚偏氟 乙烯(PVDF)是用來作為活性層以製備一前驅物薄膜, 而該刖驅物薄膜係經過一乾燥過程來延展以製備一組成 薄膜。 15 (製備一前驅物薄膜) 尚結晶性聚丙烯係用來作為支持層的一個成分。其 熔化指數為0.50 g/min,密度為〇 91 g/cc,以示差掃描 熱量計(DSC)所測得之熔點為i66^c,結晶溫度為 U4.5C,結晶度為57%、用c13核磁共振(NMR)所測 20得全同立構規整度為98%,以及在溶解在二甲苯中之後 可測彳于約2%之無規立構部分,且前驅物薄膜係使用具 有T形鑄模和拉撐裝置的一單螺軸擠壓機,而自高結晶 性聚丙稀加以製備。擠出溫度和冷卻輥的溫度係分別為 220 C與80°C、拉緊速速率是2〇公尺/分鐘,且拉伸比 16 572775 率(e>dr)係為60 〇 (退火) 該製備之前驅物薄膜係在一個乾燥的爐中以1 50 °C退火1小時。 5 (塗布作用) 在退火之後,藉由將具有低結晶度之Kynar461(Elf Atochem North America的一種產品)溶解在丙酮中而製 備之溶液’被浸塗在所製備出的前驅物薄膜之兩邊。當 的時候,該塗不作用係在相對濕度維特於6〇%之大氣 1〇下進行,而且丙酮係在相對濕度為6〇%的相同狀態下蒸 發。所塗布的Kynar461之厚度大約是3 /zm。 (低溫延展作用) 在塗布作用之後,該經塗布之薄膜係在室溫下,單 軸向地低溫延展至以薄膜的最初長度為準為50%之延 15 展比。 (局溫延展作用) 在低溫延展作用之後,該經低溫延展之薄膜係在 140 °C下,單軸地高溫延展到以薄膜最初長度為準為 100%之延展比。 20 (熱固化) 在經高溫延展的薄膜於.140°C在張力下熱固化1〇 分鐘之後,冷卻該熱固化之薄膜以製備一組成薄膜。 組成薄膜的性質係表示在表1中。 表1中顯示微孔洞如實施例1般的在活性層和支 17 572775 持層上形成,且相較於當Kynar461依據傳統製備方法 塗布在一分隔器上,而在用來作為一活性層的Kynar461 (參照第1圖與第2圖)上不形成微孔洞者,依據實施 例1之膜透氣性係被加以改良。除此之外,在支持層和 5活性層之間的界面黏附強度增加。一般認為該電解質的 浸濕速率,係由於形態上的改變與黏附強度的增大而增 加0 實施例2 :以離子束輻射照射自高結晶性聚丙稀與 Kynar461製備組成薄膜 、 10 除了離子束係在以Kynar461溶液塗布之前輻射照 射至刖驅物薄膜上之外’ 一組成薄膜係利用與實施例1 相同的方法加以製備。在前驅物薄膜利用與實施例丨相 同的方法製備之後,將其安置在一將壓力維持在1〇-5到 1(T6 torr之間的真空室之内,以離子搶將arg0I1陽離子 15 輻射照射到前驅物薄膜的兩邊,並且同時地用來作為反 應氣體之氧係以4毫升/分鐘的量注入該室之内被,以處 理該前驅物薄膜表面。離子束的能量係為〇·5千電子伏 特’且離子的輻射照射數量係為1〇16個離子/cm2。在離 子束輻射照射之後,一組成薄膜被以如實施例1中相同 20的方式製備。 在表1中,其顯示孔洞係如實施例1中般的在支 持層和活性層兩者之上形成:,且更特別地,該在支持層 和活性層之間的界面黏附強度以及電解質的浸濕速率係 少許地改善。 25 實施例3 ··自高密度聚乙烤Kynar461製備一薄膜。 18 572775 除了高密度聚乙烯係用於作為一支持層而非高結晶 性聚丙烯之外,一組成薄膜係以與實施例!相同的方式 加以製備。該高密度聚•乙烯具有〇·3克/iO分鐘的一個溶 化指數與0.964 g/cc的密度。前驅物薄膜係以與實施例 5 1相同的方式加以製備。該拉撐裝置的擠出溫度和冷卻 輥溫度分別是200°c與8(TC、該薄膜的拉撐速率是3〇 公尺/分鐘,且所製備之前驅物薄膜的拉伸比例係為8〇。 該所製備的前驅物薄膜係在乾造爐中以丨25退火j 小時。該經退火的前驅物薄膜之兩側係以與實施例i相 10同的方式塗布Kynar46卜該經塗布的前驅物薄膜係在室 溫下,單軸向地延展到以薄膜最初長度為準係為5〇%的 延展比,然後其在120°C下立刻被單軸地高溫延展到以 薄膜最初次長度為準係為5〇%的延展比。該經高溫延展 的薄膜係於120°C在張力下熱固化10分鐘,然後冷卻 15該經熱固化之薄膜以製備一組成薄膜。第1表中顯示該 所製備之組成薄膜的性質。 在表1中’可以發現孔洞係如實施例1中般的在 支持層和活性層兩者之上形成,且該界面黏附強度以及 電解質的浸濕速率係被改善。 2〇 比較例1 :由Ceigard2400和Kynar461製備之組 成薄膜 一活性層係藉由傳統的方法塗布在一個微孔薄膜 上。 僅由聚丙稀製備的Ceigard 2400 (Celanese公司的 19 572775 -個產品)係為在該多孔薄膜中作為支持層,而K,r 461係如例子丨、2和3中一樣作為一活性層,且該 Kynar461溶液係塗布在有孔洞的Ceigard 24⑼上,且 藉此製傷一組成薄膜。 5 第1和2圖表示比較例1的組成薄膜不具有孔 洞,不像依據本發明實施例之組成薄膜般的在活性層上 形成孔洞。 表1顯示該所製備的組成薄膜之特性。其顯示由 Ceigard2400和Kynar461所製備的組成薄膜,具備一個 10 太差勁而無法測量的透氣性,且界面黏附強度和電解質 的浸濕速率係較差的。
Table 1 表 1 實施例1 實施例 2 實施例 3 比較例1 厚度 (β m) 20 20 20 20 孔洞 大小 (V m) 支持 層 0.3 X 0.1 0.3 X 0.1 0.4 X 0.1 0.3 X 0.1 活性 層 0.8 X 0.3 0.8 X 0.3 0.6 X 0.3 無法測量 透氣性 (sec/100 cc) 560 565 620 無法測量 界面黏附 強度(gf) 180 250 240 85 電解質的 浸濕速率 (sec) 10 8 9 4 20 15 572775 藉著傳統的方法製備之組成薄膜具有一太差勁而無 法測量的透氣性,但$本發明的組成薄膜則具有一個介 於560到620 sec/100 cc之間的改良的透氣性,因為活 性層和支持層兩者具有一在適當的製備條件下可以製備 5之可控制大小的孔洞之致緻密結構。除此之外,位於組 成薄膜外侧上的活性層具良好的特性。也就是,本發明 的支持層具有與利用傳統的乾燥過程所製備的薄膜相同 的性質,且該活性層具有依據其加工條件而有的各種不 同大小的孔洞。 10 除此之外,當組成薄膜藉著一具有為85 gf的界面 黏附強度之傳統方法加以製備的時候,本發明的組成薄 膜將具有介於180到250 gf之間的改良界面黏附強 度。该改良的界面黏附強係源自於高溫度延伸作用與熱_ 固化作用,該界面黏附強度因為在支持和活性層的聚合 15物鏈之間的相互鍵結(mutual bond)加強而增加。界面黏 附強度可藉著離子束輻射照射作用而更進一步改良。 此外,該浸濕速率略微改善,且一般推測浸濕速率 的改善是導因於形態上的改變與界面黏強度增加。 雖然本發明已經參照較佳具體例而被詳細地描述, 2〇習於此藝者將會了解可以對其進行各種不同的修飾和替 換而不偏離在隨附的申請專利範圍中所述的本發明的精 神和範圍。 21 572775 【圖式簡單說明】 第1圖係表示根據本發明之實施例1的組成薄膜的 4 表面之掃瞄式電子顯微鏡(SEM)相片;以及 第2圖係為表示依據比較例1的一習知組成薄膜表面 5 的SEM相片。 【囷式之主要元件代表符號表】 22
Claims (1)
- 572775—Τ~Ί 拾、申請專利範圍: i· 一種具有改良的通透性之多成分組成薄膜,其包含有活性 層和支持層,其中該支持層係位於該活性層之間, 其中該活性層具有可調控大小之孔洞,該孔洞係使用 5 相轉化來形成,且 該活性層的一成分係為一或多種選自下列物質所組成 之群組的聚合物:聚乙烯、聚丙烯、聚偏氟乙烯、聚偏氟 乙烯-六氟丙烯共聚物、聚環氧乙烷、聚環氧丙烷、聚環氧 丁烷、聚胺基甲酸酯、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、 10 聚醯胺、聚丙烯醯胺、聚乙酸乙烯酯、聚乙烯吡咯啶酮、 聚三縮四乙二醇二丙婦酸酯、聚楓、聚苯醚、聚破酸酯、 聚酯、聚偏氯乙烯、聚矽氧烷和聚烯烴離聚物,以及其衍 生物。 2·如申請專利範圍第1項之多成分組成薄膜,其中該支持層 15 的一成分係至少為一選自下列物質所組成之群組的聚合 物··高密度聚乙烯、低密度聚乙烯、線性的低密度聚乙稀、 聚丙烯、高結晶性聚丙烯、聚乙烯-丙烯共聚物、聚乙烯_ 丁烯共聚物、聚乙烯-己烯共聚物,聚乙烯_辛烯共聚物、聚 苯乙烯·丁烯-苯乙烯共聚物、聚苯乙烯-乙烯_丁烯-苯乙烯共 20 聚物、聚苯乙烯、聚苯醚、聚颯、聚碳酸酯、聚酯、聚醯 胺、聚胺基甲酸酯、聚丙烯酸酯、聚偏氣乙烯、聚偏氟乙 烯、聚矽氧烷、聚烯烴、“聚物、聚甲基戊烯、與氫化募 環戊二烯(HOCP),以及其等之衍生物。 3·如申請專利範圍帛2項之多成分組成薄膜,其_該高結晶 25 性聚丙稀具有一或多項選自0.905 g/cc或更大之密度、164 23 572775 。以更高的熔點、125t或更高之結“度、50%或更大之 結晶度、96%或更大之全同立體異構規整度,以及州或 更少之無規立體異構部分所組成之群組義理性質。 4. 如申請專利範圍第1項之多成分組成薄膜,其中該支持層 的孔洞大小係介於〇·謝到1G “之間的範圍。 5. 如申请專利|&圍第1項之多成分故成薄膜,其中該支持層 的厚度係介於1到50//m之間的範圍。 6. 如申請專利範圍第i項之多成分組成薄膜,其中該活性層 的孔洞大小係介於0.01//111至1〇 em。 7·如申请專利範圍第1項之多成分組成薄膜,其中該活性層 的厚度係介於0·01到2〇//111之間。 8·如申請專利範圍第1項之多成分組成薄膜,其中該組成薄 膜的透氣性係等於或少於7,00〇 sec/10〇 cc。 9·如申請專利範圍第1項之多成分組成薄膜,其中該組成薄 膜的浸濕速率係等於或少於30秒。 10·如申請專利範圍第1項之多成分組成薄膜,其中該組成薄 膜包含二或更多之活性層與一或更多的支持層,且該組成 薄膜具有三層或複層之結構。 U·如申請專利範圍第1項之多成分組成薄膜,其中該支持層 係以申請專利範圍第2項的聚合物成分加以摻合或層合。 12·如申請專利範圍第1項之多成分組成薄膜,其中該組成薄 膜係用於水處理、血液透析作用、酵素純化、在藥物運輸 中作為貼布、氣體分離作用、過蒸發作用、逆滲透作用或 電解分離作用中。 24 572775 13.如申請專利範圍第1項之多成分組成薄膜,其係用來作為 電池之分隔器。 14·如申請專利範圍第Γ項之多成分組成薄膜,其係用來作為 可充電之鋰離子電池或可充電之鋰離子聚合物電池之分隔 5 器。 15. —種多成分組成薄膜的製備方法,其包含以下步驟: a) 藉由將一用來作為支持層之聚合物喷射入一擠壓機内 來製備一前驅物薄膜; b) 在一低於該聚合物熔點的溫度下將該前驅物薄膜退 10 火; c) 以離子束輻射照射在該經退火的前驅物薄膜之一侧或 兩侧的表面上; d) 在反應氣體的輔助下,在該經離子束輻射照射之前驅物 薄膜的兩側表面上塗布以一聚合物溶液,其係用來作為 15 一活性層; e) 乾燥該經塗布的前驅物薄膜; f) 在低於室溫的溫度下,低溫延展該經乾燥的前驅物薄 膜; g) 在一低於聚合物熔點的溫度下,高溫延展該經低溫延展 20 的前驅物薄膜;並且 h) 在低於聚合物的熔點之瀑度下,在張力下熱固化經高溫 延展的前驅物薄膜。 16.如申請專利範圍第15項的製備方法,其中步驟d)中之聚 合物溶液,係藉由浸塗作用而被塗布在該前驅物薄膜的兩 25 572775 侧上。 17. 如申請專利範圍第15項的製備方法,其中步驟(1)中之聚 合物溶液的濃度係等於或大於0.01 wt%。 18. 如申請專利範圍第15項的製備方法,其中步驟e)的乾燥 5 作用係在1到100%的相對濕度範圍之間進行。 19. 如申請專利範圍第15項的製備方法,其中步驟e)的乾燥 作用係在飽和蒸汽壓之下進行。 20. 如申請專利範圍第15項的製備方法,其中步驟e)的乾燥 作用係在一選自由氮、氧、二氧化碳和空氣所組成之群.組 10 的氣體環境之下進行。 21. 如申請專利範圍第15項的製備方法,其中該活性層具有一 範圍在0.1到20 的厚度,其係經過步驟d)和e) 之塗布作用與乾燥作用而形成。 22. 如申請專利範圍第15項的製備方法,其中步驟c)的該離 15 子束的輻射照射作用係於範圍在HT1到10_6 torr的真空 下進行。 23. 如申請專利範圍第15項的製備方法,其中步驟c)中之該 離子束輻射照射作用,係藉由活化選自以下群組之電子和氣 體而進行,該群組包含有:氦、氫、氧、氮、二氧化碳、空 20 氣、氟、氖、氬、氪、N20,以及其之混合物,因而該氣體 具有0.01到106千電子伐之間的能量;並將該離子束輻 射照射在該前驅物薄膜的表面上。 24. 如申請專利範圍第15項的製備方法,其中該離子的輻射照 射數量係介於1〇5到l〇2G離子/cm2的範圍。 26 572775 25.如申請專利範圍第15項的製備方法,其中步驟c)的輻射 照射作用係在選自於以下群組的氣體環境下進行,該群組包 含有氦、氫、氮、氨,一氧化碳、二氧化碳、氯氟甲烷、甲 烷與N20氣體環境,以及其之混合物。 5 26.如申請專利範圍第25項的製備方法,其中該反應氣體的 流速係介於0.5到20毫升/分鐘之間。 27. 如申請專利範圍第15項的製備方法,其中該多成分組成薄 膜的製備步驟,可以在不論在何種順序的結合中進行。 28. 如申請專利範圍第15項之製備方法,其中該聚合物溶液的 10 一溶劑係為一或多種選自下列物質組成之群組的溶劑:1- 甲基-2吡咯啶酮(NMP)、丙酮、乙醇、正-丙醇、正-丁醇、 正·己烷、環己醇、乙酸、乙酸乙酯、乙醚、二甲基甲醯胺 〇DMF)、二曱基乙醯胺(DMAc)、二哼烧、四氫吱喃 (THF)、二甲亞颯(DMSO)、環己烷、苯、甲苯、二曱苯與 15 水,以及其混合物。 27
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2000-0034948A KR100409017B1 (ko) | 2000-06-23 | 2000-06-23 | 다성분계 복합 분리막 및 그의 제조방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW572775B true TW572775B (en) | 2004-01-21 |
Family
ID=19673589
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW90126417A TW572775B (en) | 2000-06-23 | 2001-10-25 | Multi-component composite membrane and method for preparing the same |
Country Status (7)
Country | Link |
---|---|
US (1) | US7087269B2 (zh) |
EP (1) | EP1324817B1 (zh) |
JP (2) | JP4209669B2 (zh) |
KR (1) | KR100409017B1 (zh) |
CN (1) | CN100531874C (zh) |
TW (1) | TW572775B (zh) |
WO (1) | WO2001097957A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI393735B (zh) * | 2005-03-31 | 2013-04-21 | 聚烯烴微多孔膜及其製法 |
Families Citing this family (71)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8527026B2 (en) | 1997-03-04 | 2013-09-03 | Dexcom, Inc. | Device and method for determining analyte levels |
US6001067A (en) | 1997-03-04 | 1999-12-14 | Shults; Mark C. | Device and method for determining analyte levels |
CN1258234C (zh) * | 2000-08-12 | 2006-05-31 | Lg化学株式会社 | 多组分复合膜及其制备方法 |
US20030032874A1 (en) | 2001-07-27 | 2003-02-13 | Dexcom, Inc. | Sensor head for use with implantable devices |
JP2003062422A (ja) | 2001-08-27 | 2003-03-04 | Inst Of Physical & Chemical Res | 気体分離膜及びその製造方法 |
KR100472503B1 (ko) * | 2002-06-07 | 2005-03-10 | 삼성에스디아이 주식회사 | 세퍼레이터 및 이를 채용한 리튬전지 |
KR100573358B1 (ko) | 2002-09-17 | 2006-04-24 | 가부시키가이샤 도모에가와 세이시쇼 | 리튬이온2차전지용 세퍼레이터 및 이를 포함한리튬이온2차전지 |
KR100511634B1 (ko) * | 2003-05-20 | 2005-09-01 | 주식회사 화인폴 | 고성능 리튬폴리머 2차 전지용 분리막, 그 제조방법 및리튬폴리머 2차 전지 |
JP4610213B2 (ja) * | 2003-06-19 | 2011-01-12 | 三洋電機株式会社 | リチウム二次電池及びその製造方法 |
JP2005019156A (ja) * | 2003-06-25 | 2005-01-20 | Tomoegawa Paper Co Ltd | 電子部品用セパレータおよび電子部品 |
EP1648298A4 (en) | 2003-07-25 | 2010-01-13 | Dexcom Inc | OXYGEN-IMPROVED MEMBRANE SYSTEMS FOR IMPLANTABLE DEVICES |
US7276561B2 (en) * | 2003-08-28 | 2007-10-02 | Japan Atomic Energy Research Institute | Processes for producing nano-space controlled polymer ion-exchange membranes |
US20050202163A1 (en) * | 2004-03-09 | 2005-09-15 | Celgard Inc. | Method of making a composite microporous membrane |
KR20050093018A (ko) | 2004-03-18 | 2005-09-23 | 한국과학기술연구원 | 고효율 3차원 나노 구조 분리막 |
US8277713B2 (en) | 2004-05-03 | 2012-10-02 | Dexcom, Inc. | Implantable analyte sensor |
KR100511618B1 (ko) * | 2005-01-17 | 2005-08-31 | 이경범 | 약물방출 조절형 다층 코팅 스텐트 및 이의 제조방법 |
US8744546B2 (en) | 2005-05-05 | 2014-06-03 | Dexcom, Inc. | Cellulosic-based resistance domain for an analyte sensor |
GB2445487B (en) * | 2005-08-31 | 2011-11-02 | Sumitomo Chemical Co | Transistor, method for manufacturing same, and semiconductor device comprising such transistor |
TWI406891B (zh) | 2005-10-19 | 2013-09-01 | 聚烯烴多層微多孔膜之製法 | |
WO2007120381A2 (en) | 2006-04-14 | 2007-10-25 | Dexcom, Inc. | Analyte sensor |
CN101448563B (zh) | 2006-05-18 | 2013-01-23 | 玛里琳·雷纳 | 制造膜的方法及用于乳化的膜 |
US7811359B2 (en) * | 2007-01-18 | 2010-10-12 | General Electric Company | Composite membrane for separation of carbon dioxide |
WO2008143514A1 (en) * | 2007-05-24 | 2008-11-27 | Fujifilm Manufacturing Europe B.V. | Membrane comprising oxyethylene groups |
KR20100029775A (ko) * | 2007-05-24 | 2010-03-17 | 후지필름 매뉴팩츄어링 유럽 비.브이. | 옥시에틸렌기를 포함하는 멤브레인 |
CN101754794A (zh) * | 2007-05-24 | 2010-06-23 | 富士胶片制造欧洲有限公司 | 膜及其生产方法和用途 |
TWI367229B (en) * | 2007-10-05 | 2012-07-01 | Toray Tonen Specialty Separato | Microporous polymer membrane |
KR101151189B1 (ko) * | 2007-10-26 | 2012-06-08 | 아사히 가세이 케미칼즈 가부시키가이샤 | 기체 분리막 |
US8583204B2 (en) | 2008-03-28 | 2013-11-12 | Dexcom, Inc. | Polymer membranes for continuous analyte sensors |
US8682408B2 (en) | 2008-03-28 | 2014-03-25 | Dexcom, Inc. | Polymer membranes for continuous analyte sensors |
US11730407B2 (en) | 2008-03-28 | 2023-08-22 | Dexcom, Inc. | Polymer membranes for continuous analyte sensors |
CN102017233A (zh) * | 2008-04-08 | 2011-04-13 | Sk能源株式会社 | 具有高温热稳定层的多孔聚烯烃复合膜的制造方法 |
US8560039B2 (en) | 2008-09-19 | 2013-10-15 | Dexcom, Inc. | Particle-containing membrane and particulate electrode for analyte sensors |
DE102008054187B4 (de) * | 2008-10-20 | 2014-08-21 | Dritte Patentportfolio Beteiligungsgesellschaft Mbh & Co.Kg | Lithiumionen-Akku und Verfahren zur Herstellung eines Lithiumionen-Akkus |
KR100911753B1 (ko) | 2009-02-04 | 2009-08-10 | (주)씨에스텍 | 경피투여형 패치제 및 이의 제조방법 |
US8118910B2 (en) * | 2009-03-23 | 2012-02-21 | General Electric Company | Layered filtration membrane and methods of making same |
WO2010144057A1 (en) * | 2009-06-10 | 2010-12-16 | National University Of Singapore | Double selective-layer membranes |
KR20110032679A (ko) * | 2009-09-23 | 2011-03-30 | 현대자동차주식회사 | 광택특성이 향상된 플라스틱 및 플라스틱 표면의 광택 처리 방법 |
KR101134480B1 (ko) * | 2009-09-28 | 2012-04-13 | 현대자동차주식회사 | 나노 엠보 패턴 표면을 갖는 플라스틱 및 이의 제조 방법 |
JP2012015073A (ja) * | 2010-07-05 | 2012-01-19 | Asahi Kasei E-Materials Corp | 微多孔性フィルム、その製造方法及び電池用セパレータ |
CN102151492B (zh) * | 2011-03-28 | 2013-01-16 | 昊辰(无锡)塑业有限公司 | 用于污水处理的分离膜及其制备方法 |
EP2714250A4 (en) * | 2011-05-25 | 2015-03-11 | Dalian Chemical Physics Inst | MEMBRANES |
CN102820444B (zh) * | 2011-06-10 | 2015-09-30 | 比亚迪股份有限公司 | 一种电池隔膜及其制备方法 |
CA2836812C (en) * | 2011-07-12 | 2018-07-10 | University Of Tasmania | Use of porous polymer materials for storage of biological samples |
KR101440971B1 (ko) * | 2012-01-05 | 2014-09-17 | 주식회사 엘지화학 | 내오염성이 우수한 역삼투막 및 그 제조방법 |
JP5946909B2 (ja) * | 2012-05-24 | 2016-07-06 | エルジー・ケム・リミテッド | 逆浸透分離膜の製造方法及びそれにより製造された逆浸透分離膜 |
KR20140052412A (ko) | 2012-10-24 | 2014-05-07 | 삼성에스디아이 주식회사 | 리튬 이차 전지 및 이의 제조방법 |
KR101578582B1 (ko) | 2012-11-21 | 2015-12-17 | 주식회사 엘지화학 | 내염소성이 우수한 고유량 수처리 분리막 |
US9211507B2 (en) | 2012-11-21 | 2015-12-15 | Lg Chem, Ltd. | Water-treatment separating membrane of high flux having good chlorine resistance and method of manufacturing the same |
KR20140115275A (ko) * | 2013-03-20 | 2014-09-30 | 주식회사 엘지화학 | 전기화학소자용 분리막 및 그의 제조방법 |
EP3180113B1 (en) * | 2014-08-12 | 2020-05-06 | DuPont Safety & Construction, Inc. | Process for making membranes |
EP3051609A1 (en) * | 2015-01-29 | 2016-08-03 | Innovia Films Limited | Plasma-treated separator |
WO2016120580A1 (en) * | 2015-01-29 | 2016-08-04 | Innovia Films Limited | Separator |
CN104888625A (zh) * | 2015-05-20 | 2015-09-09 | 苏州市贝克生物科技有限公司 | 一种聚丙烯腈血液透析膜及其制备方法 |
KR102013914B1 (ko) | 2015-11-12 | 2019-08-23 | 주식회사 엘지화학 | 겔 폴리머 전해질의 제조를 위한 경화용 다이 및 이를 사용한 겔 폴리머 전지셀의 제조방법 |
KR102034459B1 (ko) * | 2015-12-30 | 2019-11-18 | 주식회사 엘지화학 | 분리막 |
JP6759511B2 (ja) * | 2016-03-16 | 2020-09-23 | 住友電工ファインポリマー株式会社 | 積層体 |
CN108452689A (zh) * | 2017-03-06 | 2018-08-28 | 青岛致用新材料科技有限公司 | 一种高选择性全脂环族聚酰胺纳滤膜及其制备方法 |
CN107065042B (zh) * | 2017-05-05 | 2020-02-14 | 湖北松诺电子有限公司 | 一种薄膜透镜及其制备工艺 |
US10896804B2 (en) * | 2017-07-27 | 2021-01-19 | Lawrence Livermore National Security, Llc | Planarization, densification, and exfoliation of porous materials by high-energy ion beams |
US11241848B2 (en) | 2017-08-17 | 2022-02-08 | Lg Chem, Ltd. | Post-processing method for polymer electrolyte membrane |
JP2019063727A (ja) * | 2017-09-29 | 2019-04-25 | 三菱製紙株式会社 | 半透膜支持体 |
CN111093811B (zh) | 2017-10-05 | 2022-05-24 | 费森尤斯医疗保健控股公司 | 聚砜-氨基甲酸酯共聚物、包含其的膜和产品及其制备和使用方法 |
JP7015159B2 (ja) * | 2017-12-08 | 2022-02-02 | 旭化成株式会社 | 多層セパレータ、並びにその捲回体及び製造方法 |
JP7495266B2 (ja) | 2019-04-18 | 2024-06-04 | 住友化学株式会社 | 電池用セパレータの製造システムおよび製造方法 |
CN110170255B (zh) * | 2019-06-03 | 2021-12-28 | 哈尔滨工业大学(威海) | 一种基于聚丙烯腈超亲水膜的制备方法 |
CN110548421B (zh) * | 2019-08-27 | 2022-03-08 | 武汉艾科滤膜技术有限公司 | 一种强吸附型超滤膜的制备方法及应用 |
CN110479102A (zh) * | 2019-09-03 | 2019-11-22 | 盐城海普润膜科技有限公司 | 渗透蒸发脱盐非对称膜及其制备方法 |
CN112973458B (zh) * | 2021-02-08 | 2022-12-27 | 中国科学院近代物理研究所 | 离子径迹多孔膜及其物理制备方法与应用 |
CN114204142B (zh) * | 2021-12-02 | 2023-08-11 | 厦门大学 | 一种全固态电池界面缓冲层、制备方法及其电池 |
CN114243222B (zh) * | 2021-12-23 | 2022-09-20 | 中材锂膜有限公司 | 截面结构一致性高的隔膜及其制备方法 |
WO2024070574A1 (ja) * | 2022-09-26 | 2024-04-04 | 日東電工株式会社 | 浸透気化膜 |
Family Cites Families (54)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3249109A (en) | 1963-11-01 | 1966-05-03 | Maeth Harry | Topical dressing |
DE2724131C2 (de) * | 1977-05-27 | 1982-06-09 | C. Conradty Nürnberg GmbH & Co KG, 8505 Röthenbach | Plattenförmiger Kohlenstoffkörper und Verfahren zu seiner Herstellung |
JPS54102292A (en) | 1978-01-30 | 1979-08-11 | Mitsubishi Rayon Co Ltd | Composite hollow yarn and gas selective permeating method used above yarn |
JPS55105968A (en) * | 1979-02-05 | 1980-08-14 | Japan Atom Energy Res Inst | Manufacturing method of separator for cell |
US4294893A (en) * | 1979-05-21 | 1981-10-13 | Centro Ricerche Fiat S.P.A. | Graphite-resin composite electrode structure, and a process for its manufacture |
US4346142A (en) | 1979-09-04 | 1982-08-24 | Celanese Corporation | Hydrophilic monomer treated microporous films and process |
JPS5695304A (en) | 1979-12-28 | 1981-08-01 | Teijin Ltd | Perm selective composite membrane and its production |
US4438185A (en) * | 1980-07-31 | 1984-03-20 | Celanese Corporation | Hydrophilic polymer coated microporous membranes capable of use as a battery separator |
JPS57212232A (en) | 1981-06-24 | 1982-12-27 | Asahi Chem Ind Co Ltd | Composite hydrophilic membrane and its preparation |
JPS5820421A (ja) * | 1981-07-30 | 1983-02-05 | Toray Ind Inc | 多孔質ポリプロピレンフイルムの製造方法 |
DE3280189D1 (de) * | 1981-12-18 | 1990-07-19 | Cuno Inc | Verstaerkte mikroporoese membran. |
US4603109A (en) * | 1984-06-01 | 1986-07-29 | Norton Company | Method and apparatus for contacting reactants in chemical and biological reactions |
JPS62117811A (ja) * | 1985-11-13 | 1987-05-29 | Mitsubishi Rayon Co Ltd | 複合中空繊維状膜の製造法 |
US4814082A (en) * | 1986-10-20 | 1989-03-21 | Memtec North America Corporation | Ultrafiltration thin film membranes |
US4863604A (en) * | 1987-02-05 | 1989-09-05 | Parker-Hannifin Corporation | Microporous asymmetric polyfluorocarbon membranes |
US5102552A (en) | 1987-12-16 | 1992-04-07 | Hoechst Celanese Corporation | Membranes from UV-curable resins |
US4919856A (en) * | 1988-02-23 | 1990-04-24 | Dainippon Ink And Chemicals, Inc. | Process for producing membranes for use in gas separation |
US5273657A (en) * | 1989-04-18 | 1993-12-28 | Daicel Chemical Industries, Ltd. | Process for preparing modified porous membrane |
ATE129430T1 (de) * | 1989-07-14 | 1995-11-15 | Dow Chemical Co | Isotrope oder anisotrope mikroporöse membranen aus syndiotaktischem polystyrol und herstellungsverfahren. |
JPH0365229A (ja) | 1989-07-31 | 1991-03-20 | Toray Ind Inc | 浸透気化用複合膜 |
US5085775A (en) | 1990-12-05 | 1992-02-04 | Allied-Signal Inc. | Thin film composite ultrafiltration membrane |
US5677360A (en) * | 1991-02-13 | 1997-10-14 | Mitsubishi Rayon Co., Ltd. | Hydrophilic polymer alloy, fiber and porous membrane comprising this polymer alloy, and methods for preparing them |
US5281491A (en) * | 1991-12-20 | 1994-01-25 | W. R. Grace & Co. | Battery separator |
US5294342A (en) | 1992-10-01 | 1994-03-15 | Hoechst Celanese Corporation | Composite porous membranes |
JPH06142468A (ja) * | 1992-11-11 | 1994-05-24 | Dainippon Ink & Chem Inc | 細孔を有する表面親水性膜の製造方法 |
US5514461A (en) * | 1993-10-05 | 1996-05-07 | Kureha Chemical Industry Co., Ltd. | Vinylidene fluoride porous membrane and method of preparing the same |
NL9401260A (nl) * | 1993-11-12 | 1995-06-01 | Cornelis Johannes Maria Van Ri | Membraan voor microfiltratie, ultrafiltratie, gasscheiding en katalyse, werkwijze ter vervaardiging van een dergelijk membraan, mal ter vervaardiging van een dergelijk membraan, alsmede diverse scheidingssystemen omvattende een dergelijk membraan. |
KR0123279B1 (ko) * | 1994-05-31 | 1997-11-11 | 하기주 | 염제거능이 우수한 복합반투막 및 그 제조방법 |
CN1038562C (zh) | 1994-06-20 | 1998-06-03 | 中国科学院化学研究所 | 聚丙烯微孔膜为基膜的离子交换膜及其制法 |
US5783079A (en) | 1994-08-29 | 1998-07-21 | Toyo Boseki Kabushiki Kaisha | Composite hollow fiber membrane and process for its production |
JP3250644B2 (ja) * | 1995-04-12 | 2002-01-28 | 東洋紡績株式会社 | 複合中空糸膜およびその製造方法 |
TW297171B (zh) * | 1994-12-20 | 1997-02-01 | Hoechst Celanese Corp | |
US5620807A (en) * | 1995-08-31 | 1997-04-15 | The Dow Chemical Company | Flow field assembly for electrochemical fuel cells |
JPH09213295A (ja) * | 1996-02-02 | 1997-08-15 | Nitto Denko Corp | 電池用セパレータ |
JP3939778B2 (ja) * | 1996-02-09 | 2007-07-04 | 日東電工株式会社 | 電池用セパレータ |
DE19629154C2 (de) | 1996-07-19 | 2000-07-06 | Dornier Gmbh | Bipolare Elektroden-Elektrolyt-Einheit |
JP3645051B2 (ja) * | 1996-11-22 | 2005-05-11 | 三菱樹脂株式会社 | 多孔質複層プラスチックフィルタおよびその製造方法 |
US5716421A (en) * | 1997-04-14 | 1998-02-10 | Motorola, Inc. | Multilayered gel electrolyte bonded rechargeable electrochemical cell and method of making same |
JPH1149882A (ja) | 1997-08-05 | 1999-02-23 | Nitto Denko Corp | 多孔質膜およびそれを用いた電池用セパレータ |
KR19990040319A (ko) * | 1997-11-17 | 1999-06-05 | 성재갑 | 고분자 표면의 이온 입자 조사에 의한 미세 기공 막의 제조 |
DE19751297A1 (de) * | 1997-11-19 | 1999-05-20 | Siemens Ag | Gasdiffusionselektrode und deren Herstellung |
US6322923B1 (en) * | 1998-01-30 | 2001-11-27 | Celgard Inc. | Separator for gel electrolyte battery |
EP0973223A1 (en) * | 1998-02-05 | 2000-01-19 | Mitsubishi Denki Kabushiki Kaisha | Lithium battery and method for manufacturing the same |
JPH11300180A (ja) * | 1998-02-20 | 1999-11-02 | Mitsubishi Chemical Corp | 多孔質樹脂膜 |
JPH11297297A (ja) | 1998-04-10 | 1999-10-29 | Ube Ind Ltd | 多孔質フイルムの製造方法および多孔質フイルム |
US6753114B2 (en) * | 1998-04-20 | 2004-06-22 | Electrovaya Inc. | Composite electrolyte for a rechargeable lithium battery |
KR100271926B1 (ko) * | 1998-08-27 | 2000-12-01 | 장용균 | 미다공성 폴리올레핀 필름의 제조방법 |
JP2000093768A (ja) * | 1998-09-21 | 2000-04-04 | Nok Corp | 複合多孔質中空糸膜 |
WO2000032294A1 (en) | 1998-12-02 | 2000-06-08 | Lg Chemical Ltd. | Methods for reforming polymer surface for improved wettability |
JP2000317280A (ja) * | 1999-05-06 | 2000-11-21 | Teijin Ltd | 超高分子量ポリエチレン多孔膜を濾過媒体とするフィルター |
US6451864B1 (en) * | 1999-08-17 | 2002-09-17 | Battelle Memorial Institute | Catalyst structure and method of Fischer-Tropsch synthesis |
US6830849B2 (en) * | 2000-01-10 | 2004-12-14 | Lg Chemical Co., Ltd. | High crystalline polypropylene microporous membrane, multi-component microporous membrane and methods for preparing the same |
CN1258234C (zh) * | 2000-08-12 | 2006-05-31 | Lg化学株式会社 | 多组分复合膜及其制备方法 |
US6579342B2 (en) * | 2001-02-07 | 2003-06-17 | Pall Corporation | Oleophobic membrane materials by oligomer polymerization for filter venting applications |
-
2000
- 2000-06-23 KR KR10-2000-0034948A patent/KR100409017B1/ko active IP Right Grant
-
2001
- 2001-06-22 JP JP2002503431A patent/JP4209669B2/ja not_active Expired - Lifetime
- 2001-06-22 CN CNB018017517A patent/CN100531874C/zh not_active Expired - Lifetime
- 2001-06-22 US US10/049,212 patent/US7087269B2/en not_active Expired - Lifetime
- 2001-06-22 WO PCT/KR2001/001076 patent/WO2001097957A1/en active Application Filing
- 2001-06-22 EP EP01943923.1A patent/EP1324817B1/en not_active Expired - Lifetime
- 2001-10-25 TW TW90126417A patent/TW572775B/zh not_active IP Right Cessation
-
2008
- 2008-06-26 JP JP2008167991A patent/JP4988656B2/ja not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI393735B (zh) * | 2005-03-31 | 2013-04-21 | 聚烯烴微多孔膜及其製法 |
Also Published As
Publication number | Publication date |
---|---|
US20040213985A1 (en) | 2004-10-28 |
EP1324817A4 (en) | 2006-08-23 |
US7087269B2 (en) | 2006-08-08 |
KR20020001035A (ko) | 2002-01-09 |
CN1383390A (zh) | 2002-12-04 |
JP4988656B2 (ja) | 2012-08-01 |
JP2008302359A (ja) | 2008-12-18 |
KR100409017B1 (ko) | 2003-12-06 |
EP1324817A1 (en) | 2003-07-09 |
JP4209669B2 (ja) | 2009-01-14 |
WO2001097957A1 (en) | 2001-12-27 |
JP2003535683A (ja) | 2003-12-02 |
CN100531874C (zh) | 2009-08-26 |
EP1324817B1 (en) | 2013-09-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW572775B (en) | Multi-component composite membrane and method for preparing the same | |
KR100435233B1 (ko) | 미세 기공막 및 그의 제조 방법 | |
EP1310005B9 (en) | Multi-component composite film method for preparing the same | |
US20150306539A1 (en) | Microporous laminated membrane and method for producing the same | |
JP2002355938A (ja) | 複合膜、その製造方法及びそれを用いた電池用セパレータ又はフィルター | |
KR20210029294A (ko) | 리튬 이온 이차 전지용 다층 하이브리드 전지 분리기 및 이의 제조방법 | |
KR100373204B1 (ko) | 고분자 전해질용 다성분계 복합 분리막 및 그의 제조방법 | |
KR100378022B1 (ko) | 두께방향으로기공크기차이를갖는미세기공막의제조 | |
KR100417254B1 (ko) | 고결정성 폴리프로필렌의 미세 기공막 및 이의 제조방법 | |
JP2023054658A (ja) | ポリアミド多孔質膜及びポリアミド多孔質膜の製造方法 | |
KR20000051284A (ko) | 미세 기공막 및 그의 제조 방법 | |
KR20000055678A (ko) | 다단계 공정을 이용한 미세 기공막의 제조 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GD4A | Issue of patent certificate for granted invention patent | ||
MM4A | Annulment or lapse of patent due to non-payment of fees |