CN1235953C - 多孔薄膜 - Google Patents
多孔薄膜 Download PDFInfo
- Publication number
- CN1235953C CN1235953C CNB021055297A CN02105529A CN1235953C CN 1235953 C CN1235953 C CN 1235953C CN B021055297 A CNB021055297 A CN B021055297A CN 02105529 A CN02105529 A CN 02105529A CN 1235953 C CN1235953 C CN 1235953C
- Authority
- CN
- China
- Prior art keywords
- porous membrane
- film
- fibril
- average pore
- branch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011148 porous material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 5
- 238000002459 porosimetry Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 71
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 230000010220 ion permeability Effects 0.000 abstract description 23
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- 230000005855 radiation Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 polybutylene terephthalate Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 235000009814 Luffa aegyptiaca Nutrition 0.000 description 5
- 244000302544 Luffa aegyptiaca Species 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
-
- 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
- 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
- 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
- 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
- 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
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; Separators
-
- 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
-
- 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
- H01M50/44—Fibrous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0658—PE, i.e. polyethylene characterised by its molecular weight
- B29K2023/0683—UHMWPE, i.e. ultra high molecular weight polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2091/00—Use of waxes as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
-
- 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
- H01M50/497—Ionic conductivity
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
Abstract
本发明提供了一种实际具有足够机械强度和优异离子透过性的多孔薄膜。公开了一种具有微孔的由热塑性树脂制成的多孔薄膜,其中,所述微孔由三维网络形成,这种三维网络由在薄膜的一个方向延伸的主干原纤和分支原纤形成的,主干原纤通过分支原纤相互连接,并且所形成的分支原纤的密度高于所形成的主干原纤的密度,由泡点法(ASTM-F316-86)测定的微孔平均孔隙直径d(μm)和由水银孔隙度法(JIS K1150)测定的微孔平均孔隙半径r(μm)满足下列关系:1.20≤2r/d≤1.70。
Description
技术领域
本发明涉及一种由热塑性树脂制成的多孔薄膜。本发明具体涉及一种由热塑性树脂制成的多孔薄膜,它优选地用作电解电容器、锂电池、蓄电池等的隔板。
背景技术
热塑性树脂制成的多孔薄膜用作透湿性雨衣;反渗透或超滤的薄膜;和电解电容器、锂电池、蓄电池等的隔板。
希望用作隔板的薄膜不仅含有电解质以防在阳极和阴极之间的电短路并具有机械稳定性,而且希望在电解质中的离子透过性优异。特别地,随着近来电池容量的增大,非常希望改善离子透过性的改善。
作为使用热塑性树脂作为原料的隔板,在例如JP-B50-2176中公开了一种聚烯烃多孔薄膜。在该出版物中公开的多孔薄膜中的孔隙结构不是网络结构,而是在薄膜深度方向笔直地形成空隙的结构,这种多孔薄膜机械强度优异,但是离子透过性差。
为了改善离子透过性,在现有技术中已经提出了使多孔薄膜更薄,但是在使薄膜更薄时,产生例如机械强度降低、危险的电短路等问题。另一方面,为了防止电短路并改善机械强度而使多孔薄膜更厚时,离子透过性降低。所以,不能同时获得这些希望的性能,并且需要开发一种多孔薄膜,这种多孔薄膜与传统的多孔薄膜相比,尽管具有相同的厚度,但是离子透过性更好。
发明内容
在上述情况下,本发明的目的是提供一种多孔薄膜,它实际上具有足够的机械强度,同时离子透过性优异。
为了开发一种主要用作电池隔板时的离子透过性优异的薄膜,本发明人进行了广泛的研究,结果,他们发现在薄膜中的特定孔隙结构可以解决上述问题,因此完成了本发明。
本发明涉及一种具有微孔的由热塑性树脂制成的多孔薄膜,其中,微孔由三维网络形成,这种三维网络由在薄膜的一个方向延伸的主干原纤和分支原纤形成,主干原纤通过分支原纤相互连接,并且所形成的分支原纤的密度高于所形成的主干原纤的密度,由泡点法(ASTM-F316-86)测定的微孔平均孔隙直径d(μm)和由水银孔隙率法(JIS K1150)测定的微孔平均孔隙半径r(μm)满足下列关系:
1.20≤2r/d≤1.70
这样构成的多孔薄膜比具有另一种孔隙结构的多孔薄膜离子透过性更高,因此作为电解电容器、锂电池、蓄电池等的隔板是优选的。
通过使所形成的分支原纤的密度高于所形成的主干原纤的密度,这种多孔薄膜在最大热收缩方向和与其垂直的方向之间的物理强度方面进行了良好的平衡。分支原纤和主干原纤在直线上的延伸不总是必须的。可以在电子显微镜下证实的主干原纤延伸的方向不特别限制,因为该方向在切割薄膜时决定。“在一个方向延伸”并不意味着所有的主干原纤在特定方向上平行延伸,而是指主干原纤在特定方向上平均定向同时有一定程度的弯曲。
所形成的分支原纤或主干原纤的密度是指在面积为1μm2的薄膜上存在的原纤数,并通过在扫描电子显微镜下观察薄膜表面来测定。具体地,通过数出在5×5μm2的区域内存在的原纤数来确定密度。本发明的多孔薄膜的孔隙结构称为“丝瓜结构”。
优选地,本发明的多孔薄膜的Gurley值为10-500秒/100cc,孔隙体积为40-80%,由泡点法测定的平均孔隙直径d为0.06-3μm。另外,薄膜的厚度优选的是1-200μm。这样构成的多孔薄膜在强度和离子透过性两方面都是明显优良的。
本发明的多孔薄膜特征在于由泡点法(ASTM-F316-86)测定的微孔平均孔隙直径d(μm)和由水银孔隙率法(JIS K1150)测定的微孔平均孔隙半径r(μm)满足下列关系:
1.20≤2r/d≤1.70
当2r/d的值小于1.20时,多孔薄膜的离子透过性差,而超过1.70时,多孔薄膜强度差。从薄膜强度方面来看,2r/d的值优选的是1.65或更小,更优选的是1.60或更小。
本发明的多孔薄膜的厚度(Y)通常为1-200μm,优选的是5-50μm,更优选的是5-30μm。当薄膜太厚时,薄膜的离子透过性差,而当薄膜太薄时,薄膜的物理强度差。当平均孔隙直径d(μm)和平均孔隙半径r(μm)偏离上面确定的关系时,薄膜不适合于用作隔板。
在上述多孔薄膜中,分支原纤优选的是在薄膜的最大热收缩方向上定向。
通过使分支原纤在薄膜的最大热收缩方向上定向,薄膜在最大热收缩方向上具有更高的机械强度。
在本发明的多孔薄膜中的微孔的平均孔隙直径优选的是0.06-3μm。
附图说明
图1是测量多孔薄膜的离子电导率的装置的示意图。
图2是实施例1中的多孔薄膜的电子显微照片。
图3是对比实施例1中的商品多孔薄膜的电子显微照片。
图4是表示比电导率随时间变化的测量结果图。
作为本发明的多孔薄膜的主要原料的热塑性树脂包括烯烃如乙烯、丙烯、丁烯和己烯的均聚物,或者两种或多种烯烃的共聚物的聚烯烃树脂,丙烯酸树脂如聚丙烯酸甲酯、聚甲基丙烯酸甲酯和乙烯-丙烯酸乙酯共聚物,苯乙烯树脂如丁二烯-苯乙烯共聚物、丙烯腈-苯乙烯共聚物、聚苯乙烯、苯乙烯-丁二烯-苯乙烯同聚物、苯乙烯-异戊二烯-苯乙烯共聚物和苯乙烯-丙烯酸共聚物,氯乙烯树脂如丙烯腈-氯乙烯共聚物和氯乙烯-乙烯共聚物,氟乙烯树脂如聚氟乙烯和聚偏二氟乙烯,聚酰胺树脂如6-尼龙、6,6-尼龙和12-尼龙,饱和的聚酯树脂如聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯,以及聚碳酸酯、聚苯醚、聚缩醛、聚苯硫醚、硅氧烷树脂、热塑性聚氨酯树脂、聚醚醚酮、聚醚酰亚胺和热塑性合成橡胶和它们的交联产物。
构成本发明的多孔薄膜的热塑性树脂可以是一种或多种树脂的混合物。
作为热塑性树脂,优选使用聚烯烃型树脂,因为其电化学稳定性或在电解质中的稳定性优良,并且可以在各种用途中用作离子透过性优良的多孔薄膜。
这种聚烯烃型树脂基于一种烯烃的聚合物或两种或多种烯烃的共聚物。用作聚烯烃树脂的原料的烯烃包括乙烯、丙烯、丁烯、己烯等。聚烯烃树脂的实例包括聚乙烯树脂如低密度聚乙烯、线型聚乙烯(乙烯-α-烯烃共聚物)和高密度聚乙烯,聚丙烯树脂如聚丙烯和乙烯-丙烯共聚物,以及聚(4-甲基戊烯-1)、聚(丁烯-1)和乙烯-醋酸乙烯酯共聚物。特别地,含有分子链长度为2850nm或更长的高分子链聚烯烃的多孔薄膜强度优良,因此可以使其更薄,同时保持机械强度。因此,可以进一步改善离子透过性。从多孔薄膜的强度方面来看,聚烯烃树脂优选的是含有至少10重量%,更优选的是至少20重量%,最优选的是至少30重量%的分子链长度为2850nm或更长的高分子链聚烯烃。
聚烯烃的分子链长度、重均分子链长度、分子量和重均分子量可以由GPC(凝胶渗透色谱法)测定,在特定分子链长度范围或特定分子量范围内混合的聚烯烃的比例(重量%)可以由GPC测量所获得的分子量分布曲线的积分来确定。
使用聚苯乙烯标样由GPC(凝胶渗透色谱法)测定的聚烯烃的分子链长度具体是由下列过程测定的参数。
即,在GPC测量中所用的移动相是一种溶剂,其中可以溶解待测的未知试样和已知分子量的聚苯乙烯标样。首先,由GPC测量具有不同分子量的许多聚苯乙烯标样,以确定每种聚苯乙烯标样的停留时间。使用聚苯乙烯的因子Q,测定每种聚苯乙烯标样的分子链长度,从而获知每种聚苯乙烯标样的分子链长度和其相应的停留时间。每种聚苯乙烯标样的分子量和分子链长度与因子Q具有下列关系:
分子量=分子链长度×因子Q
然后,由GPC测量未知试样,以获得停留时间与其流出成分之间的关系图。当用GPC测量聚苯乙烯标样过程中的停留时间为T的聚苯乙烯标样的分子链长度为L时,在用GPC测量未知试样过程中其停留时间同样为T的流出成分的分子链长度假定同样为L。从这一关系和聚苯乙烯标样的分子量与未知试样的流出成分的停留时间之间的关系出发,分子链长度的分布,即分子链长度与流出成分之间的关系被确定。
本发明的多孔薄膜可以含有填料,如有机或无机填料。
本发明的多孔薄膜可以包含添加剂,如拉伸助剂(例如脂肪酯和低分子量聚烯烃树脂)、稳定剂、抗氧化剂、紫外光吸收剂和阻燃剂。
当使用含有长度为2850nm或更长的高分子链的聚烯烃树脂作为本发明的多孔薄膜的原料时,用分段设计的双螺杆捏合机捏合原料树脂和无机化合物和/或树脂的细粉,使得这些材料被强制捏合,所捏合的混合物然后通过压延形成薄膜,所得的原膜用拉伸机拉伸,以获得本发明的多孔薄膜。
作为拉伸用的设备,可以使用任何已知的拉伸机而没有限制,一种优选的实例是拉幅机。
无机化合物细粉包括平均粒径为0.1-1μm的无机化合物,如氧化铝、氢氧化铝、氧化镁、氢氧化镁、水滑石、氧化锌、氧化铁、氧化钛、碳酸钙、碳酸镁等。特别地,使用碳酸钙或碳酸镁,在多孔薄膜制备后,优选的使用酸性水溶解并去除上述材料,以改善离子导电性。
组成本发明多孔薄膜的热塑性树脂可以已经通过辐射照射而交联。其中含有已交联的热塑性树脂的多孔薄膜在耐热性和强度方面优于用未交联的热塑性树脂制成的多孔薄膜。
当本发明的多孔薄膜用作可透过离子的薄膜时,在获得高离子导电性方面,厚度约为3-50μm的多孔薄膜是有效的。在这种情况下,通过辐射照射交联的热塑性树脂制成的多孔薄膜是更有效的。通常,当多孔薄膜成型成薄膜时,存在薄膜强度降低的问题。但是,厚度约为3-50μm并由辐射照射交联的热塑性树脂制成的本发明的薄膜可以用作离子导电性优异的高强度可透过离子的薄膜。
使用未交联的热塑性树脂生产的本发明的多孔薄膜用辐射照射后,可以获得交联的热塑性树脂制成的本发明的多孔薄膜。
虽然照射待交联的本发明的多孔薄膜的辐射种类不特别限制,但是,优选的是使用γ射线、α射线、电子射线等,其中,就生产率和安全性来说,特别优选的是使用电子射线。
作为辐射源,优选的是使用加速电压为100-3000kV的电子射线加速器。如果加速电压小于100kV,电子射线的穿透深度可能不够,而如果加速电压高于3000kV,照射设备的规模可能太大,并且经济上是不利的。用于辐射照射设备的实例包括Van de Graaff型电子射线扫描设备和电子幕型电子射线固定传送器传送装置。
辐射的吸收剂量优选的是0.1-100Mrad(毫拉德),更优选的是0.5-50Mrad。从辐射对树脂交联的作用来看,吸收的剂量优选的是0.1Mrad或更大,从树脂强度方面来看,吸收剂量优选的是100Mrad或更小。
用辐射照射本发明的多孔薄膜的气氛可以是空气,优选的是惰性气体,如氮气。
对于用辐射照射,本发明的多孔薄膜也可以通过事先把它与另一种单体化合物或聚合物混合或浸渍,然后通过辐射照射使其反应来交联或接枝聚合。与本发明的多孔薄膜混合或浸渍的化合物包括一种或多种化合物,例如苯乙烯、二乙烯基苯、丙烯酸、丙烯酸酯、甲基丙烯酸、甲基丙烯酸酯、氟化的化合物、这些单体或聚合物的磺酸酯衍生物和磷酸酯衍生物。
无论是否用辐射照射,本发明的多孔薄膜可以在其孔隙中浸渍另一种有机或无机化合物。浸渍多孔薄膜的化合物可以根据多孔薄膜的预期用途适当选择,并且该化合物的实例包括离子导电化合物如磷酸、硫酸、电解质和离子交换树脂、以及化学品如杀虫剂和农用化学品。
具体实施方式
实施例
下文中,参考实施例更详细地描述本发明,这些实施例不限制本发明。
实施例和对比实施例中的多孔薄膜的物理性质用下列评价方法来评价。
[评价方法]
(1)离子透过性的评价
通过测量比电导率来评价离子透过性。用于测量比电导率的实验室装置在图1中表明。测量装置11有一对电池12和13,待评价的多孔薄膜15布置在电池12和13之间。
如图1所示,多孔薄膜15布置在电池12和13之间,向电池12中引入电解质,而向另一个电池13中仅引入溶剂,用电池13中布置的电极16测量由离子传递引起的溶液比电导率随时间的变化。
使用其中LiPF6以1摩尔/升的浓度作为电解质溶解在体积比为30∶35∶35的碳酸乙二酯、碳酸甲乙酯和碳酸二甲酯的混合溶剂中的电解质溶液进行该测量实验。在图1中,Li+离子用符号○表示。通过测量溶液的电阻根据电池常数计算溶液的比电导率。
比电导率表现出通过薄膜透过的离子量,随着时间变化,更高的比电导率表示更高的离子透过性。
(2)Gurley值
薄膜的Gurley值(秒/100cc)根据JIS P8117由B型比重计(ToyoSeiki Seisaku-sho,LTD.)测量。
(3)平均孔隙直径
使用Perm-Porometer(由PMI Ltd.制造)根据ASTM F316-86通过泡点法测量平均孔隙直径d(μm)。
(4)平均孔隙半径
使用Auto-Pore III9420(由MICROMETRICS Ltd.制造)根据JISK1150用水银孔隙率法测量平均孔隙半径r(μm)。通过测量孔隙半径在0.0032-7.4μm范围内的分布来测定平均孔隙半径。
(5)穿透强度(字面翻译)
为了测定穿透强度,直径为1mm、针尖曲率半径为0.5mm的金属针以200毫米/分钟的速度刺入用直径12毫米的垫圈固定的薄膜,测量在薄膜中形成孔的最大负荷并表示为穿透强度。
[多孔薄膜的生产]
实施例1
使用分段设计的双螺杆捏合机(由Research Laboratory ofPlastics Technology Co.,Ltd.生产)使得30体积%的碳酸钙Starpigot 15A(平均粒径为0.15μm,由Shiraishi Calcium Co.,Ltd.生产)可以与70体积%的混合聚乙烯树脂强制捏合,以便捏合这些物料,从而获得一种树脂组合物,所述聚乙烯树脂由70重量%聚乙烯薄膜(Highzex Million 340M,重均分子链长为17000nm,平均分子量为3,000,000,熔点为136℃,由Mitsui Chemical生产)和30重量%聚乙烯蜡(High Wax 110P,重均分子量为100,熔点为110℃,由MitsuiChemicals生产)组成。
在这种树脂组合物中分子链长度为2850nm或更长的聚乙烯的含量为27重量%。这种树脂组合物经过压延(辊子温度为150℃),从而制备厚度约70μm的原膜。
所得的原纤滤料用拉幅机在110℃的拉伸温度下拉伸约5倍,以获得具有丝瓜结构的多孔薄膜。在图2中表示了所得多孔薄膜的表面的扫描电子显微照片。在图2中定向并在V方向弯曲的略粗的原纤是主干原纤,而分支原纤在与V方向垂直的方向上形成。从图2中明显看出,所形成的分支原纤的密度高于主干原纤的密度。由分支原纤和主干原纤形成了大量微孔。
在实施例1中获得的多孔薄膜的空气透过率、平均孔隙直径、厚度、平均孔隙直径d、平均孔隙半径r和2r/d、和穿透强度一起表示在表1中。另外,测量比电导率随时间的变化作为离子透过性指标,并表示在图4中。
对比实施例1
商品多孔薄膜的空气透过性、平均孔隙直径和厚度表示在表1中。其电子显微照片表示在图3中,离子透过性的测量结果表示在图4中。这种多孔薄膜是通过高拉伸比(引出速度/挤出速度)模塑由聚丙烯层/聚乙烯层/聚丙烯层组成的叠层薄膜,使叠层薄膜经过结晶化热处理,在低温拉伸,在高温拉伸以便从中释放晶界所形成的薄膜。从图3中明显看出,这种多孔薄膜不具有丝瓜结构。
在对比实施例1中获得的多孔薄膜的空气透过率、平均孔隙直径、厚度、平均孔隙直径d、平均孔隙半径r和2r/d、和穿透强度一起表示在表1中。另外,测量比电导率随时间的变化作为离子透过性指标,并表示在图4中。
如图4所示,具有实施例1中的丝瓜结构的本发明的多孔薄膜约为对比实施例1中的多孔薄膜厚度的1.7倍,但是其比电导率随时间的变化(=斜率)更大,因此表明单位时间从其中透过的离子量更高,即其离子透过性更高。
表1
Gurley空气透过率(秒/100cc) | 薄膜厚度(μm) | 平均孔隙直径d(μm) | 平均孔隙半径r(μm) | 2r/d | 穿透强度(N) | |
实施例1 | 90 | 42 | 0.129 | 0.095 | 1.47 | 6.9 |
对比实施例1 | 610 | 25 | 0.050 | 0.029 | 1.16 | 3.3 |
如上所述,本发明的多孔薄膜通过具有丝瓜结构,可以改善离子透过性。
Claims (3)
1.一种具有微孔的由聚烯烃制成的多孔薄膜,其中,由泡点法测定的所述微孔的平均孔隙直径为0.06-3μm,所述微孔由三维网络形成,这种三维网络由在薄膜的一个方向延伸的主干原纤和分支原纤形成,主干原纤通过分支原纤相互连接,并且所形成的分支原纤的密度高于所形成的主干原纤的密度,由ASTM-F316-86泡点法测定的微孔平均孔隙直径d,以μm计,和由JIS K1150水银孔隙率法测定的微孔平均孔隙半径r,以μm计,满足下列关系:
1.20≤2r/d≤1.70
2.根据权利要求1的多孔薄膜,其中,分支原纤在薄膜的最大热收缩方向上取向。
3.根据权利要求1或2的多孔薄膜,其中,所述聚烯烃包含至少10%的分子链长为2850nm或更长的聚烯烃。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001113832A JP4880824B2 (ja) | 2001-04-12 | 2001-04-12 | 多孔性フィルム |
JP113832/01 | 2001-04-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1381515A CN1381515A (zh) | 2002-11-27 |
CN1235953C true CN1235953C (zh) | 2006-01-11 |
Family
ID=18965002
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB021055297A Expired - Lifetime CN1235953C (zh) | 2001-04-12 | 2002-04-12 | 多孔薄膜 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20020192454A1 (zh) |
EP (1) | EP1249269B1 (zh) |
JP (1) | JP4880824B2 (zh) |
KR (2) | KR20020079581A (zh) |
CN (1) | CN1235953C (zh) |
CA (1) | CA2381509A1 (zh) |
TW (1) | TWI280255B (zh) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5070660B2 (ja) * | 2000-10-30 | 2012-11-14 | 住友化学株式会社 | 多孔性フィルム、電池用セパレータおよび電池 |
JP4833486B2 (ja) * | 2002-05-28 | 2011-12-07 | 住友化学株式会社 | ミクロフィルター用濾材の製造方法およびミクロフィルター用濾材 |
DE602004021402D1 (de) | 2003-09-30 | 2009-07-16 | Sumitomo Chemical Co | Blockcopolymere und verwendung davon |
JP4806159B2 (ja) * | 2003-12-01 | 2011-11-02 | 三菱樹脂株式会社 | 多孔性フィルム |
EP2472639A1 (en) | 2003-12-15 | 2012-07-04 | Mitsubishi Chemical Corporation | Nonaqueous-electrolyte secondary battery |
CN1304094C (zh) * | 2004-04-01 | 2007-03-14 | 中国科学院化学研究所 | 三维有序微米孔聚合物膜及其制备方法 |
WO2006064729A1 (ja) * | 2004-12-17 | 2006-06-22 | Maruo Calcium Company Limited | 多孔質フィルム用填剤及び該填剤を配合してなる多孔質フィルム |
JP2007293287A (ja) * | 2006-03-31 | 2007-11-08 | Sumitomo Chemical Co Ltd | インジケーター |
CN101580299B (zh) * | 2009-06-26 | 2012-09-19 | 哈尔滨工业大学深圳研究生院 | 用膜曝气方式进行污水脱氮反硝化处理的方法及装置 |
JP2011100694A (ja) * | 2009-11-09 | 2011-05-19 | Panasonic Corp | 非水電解質二次電池 |
JP5202604B2 (ja) * | 2010-11-08 | 2013-06-05 | 三菱樹脂株式会社 | 多孔性フィルムの製造方法 |
JP5828711B2 (ja) * | 2011-08-11 | 2015-12-09 | テクノポリマー株式会社 | 熱可塑性樹脂組成物及び成形品 |
TR201820579T4 (tr) * | 2011-10-28 | 2019-01-21 | Lubrizol Advanced Mat Inc | Elektrokimyasal Piller İçin Poliüretan Bazlı Membranlar Ve/Veya Ayırıcılar |
KR102089256B1 (ko) * | 2012-06-07 | 2020-03-16 | 미쯔비시 케미컬 주식회사 | 폴리올레핀계 수지 다공성 필름 |
JP6131538B2 (ja) * | 2012-07-10 | 2017-05-24 | シヤチハタ株式会社 | 多孔質印材およびその製造方法およびスタンプ |
CN105659410B (zh) * | 2013-11-06 | 2018-12-04 | Lg化学株式会社 | 电化学装置用隔膜 |
TWI673154B (zh) * | 2014-06-20 | 2019-10-01 | 日商東京應化工業股份有限公司 | 多孔性之醯亞胺系樹脂膜製造系統、分隔膜及多孔性之醯亞胺系樹脂膜製造方法 |
JP6662290B2 (ja) * | 2014-06-20 | 2020-03-11 | 東レ株式会社 | ポリオレフィン多層微多孔質膜、その製造方法及び電池用セパレータ |
CN106716679B (zh) * | 2014-10-01 | 2020-08-11 | 日本碍子株式会社 | 使用了层状双氢氧化物的电池 |
EP3675675A1 (de) * | 2017-09-01 | 2020-07-08 | Basf Se | VERFAHREN ZUM VERSCHWEIßEN VON PORÖSEN MEMBRANEN |
EP3586948A1 (en) * | 2018-06-29 | 2020-01-01 | 3M Innovative Properties Company | Low protein binding polyethersulfone microfiltration membranes |
CN110729440B (zh) * | 2019-09-29 | 2023-02-17 | 深圳中兴新材技术股份有限公司 | 一种锂离子电池涂层隔膜、制备方法及锂离子电池 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4579698A (en) * | 1982-05-28 | 1986-04-01 | Amf, Inc. | Process for producing a microporous polymeric filter membrane with adjacent non-porous edge layers and a pleated filter element formed from the membrane |
JPS6335818A (ja) * | 1986-07-31 | 1988-02-16 | Ube Ind Ltd | 微多孔性中空糸膜 |
JPH022849A (ja) * | 1987-06-26 | 1990-01-08 | Ube Ind Ltd | 多孔性中空糸膜 |
US4859535A (en) * | 1987-06-26 | 1989-08-22 | Ube Industries, Ltd | Porous hollow-fiber |
JPH0657142B2 (ja) * | 1988-03-01 | 1994-08-03 | 宇部興産株式会社 | 菌体濃縮分離用モジュール |
US4994335A (en) * | 1988-09-10 | 1991-02-19 | Ube Industries, Ltd. | Microporous film, battery separator employing the same, and method of producing them |
US5294338A (en) * | 1990-11-28 | 1994-03-15 | Mitsubishi Rayon Co., Ltd. | Porous polyethylene hollow fiber membrane of large pore diameter, production process thereof, and hydrophilized porous polyethylene hollow fiber membranes |
US5624627A (en) * | 1991-12-27 | 1997-04-29 | Mitsui Petrochemical Industries, Ltd. | Process for preparing surface-modified biaxially oriented film of high molecular weight polyethylene |
JPH0676808A (ja) * | 1992-06-29 | 1994-03-18 | Japan Gore Tex Inc | 電池用隔膜及び電池 |
US5830603A (en) * | 1993-09-03 | 1998-11-03 | Sumitomo Electric Industries, Ltd. | Separator film for a storage battery |
WO1996027633A1 (en) * | 1995-03-03 | 1996-09-12 | Asahi Kasei Kogyo Kabushiki Kaisha | Microporous polyethylene film and process for producing the film |
TW408134B (en) * | 1995-07-18 | 2000-10-11 | Mitsui Chemicals Inc | Microporous film of high molecular weight polyolefin and process for producing same |
US5814405A (en) * | 1995-08-04 | 1998-09-29 | W. L. Gore & Associates, Inc. | Strong, air permeable membranes of polytetrafluoroethylene |
TW431962B (en) * | 1996-11-19 | 2001-05-01 | Mitsui Chemicals Inc | Porpus film of high molecular wight polyolefin and process for producing same |
US6010776A (en) * | 1998-05-19 | 2000-01-04 | 3M Innovative Properties Company | Microporous materials containing cross-linked oil |
-
2001
- 2001-04-12 JP JP2001113832A patent/JP4880824B2/ja not_active Expired - Fee Related
-
2002
- 2002-04-03 US US10/114,254 patent/US20020192454A1/en not_active Abandoned
- 2002-04-03 TW TW091106729A patent/TWI280255B/zh not_active IP Right Cessation
- 2002-04-11 CA CA002381509A patent/CA2381509A1/en not_active Abandoned
- 2002-04-11 EP EP02008134.5A patent/EP1249269B1/en not_active Expired - Lifetime
- 2002-04-11 KR KR1020020019709A patent/KR20020079581A/ko not_active Application Discontinuation
- 2002-04-12 CN CNB021055297A patent/CN1235953C/zh not_active Expired - Lifetime
-
2009
- 2009-02-26 KR KR1020090016430A patent/KR100995267B1/ko active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
KR20020079581A (ko) | 2002-10-19 |
KR100995267B1 (ko) | 2010-11-19 |
KR20090036090A (ko) | 2009-04-13 |
CN1381515A (zh) | 2002-11-27 |
EP1249269B1 (en) | 2013-06-05 |
US20020192454A1 (en) | 2002-12-19 |
TWI280255B (en) | 2007-05-01 |
EP1249269A2 (en) | 2002-10-16 |
JP4880824B2 (ja) | 2012-02-22 |
CA2381509A1 (en) | 2002-10-12 |
JP2002309024A (ja) | 2002-10-23 |
EP1249269A3 (en) | 2007-08-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1235953C (zh) | 多孔薄膜 | |
TW570837B (en) | Porous film, separator for cell, and cell | |
JP5967589B2 (ja) | ポリオレフィン微多孔膜及びその製造方法 | |
JP4195810B2 (ja) | ポリオレフィン微多孔膜及びその製造方法並びに用途 | |
KR101943126B1 (ko) | 개선된 배터리 분리막 및 그의 형성 방법 | |
JP5005387B2 (ja) | ポリオレフィン微多孔膜の製造方法 | |
CN1383390A (zh) | 多组分复合膜及其制备方法 | |
JP2009242631A (ja) | ポリオレフィン微多孔膜 | |
WO2016104790A1 (ja) | ポリオレフィン微多孔膜、その製造方法及び電池用セパレータ | |
JP2004149637A (ja) | 微多孔膜及びその製造方法並びに用途 | |
JP2001200081A (ja) | ポリエチレン微多孔膜及びその製造方法 | |
WO2016104791A1 (ja) | ポリオレフィン樹脂組成物およびポリオレフィン微多孔膜の製造方法 | |
KR101674985B1 (ko) | 분리막 조성물, 상기 조성물로 형성된 분리막 및 이를 이용한 전지 | |
JP2001200082A (ja) | ポリエチレン微多孔膜及びその製造方法 | |
JP2019102126A (ja) | 電池用セパレータ及び非水電解液二次電池 | |
JP6988880B2 (ja) | ポリオレフィン微多孔膜 | |
CN1319633C (zh) | 用于微型过滤器的过滤材料 | |
WO2022163714A1 (ja) | 蓄電デバイス用セパレータ、及びこれを含む蓄電デバイス | |
JPWO2019189522A1 (ja) | ポリオレフィン微多孔膜の製造方法及びポリオレフィン微多孔膜 | |
KR20150035168A (ko) | 코팅층을 포함하는 분리막 및 이를 이용한 전지 | |
JP2002200670A (ja) | 多孔性フィルムの製造方法 | |
WO2023095885A1 (ja) | 蓄電デバイス用セパレータ及びこれを用いた蓄電デバイス | |
JP3779589B2 (ja) | 建築用下地材フィルム | |
CN118318346A (zh) | 蓄电装置用分隔件及使用其的蓄电装置 | |
WO2020148946A1 (ja) | ポリオレフィン微多孔膜の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CX01 | Expiry of patent term |
Granted publication date: 20060111 |
|
CX01 | Expiry of patent term |