US20150210821A1 - Nanoporous linear polyolefin membranes and block copolymer precursors for same - Google Patents
Nanoporous linear polyolefin membranes and block copolymer precursors for same Download PDFInfo
- Publication number
- US20150210821A1 US20150210821A1 US14/645,952 US201514645952A US2015210821A1 US 20150210821 A1 US20150210821 A1 US 20150210821A1 US 201514645952 A US201514645952 A US 201514645952A US 2015210821 A1 US2015210821 A1 US 2015210821A1
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- United States
- Prior art keywords
- lel
- block
- block copolymer
- nano
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 19
- 239000012528 membrane Substances 0.000 title claims description 28
- 239000002243 precursor Substances 0.000 title description 6
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
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- 239000000463 material Substances 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- 229920000428 triblock copolymer Polymers 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-JGUCLWPXSA-N toluene-d8 Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C([2H])=C1[2H] YXFVVABEGXRONW-JGUCLWPXSA-N 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VZUAUHWZIKOMFC-ARJAWSKDSA-N [(z)-4-acetyloxybut-2-enyl] acetate Chemical compound CC(=O)OC\C=C/COC(C)=O VZUAUHWZIKOMFC-ARJAWSKDSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
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- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
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- 229940030980 inova Drugs 0.000 description 2
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- MXRMOMNDWPCTCI-UHFFFAOYSA-N CCC=CCCCCCCC=CCOC(C)=O Chemical compound CCC=CCCCCCCC=CCOC(C)=O MXRMOMNDWPCTCI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- HPABSAOLGBMKCM-UHFFFAOYSA-N OCC=CCCCCCCC=CCO Chemical compound OCC=CCCCCCCC=CCO HPABSAOLGBMKCM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N OCCCCCCO Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- MFVXWTUIQDVEED-UHFFFAOYSA-N [H]OC(C)C(=O)OC(C)C(=O)OCCCCCCOC(=O)C(C)OC(=O)C(C)O[H] Chemical compound [H]OC(C)C(=O)OC(C)C(=O)OCCCCCCOC(=O)C(C)OC(=O)C(C)O[H] MFVXWTUIQDVEED-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- FCDPQMAOJARMTG-UHFFFAOYSA-L benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphane Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-L 0.000 description 1
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 238000003384 imaging method Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 230000008520 organization Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 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
- 238000010926 purge Methods 0.000 description 1
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- 238000012607 small angle X-ray scattering experiment Methods 0.000 description 1
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- 238000001757 thermogravimetry curve Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
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- C—CHEMISTRY; METALLURGY
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- 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
- C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
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- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
- B01D67/0031—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching by elimination of at least one of the blocks of a block copolymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
- B01D71/26—Polyalkenes
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- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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- H—ELECTRICITY
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- 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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- This invention relates to polymer membranes and processes for preparing same.
- Block copolymers are versatile hybrid materials that have been used in the preparation of a wide variety of nano-structured materials.
- the incompatibility of distinct chemical segments leads to nanometer-scale self-organization, and thus utility as structure directing agents.
- a process for preparing a polymer composite includes reacting a hydroxyl-terminated, linear polyolefin polymer with a cyclic ester in the presence of a ring opening catalyst to form a block copolymer having at least one polyester block and at least one linear polyolefin block.
- the block copolymer is in the form of a nano-structured, bicontinuous composite.
- the composite includes a continuous matrix phase and a second continuous phase, where the continuous matrix phase comprises the linear polyolefin block of the block copolymer, and the second continuous phase comprises the polyester block of the block copolymer.
- nano-structured, bicontinuous composite refers to a polymer-polymer composite characterized by two continuous polymer phases interspersed throughout each other that exhibits compositional heterogeneity on a nanometer (i.e., 1-500 nanometer) length scale.
- the process may include treating the composite to selectively remove the polyester blocks of the block copolymer in the second continuous phase to form a plurality of pores.
- the composite may be treated by a chemical etchant.
- the pores may have an average pore diameter of about 1 to about 500 nanometers.
- the pores may also have an average pore diameter of about 10 to about 50 nanometers.
- the resultant composite is in the form of a nano-porous membrane that may be a battery separator or water purification membrane.
- suitable polyolefins include polyethylene and polypropylene.
- suitable cyclic esters include D,L-lactide, glycolide, caprolactone, menthide, and dihydrocarvide. When the cyclic ester is D,L-lactide, the resulting triblock copolymer includes polylactide blocks.
- a composition in another general aspect, includes a block copolymer that includes at least one polyester block and at least one linear polyolefin block in the form of a nano-structured, bicontinuous composite that includes a continuous matrix phase and a second continuous phase.
- the continuous matrix phase includes the linear polyolefin block of the block copolymer
- the second continuous phase comprises the polyester block of the block copolymer.
- suitable polyolefins include polyethylene and polypropylene.
- suitable polyesters include polylactide.
- the composition exhibits good mechanical properties, including modulus, tensile strength, and elongation at break.
- a composition in another general aspect, includes a nano-structured, bicontinuous composite having a continuous matrix phase comprising a linear polyolefin and a second continuous phase comprising a plurality of nano-pores.
- the pores may have an average pore diameter of about 1 to about 500 nanometers.
- the pores may also have an average pore diameter of about 10 to about 50 nanometers.
- the composition is in the form of a nano-porous membrane that may be a battery separator or water purification membrane.
- the polyolefin can be polyethylene or propylene.
- FIG. 1 shows a reaction scheme for synthesizing a polylactide-linear polyethylene-polylactide (LEL) triblock copolymer.
- FIG. 2 is a table reporting the molecular and thermal characteristics for the linear polyethylene (LPE) homopolymer, LEL triblock copolymers, and porous LPE samples prepared according to the Examples described herein.
- LPE linear polyethylene
- FIG. 3 is a 1H NMR spectrum of the polycyclooctene (PCOE) precursor used to prepare the LEL triblock copolymers, with the two insets depicting a portion of the spectrum both with acetoxy end-groups (top) and hydrolysis (bottom) to afford hydroxyl end-groups.
- PCOE polycyclooctene
- FIG. 4 is a 1 H NMR spectrum of hydroxyl telechelic LPE from hydrogenation of the PCOE, giving completely linear chains, with the end methylene proton signal magnified for clarity in the inset. Measured in toluene-d 8 at 100° C.
- FIG. 5 is a 1 H NMR spectrum of block polymer LEL [14-28-14] with the inset showing a magnified portion that accentuates the methylene protons at the junction between the two components [H d ; —CH 2 —CH 2 —O—C(O)—CH(CH 3 )—] and the PLA end-group methine protons [H e ; —O—C(O)—CH(CH 3 )—OH]. Measured in toluene-d 8 at 100° C.
- FIG. 6 depicts size exclusion chromatograms of the block polymers showing the difference in elution volume between LEL [14-28-14] ( ) and LEL [37-28-37] ( ).
- FIG. 7( b ) presents thermograms from cooling the samples to accentuate the relative crystallization exotherm magnitudes and show the crystallization temperatures.
- FIG. 7( c ) presents DSC thermograms accentuating the T g of the PLA in block polymer samples. Heating and cooling rates were 10° C. min ⁇ 1 , and the samples were initially heated to 180° C. and isothermally annealed before analysis to homogenize thermal histories of the samples.
- FIGS. 8( a )-( c ) present SAXS analysis for the various samples showing the broad scattering reflections associated with the bicontinuous disordered structure. The primary peak appears in all cases to nestle against the beam stop at ⁇ 0.05 nm ⁇ 1 .
- FIG. 8( a ) triblock copolymers in the melt at 160° C.
- FIG. 8( b ) triblock copolymers after cooling at ⁇ 20° C. min ⁇ 1 from the melt.
- FIG. 8( c ) membranes at ambient temperature after PLA removal.
- FIGS. 9( a ) and ( b ) present infrared spectra of the film prepared from sample LEL [37-28-37] both FIG. 9( a ) before and FIG. 9( b ) after removing the PLA.
- FIG. 10 is a scanning electron microscopy (SEM) microphotograph of a freeze-fractured LEL film after PLA etching (the length scale bar represents 300 nm). Surfaces were sputter coated with platinum to prevent charging.
- SEM scanning electron microscopy
- FIG. 11 presents SEM images at a variety of different magnifications for freeze-fractured membrane from sample LEL [37-28-37] showing the disordered bicontinuous nature of the structure where the narrow pore-size distribution and the homogeneity of the pore structure are accentuated at high and low magnification, respectively. ( ⁇ 2 nm Pt coating).
- FIG. 12 presents SEM images from the membrane derived from sample LEL [14-28-24] showing the similarly bicontinuous disordered morphological characteristics despite the significant difference in composition compared with the other sample described. ( ⁇ 2 nm Pt coating).
- FIG. 13( a ) membrane from LEL [37-28-37].
- FIG. 13( b ) membrane from LEL [14-28-14].
- FIG. 14 is a graph illustrating the pore size distribution for two different LEL films (LEL [37-38-37] (filled triangles) and LEL [14-28-14] (empty triangles)) after PLA etching calculated from nitrogen desorption isotherms.
- FIGS. 15( a )-( b ) are graphs illustrating pore-size distributions from nitrogen adsorption (filled triangles) and desorption (empty triangles) isotherms using the BJH method.
- FIG. 15( a ) is derived from LEL [37-28-37].
- FIG. 15( b ) is derived from LEL [14-28-14].
- FIGS. 16( a )-( b ) are SEM images of porous LPE derived from LEL films cast from 10 wt % tetralin solutions at 140° C.
- FIG. 16( a ) is derived from LEL [14-28-14].
- FIG. 16( b ) is derived from LEL [37-28-37]. ( ⁇ 2 nm Pt coating).
- FIGS. 17( a )-( b ) are stress-strain curves representing the results of tensile testing of block copolymer precursors ( ) and membranes (- - - -) from samples LEL [14-28-14] ( FIG. 17( a )) and LEL [37-28-37] ( FIG. 17( b )).
- FIGS. 18( a ) and ( b ) are SEM microphotographs corresponding to a freeze-fractured LEL [14-28-14] film after PLA etching (the length scale bars represent 500 nm).
- FIG. 18( a ) corresponds to the film prior to annealing
- FIG. 18( b ) corresponds to the film after annealing at 150° C. for 5 minutes.
- FIGS. 19( a )-( d ) are SEM microphotographs of surfaces exposed to (top, left and right) concentrated sulfuric acid (Fig[[s]]. 19 ( a ) and Fig. (b)) and concentrated nitric acid for 24 h at RT (Fig[[s]]. 19 ( c ) and Fig. (d)) for porous sample derived from LEL [37-28-37]. The bicontinuous morphology is well-preserved. ( ⁇ 2 nm Pt coating)
- FIG. 20 is a graph illustrating pore size distributions calculated using the BJH method from desorption isotherms for the membrane from LEL [14-28-14] before (curve (a)) and after (curve (b)) soaking in concentrated hydrochloric acid at 50° C. for 24 h. The overall pore size distribution is minimally affected.
- Polymer composites are prepared generally according to the reaction scheme shown in FIG. 1 .
- the nano-structured nature of the composite results in films that exhibit good mechanical properties, including modulus, tensile strength, and ultimate elongation, that make them useful in a variety of applications.
- polyester blocks e.g., polylactide blocks
- linear polyolefin block e.g., polyethylene block
- the polyester blocks may be selectively removable, e.g., by chemically etching using base or acid. Removal creates a plurality of nano-sized pores.
- the pores are small (e.g., pore diameters on the order of about 1 to about 500 nanometers, or about 10 to about 50 nanometers).
- the pores are characterized by a relatively narrow size distribution, and are substantially homogeneously distributed throughout the film. These features make the nano-porous film particularly useful for applications such as separation membranes (e.g., battery separators).
- the films are useful in a variety of applications, including separation membranes (e.g., battery separators), membranes for water purification, fuel cell membranes, catalytic reactors, nanotemplates, and the like.
- separation membranes e.g., battery separators
- membranes for water purification e.g., fuel cell membranes, catalytic reactors, nanotemplates, and the like.
- the nanoscopic, bicontinuous structure that results from the aforementioned process contains interpenetrating domains that both percolate through the entire material. This co-continuity allows for one mechanically robust phase to support the entire structure and another percolating domain that endows the material with some specific functionality.
- Generating a nanoporous structure by removal of the functional domain gives a material with a percolating pore structure. Since the pore size distribution is narrow and the pore structure permeates the entire film, such membrane materials are useful as battery separators.
- Hewlett-Packard (Agilent Technologies) 1100 Series liquid chromatograph housing three PlGel 5 ⁇ m Mixed-C (Polymer Laboratories) columns with pore sizes of 500 ⁇ , 1 ⁇ 10 3 , and 1 ⁇ 10 4 ⁇ with chloroform as eluent.
- the refractive index signal was recorded with a Hewlett Packard 1047A refractive index detector.
- the other instrument operating at a flow rate of 1.0 mL min ⁇ 1 and 135° C.
- DSC Differential scanning calorimetric
- SEM Scanning electron microscopy
- Nitrogen adsorption/desorption was carried out at 77 K using an Autosorb-1 system.
- the specific surface area of the membranes was calculated using the Brunauer-Emmet-Teller method (Brunauer, S.; Deming, L. S.; Deming, W. E.; Teller, E. J. J. Am. Chem. Soc. 1940, 62, 1723-1732), while the pore-size distributions were determined using the Barret-Joyner-Halenda model (Barrett, E. P.; Joyner, L. G.; Halenda, P. P. J. Am. Chem. Soc. 1951, 73, 373-380).
- the hydroxy-telechelic PCOE (HO-PCOE-OH) (10.0 g; 45.4 mmol double bonds) was dissolved in 150 mL cyclohexane and the solution was purged with bubbling argon for 20 minutes.
- a silica supported Pt/Re catalyst (1.0 g of 10%) was placed in the high-pressure reactor, which was sealed, evacuated of air, and refilled with Ar.
- the polymer solution was added to the reactor at which point hydrogen was introduced (500 psig) and the temperature increased to 90° C.
- the reaction mixture was stirred for 24 hours, after which the solvent was removed and replaced with 150 mL toluene.
- the catalyst was removed by filtering the solution at 110° C.
- the block copolymers were cast as films in aluminum pans by first dissolving the polymer as a 10% solution in tetralin at 140° C. The hot solution was transferred to the aluminum pan and the high temperature was maintained while the solvent slowly evaporated over 2 h. This was initially done to attempt to adopt an equilibrium microphase separated structure. The dry polymer film was kept at 140° C. for an additional 4 h. The polymer films stuck to the aluminum. They were separated by dissolving the aluminum in a 4 M solution of HCl (aq). Melt-pressing of the block polymer precursors into cylindrical discs was done in a hot press using molds with 13 mm diameter and 1 mm thickness.
- the porous samples were prepared by submerging pieces of the block polymer (either bulk melt-pressed or solvent cast) in a 0.5 M NaOH solution in 40% (aq) MeOH. The solutions were kept at 70° C. for 3 days and the porous pieces were washed with slightly acidic MeOH (aq) and then pure MeOH and further dried for 2 days at 60° C. in vacuo. Subsequent mechanical testing was performed on the solvent-cast films.
- FIG. 2 The molecular and thermal characteristics for the LPE homopolymer, LEL block copolymers, and porous LPE samples, prepared as described above, are set forth in FIG. 2 .
- a 1 H NMR spectrum of the polycyclooctene precursor (PCOE) is shown in FIG. 3 .
- a 1 H NMR spectrum of the hydroxyl telechelic LPE from hydrogenation of the PCOE is shown in FIG. 4 .
- FIG. 5 A 1H NMR spectrum of triblock copolymer LEL [14-28-14] is shown in FIG. 5 .
- Size exclusion chromatograms of LEL [14-28-14] and LEL [37-28-37] are shown in FIG. 6 .
- FIGS. 8( a )-( c ) SAXS analysis for either sample at 25° C. ( FIGS. 8( a )-( c )) gave virtually indistinguishable profiles compared to the 160° C. data, which is indicative of confined LPE crystallization and consistent with behavior of other block polymers of polyethylene (i.e., hPB) and a highly incompatible component.
- hPB polyethylene
- Thin ( ⁇ 150 ⁇ m) films of the LEL samples were cast at 140° C. from tetralin for tensile testing evaluation as described above. These solvent cast films adopted the same disordered bicontinuous morphologies as the molded samples, as determined by SEM ( FIGS. 16( a ) and ( b )). From the stress-strain curves of these samples ( FIGS. 17( a ) and ( b )) the tensile toughness values were determined to be 1.54 and 4.91 MJ m ⁇ 3 for nanoporous versions of LEL [37-28-37] and LEL [14-28-14], respectively.
- Temperature-induced pore collapse is an important attribute in battery separators for preventing thermal runaway and minimizing the potential for ignition upon fortuitous anode/cathode contact.
- the DSC analysis of the nanoporous LPE membranes ( FIGS. 2 and 7( a )-( c )) gave high melting temperatures (T m,PE ⁇ 130° C.) and levels of crystallinity ( ⁇ 60%) as compared to typical values for hPB. Annealing the nanoporous LPE membranes at 150° C. for 5 min causes pore collapse, as confirmed by SEM analysis ( FIGS. 18( a ) and ( b )).
Abstract
A composition comprising a block copolymer that includes at least one polyester block and at least one linear polyolefin block, wherein the composition is in the form of a nano-structured, bicontinuous composite that includes a continuous matrix phase and a second continuous phase. The continuous matrix phase comprises the linear polyolefin block of the block copolymer, and the second continuous phase comprises the polyester block of the block copolymer. The composite may be treated to remove the polyester block, thereby forming a plurality of nano-pores.
Description
- This application is a continuation of U.S. application Ser. No. 13/634,175 having a filing date of Oct. 23, 2012, which is a National Stage application under 35 U.S.C. §371 of International Application No. PCT/US2011/028038 having an International Filing Date of Mar. 11, 2011, which claims the benefit of priority of U.S. Provisional Application No. 61/312,922 having a filing date of Mar. 11, 2010.
- This invention was made with government support under DMR-0605880 awarded by the National Science Foundation. The government has certain rights in the invention.
- This invention relates to polymer membranes and processes for preparing same.
- Block copolymers are versatile hybrid materials that have been used in the preparation of a wide variety of nano-structured materials. The incompatibility of distinct chemical segments leads to nanometer-scale self-organization, and thus utility as structure directing agents.
- In one general aspect, a process for preparing a polymer composite is described that includes reacting a hydroxyl-terminated, linear polyolefin polymer with a cyclic ester in the presence of a ring opening catalyst to form a block copolymer having at least one polyester block and at least one linear polyolefin block. The block copolymer is in the form of a nano-structured, bicontinuous composite. The composite includes a continuous matrix phase and a second continuous phase, where the continuous matrix phase comprises the linear polyolefin block of the block copolymer, and the second continuous phase comprises the polyester block of the block copolymer.
- As used herein, a “nano-structured, bicontinuous composite” refers to a polymer-polymer composite characterized by two continuous polymer phases interspersed throughout each other that exhibits compositional heterogeneity on a nanometer (i.e., 1-500 nanometer) length scale.
- In various implementations, the process may include treating the composite to selectively remove the polyester blocks of the block copolymer in the second continuous phase to form a plurality of pores. The composite may be treated by a chemical etchant. The pores may have an average pore diameter of about 1 to about 500 nanometers. The pores may also have an average pore diameter of about 10 to about 50 nanometers. In some embodiments, the resultant composite is in the form of a nano-porous membrane that may be a battery separator or water purification membrane.
- Examples of suitable polyolefins include polyethylene and polypropylene. Examples of suitable cyclic esters include D,L-lactide, glycolide, caprolactone, menthide, and dihydrocarvide. When the cyclic ester is D,L-lactide, the resulting triblock copolymer includes polylactide blocks.
- In another general aspect, a composition is described that includes a block copolymer that includes at least one polyester block and at least one linear polyolefin block in the form of a nano-structured, bicontinuous composite that includes a continuous matrix phase and a second continuous phase. The continuous matrix phase includes the linear polyolefin block of the block copolymer, and the second continuous phase comprises the polyester block of the block copolymer. Examples of suitable polyolefins include polyethylene and polypropylene. Examples of suitable polyesters include polylactide. The composition exhibits good mechanical properties, including modulus, tensile strength, and elongation at break.
- In another general aspect, a composition is described that includes a nano-structured, bicontinuous composite having a continuous matrix phase comprising a linear polyolefin and a second continuous phase comprising a plurality of nano-pores. The pores may have an average pore diameter of about 1 to about 500 nanometers. The pores may also have an average pore diameter of about 10 to about 50 nanometers. In some embodiments, the composition is in the form of a nano-porous membrane that may be a battery separator or water purification membrane. The polyolefin can be polyethylene or propylene.
- The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages will be apparent from the description and from the claims.
-
FIG. 1 shows a reaction scheme for synthesizing a polylactide-linear polyethylene-polylactide (LEL) triblock copolymer. -
FIG. 2 is a table reporting the molecular and thermal characteristics for the linear polyethylene (LPE) homopolymer, LEL triblock copolymers, and porous LPE samples prepared according to the Examples described herein. -
FIG. 3 is a 1H NMR spectrum of the polycyclooctene (PCOE) precursor used to prepare the LEL triblock copolymers, with the two insets depicting a portion of the spectrum both with acetoxy end-groups (top) and hydrolysis (bottom) to afford hydroxyl end-groups. -
FIG. 4 is a 1H NMR spectrum of hydroxyl telechelic LPE from hydrogenation of the PCOE, giving completely linear chains, with the end methylene proton signal magnified for clarity in the inset. Measured in toluene-d8 at 100° C. -
FIG. 5 is a 1H NMR spectrum of block polymer LEL [14-28-14] with the inset showing a magnified portion that accentuates the methylene protons at the junction between the two components [Hd; —CH2—CH2—O—C(O)—CH(CH3)—] and the PLA end-group methine protons [He; —O—C(O)—CH(CH3)—OH]. Measured in toluene-d8 at 100° C. -
-
FIG. 7( a) presents DSC measurements for the unsaturated PCOE precursor (HO-PCOE-OH) (Mn=27.6 kg mol−1, PDI=1.76), the saturated HO-LPE-OH (Mn=28 kg mol−1, PDI=2.5) and triblock polymer samples LEL [14-28-14] (Mn=55.7 kg mol−1; fPLA=0.38) and LEL [37-28-37] (Mn=102 kg mol−1; fPLA=0.62). -
FIG. 7( b) presents thermograms from cooling the samples to accentuate the relative crystallization exotherm magnitudes and show the crystallization temperatures. -
FIG. 7( c) presents DSC thermograms accentuating the Tg of the PLA in block polymer samples. Heating and cooling rates were 10° C. min−1, and the samples were initially heated to 180° C. and isothermally annealed before analysis to homogenize thermal histories of the samples. -
FIGS. 8( a)-(c) present SAXS analysis for the various samples showing the broad scattering reflections associated with the bicontinuous disordered structure. The primary peak appears in all cases to nestle against the beam stop at ˜0.05 nm−1.FIG. 8( a): triblock copolymers in the melt at 160° C.FIG. 8( b): triblock copolymers after cooling at ˜20° C. min−1 from the melt.FIG. 8( c): membranes at ambient temperature after PLA removal. -
FIGS. 9( a) and (b) present infrared spectra of the film prepared from sample LEL [37-28-37] bothFIG. 9( a) before andFIG. 9( b) after removing the PLA. The characteristic signal attributed to the carbonyl functionality of the PLA (v=1750 cm−1) is clearly absent after etching, suggesting complete PLA removal. -
FIG. 10 is a scanning electron microscopy (SEM) microphotograph of a freeze-fractured LEL film after PLA etching (the length scale bar represents 300 nm). Surfaces were sputter coated with platinum to prevent charging. -
FIG. 11 presents SEM images at a variety of different magnifications for freeze-fractured membrane from sample LEL [37-28-37] showing the disordered bicontinuous nature of the structure where the narrow pore-size distribution and the homogeneity of the pore structure are accentuated at high and low magnification, respectively. (≈2 nm Pt coating). -
FIG. 12 presents SEM images from the membrane derived from sample LEL [14-28-24] showing the similarly bicontinuous disordered morphological characteristics despite the significant difference in composition compared with the other sample described. (≈2 nm Pt coating). -
FIGS. 13( a)-(b) represent nitrogen adsorption measurements on membranes measured at T=77K showing the adsorption (filled triangles) and desorption (empty triangles) isotherms with the inset in each plot showing the average pore size distribution calculated using the BJH method from the desorption data.FIG. 13( a): membrane from LEL [37-28-37].FIG. 13( b): membrane from LEL [14-28-14]. -
FIG. 14 is a graph illustrating the pore size distribution for two different LEL films (LEL [37-38-37] (filled triangles) and LEL [14-28-14] (empty triangles)) after PLA etching calculated from nitrogen desorption isotherms. -
FIGS. 15( a)-(b) are graphs illustrating pore-size distributions from nitrogen adsorption (filled triangles) and desorption (empty triangles) isotherms using the BJH method.FIG. 15( a) is derived from LEL [37-28-37].FIG. 15( b) is derived from LEL [14-28-14]. -
FIGS. 16( a)-(b) are SEM images of porous LPE derived from LEL films cast from 10 wt % tetralin solutions at 140° C.FIG. 16( a) is derived from LEL [14-28-14].FIG. 16( b) is derived from LEL [37-28-37]. (˜2 nm Pt coating). -
-
FIGS. 18( a) and (b) are SEM microphotographs corresponding to a freeze-fractured LEL [14-28-14] film after PLA etching (the length scale bars represent 500 nm).FIG. 18( a) corresponds to the film prior to annealing, andFIG. 18( b) corresponds to the film after annealing at 150° C. for 5 minutes. -
FIGS. 19( a)-(d) are SEM microphotographs of surfaces exposed to (top, left and right) concentrated sulfuric acid (Fig[[s]]. 19(a) and Fig. (b)) and concentrated nitric acid for 24 h at RT (Fig[[s]]. 19(c) and Fig. (d)) for porous sample derived from LEL [37-28-37]. The bicontinuous morphology is well-preserved. (˜2 nm Pt coating) -
FIG. 20 is a graph illustrating pore size distributions calculated using the BJH method from desorption isotherms for the membrane from LEL [14-28-14] before (curve (a)) and after (curve (b)) soaking in concentrated hydrochloric acid at 50° C. for 24 h. The overall pore size distribution is minimally affected. - Polymer composites are prepared generally according to the reaction scheme shown in
FIG. 1 . The nano-structured nature of the composite results in films that exhibit good mechanical properties, including modulus, tensile strength, and ultimate elongation, that make them useful in a variety of applications. - The polyester blocks (e.g., polylactide blocks) are incompatible with the linear polyolefin block (e.g., polyethylene block). The incompatibility results in microphase at some point after the block copolymer synthesis from the initial homogeneous state, and creating a multi-phase composite having a nano-structured, bicontinuous microstructure in which one of the phases includes the polyester blocks.
- In some embodiments, the polyester blocks may be selectively removable, e.g., by chemically etching using base or acid. Removal creates a plurality of nano-sized pores. The pores are small (e.g., pore diameters on the order of about 1 to about 500 nanometers, or about 10 to about 50 nanometers). In addition, the pores are characterized by a relatively narrow size distribution, and are substantially homogeneously distributed throughout the film. These features make the nano-porous film particularly useful for applications such as separation membranes (e.g., battery separators). In general, the films are useful in a variety of applications, including separation membranes (e.g., battery separators), membranes for water purification, fuel cell membranes, catalytic reactors, nanotemplates, and the like. The nanoscopic, bicontinuous structure that results from the aforementioned process contains interpenetrating domains that both percolate through the entire material. This co-continuity allows for one mechanically robust phase to support the entire structure and another percolating domain that endows the material with some specific functionality. Generating a nanoporous structure by removal of the functional domain gives a material with a percolating pore structure. Since the pore size distribution is narrow and the pore structure permeates the entire film, such membrane materials are useful as battery separators.
- All bulk solvents were purchased from Mallinkrodt and used as received unless otherwise specified. Tetralin was purchased from TCI Chemicals and was vacuum distilled prior to use. The second generation Grubbs catalyst was purchased from Aldrich and used as received. Both cis-cyclooctene from Acros (95%) and cis-1,4-diacetoxy-2-butene from TCI Chemical (95%) were distilled over CaH2 prior to polymerizations. Tetrahydrofuran (THF) and toluene were passed through alumina columns and thoroughly degassed. Purac provided the
D,L -lactide (99%), which was recrystallized twice from toluene prior to being stored in a glove box under N2 atmosphere. Sn(Oct)2 from Aldrich was distilled using a Kugelrohr apparatus and stored under N2. The catalyst used in hydrogenation reactions was a silica-supported Pt catalyst supplied from Dow Chemical Company. - Characterization
- 1H NMR spectra obtained using CDCl3 as a solvent were measured on a
Varian Inova 500 operating at 500 MHz, whereas those in toluene-d8 solvent were measured on a Varian Inova VI-300 operating at 300 MHz with variable temperature capability up to 100° C. Size-exclusion chromatography (SEC) analysis was performed on two different instruments, depending on the relative solubility of the materials and temperature capabilities of the instruments. Operating at a flow rate of 1.0 mL min−1 and 35° C. is a Hewlett-Packard (Agilent Technologies) 1100 Series liquid chromatograph housing threePlGel 5 μm Mixed-C (Polymer Laboratories) columns with pore sizes of 500 Å, 1×103, and 1×104 Å with chloroform as eluent. The refractive index signal was recorded with a Hewlett Packard 1047A refractive index detector. The other instrument, operating at a flow rate of 1.0 mL min−1 and 135° C. with 1,2,4-trichlorobenzene as eluent, is a Polymer Laboratories GPC-220 liquid chromatograph holding three PlGel 10 μm Mixed-B columns and equipped with a refractometer used for samples with saturated polyethylene portions. - Small-angle X-ray scattering experiments were performed at the Advanced Photon Source (APS) at Argonne National Laboratories at Sector 5-ID-D beamline. The beamline is maintained by the Dow-Northwestern-Dupont Collaborative Access Team (DND-CAT). The source produces X-rays with a wavelength of 0.84 Å. The sample to detector distance was 5.65 m and the detector radius is 81 mm. Scattering intensity was monitored by a Mar 165 mm diameter CCD detector with a resolution of 2048×2048. The two-dimensional scattering patterns were azimuthally integrated to afford one-dimensional profiles presented as spatial frequency (q) versus scattered intensity.
- Differential scanning calorimetric (DSC) measurements were obtained using a DSC Q-1000 calorimeter from TA Instruments that was calibrated with an indium standard. Samples were loaded into hermetically sealed aluminum pans prior to analysis. The thermal history of the samples were all erased by heating the samples to 180° C. and isothermally annealing for 5 min. The samples were then cooled at 10° C. min−1 to −120° C. followed by a second heating cycle to 180° C. at a rate of 10° C. min−1, all under a helium purge. Melting enthalpies were evaluated by integration of the melting endotherm using TA Universal Analysis software.
- Scanning electron microscopy (SEM) was performed on a Hitachi S-900 FE-SEM operating at 3.0 kV accelerating voltage. Samples were prepared by fracturing small pieces of the films immediately after submerging in liquid N2. Before imaging, the samples were coated with platinum using a VCR high-resolution indirect ion-beam sputtering system. The samples were coated for 10 min depositing approximately 2 nm of platinum.
- Nitrogen adsorption/desorption was carried out at 77 K using an Autosorb-1 system. The specific surface area of the membranes was calculated using the Brunauer-Emmet-Teller method (Brunauer, S.; Deming, L. S.; Deming, W. E.; Teller, E. J. J. Am. Chem. Soc. 1940, 62, 1723-1732), while the pore-size distributions were determined using the Barret-Joyner-Halenda model (Barrett, E. P.; Joyner, L. G.; Halenda, P. P. J. Am. Chem. Soc. 1951, 73, 373-380).
- General Procedure for Synthesis of HO-LPE-OH Macroinitiator
- The procedure for preparing hydroxy-telechelic polyolefins by ring-opening metathesis polymerization is generally described in (a) Bielawski, C. W.; Scherman, O. A.; Grubbs, R. H. Polymer 2002, 42, 4939-4045, and (b) Pitet, L. M.; Hillmyer, M. A. Macromolecules 2009, 42, 3674-3680. Briefly, 0.25 g (0.23 mL; 1.45 mmol) of the chain transfer agent (CTA) cis-1,4-diacetoxy-2-butene was transferred to an air-free flask through a rubber septum along with 180 mL of THF. This mixture was rapidly stirred and the temperature was maintained at 35° C. Using a syringe pump, 40 g (47 mL; 363 mmol) of cis-cyclooctene were added to the mixture over 1.5 h. Shortly (˜5 min) after starting the gradual monomer addition, 15 mg (18 μmol) of
Grubbs 2nd Generation catalyst was added as a solution in 1 mL THF. After 6 h, the reaction contents were slowly poured into 2 L of cold MeOH made slightly acidic with 20 mL of 1M HCl (aq). The precipitated polymer was isolated and dried under reduced pressure at 40° C. for 2 days. - The entire yield was dissolved into 200 mL of THF and stirred at 0° C. for 6 h after adding 10 mL of a 0.7 M solution of NaOMe in MeOH (7 mmol NaOMe). The polymer solution was again precipitated into 2 L of slightly acidic MeOH, isolated, and dried for 2 days, yielding 37.5 g (94%). 1H NMR (CDCl3, 25° C.): δ 5.40 (m, (E)-CH═CHCH2CH2—, backbone), 5.35 (m, (Z)—CH═CHCH2CH2—, backbone), 4.20 (t, (Z)—CH═CHCH2OH), 4.10 (t, (E)-CH═CHCH2OH), 2.05 (Z)—CH═CHCH2CH2— backbone), 1.95 (m, (E)-CH═CHCH2CH2 backbone), 1.30 (m, (Z)—CH═CHCH2CH2— backbone).
- The hydroxy-telechelic PCOE (HO-PCOE-OH) (10.0 g; 45.4 mmol double bonds) was dissolved in 150 mL cyclohexane and the solution was purged with bubbling argon for 20 minutes. A silica supported Pt/Re catalyst (1.0 g of 10%) was placed in the high-pressure reactor, which was sealed, evacuated of air, and refilled with Ar. The polymer solution was added to the reactor at which point hydrogen was introduced (500 psig) and the temperature increased to 90° C. The reaction mixture was stirred for 24 hours, after which the solvent was removed and replaced with 150 mL toluene. The catalyst was removed by filtering the solution at 110° C. and the solvent was again evaporated to afford 8.2 g of HO-LPE-OH (82% yield). 1H NMR (toluene-
d 8 100° C.): δ 3.37 (t, —CH2OH), 1.35 (s, —CH2—, backbone). - General Procedure for Synthesis of LEL Triblock Polymers
- The synthesis of one triblock is described, which is representative of all samples where the
D,L -lactide feedstock was adjusted accordingly to target the desired polymer compositions. The concentration of LA was kept constant at 1 M. HO-LPE-OH (2.0 g; 0.14 mmol OH) was placed with a stir-bar in a pressure vessel fitted with a Teflon screw-cap and Viton o-ring seal. This was transferred to a glove box, whereinD,L -lactide (2.5 g; 17 mmol), toluene (17 mL) and Sn(Oct)2 (7 mg; 17 μmol) were added before sealing and removing from the box. The flask was immersed in an oil-bath at 110° C. for 6 h followed by precipitation into a ten-fold excess by volume of MeOH. The isolated polymer was dried at 60° C. for 24 h to yield 4.2 g (93%). 1H NMR (toluene-d 8 100° C.): δ 5.10 (bm, —C(O)CH(CH3)O— backbone), 4.05-4.25 (m, —C(O)CH(CH3)OH), 3.70-4.00 (m, —H═CHCH2OC(O)CH(CH3)O—) 1.40-1.45 (—C(O)CH(CH3)O— backbone), 1.30-1.40 (—CH2—, backbone). - General Procedure for Preparation of Block Copolymer Films and Nanoporous Membranes.
- The block copolymers were cast as films in aluminum pans by first dissolving the polymer as a 10% solution in tetralin at 140° C. The hot solution was transferred to the aluminum pan and the high temperature was maintained while the solvent slowly evaporated over 2 h. This was initially done to attempt to adopt an equilibrium microphase separated structure. The dry polymer film was kept at 140° C. for an additional 4 h. The polymer films stuck to the aluminum. They were separated by dissolving the aluminum in a 4 M solution of HCl (aq). Melt-pressing of the block polymer precursors into cylindrical discs was done in a hot press using molds with 13 mm diameter and 1 mm thickness.
- The porous samples were prepared by submerging pieces of the block polymer (either bulk melt-pressed or solvent cast) in a 0.5 M NaOH solution in 40% (aq) MeOH. The solutions were kept at 70° C. for 3 days and the porous pieces were washed with slightly acidic MeOH (aq) and then pure MeOH and further dried for 2 days at 60° C. in vacuo. Subsequent mechanical testing was performed on the solvent-cast films.
- Results
- The molecular and thermal characteristics for the LPE homopolymer, LEL block copolymers, and porous LPE samples, prepared as described above, are set forth in
FIG. 2 . A 1H NMR spectrum of the polycyclooctene precursor (PCOE) is shown inFIG. 3 . A 1H NMR spectrum of the hydroxyl telechelic LPE from hydrogenation of the PCOE is shown inFIG. 4 . A 1H NMR spectrum of triblock copolymer LEL [14-28-14] is shown inFIG. 5 . Size exclusion chromatograms of LEL [14-28-14] and LEL [37-28-37] are shown inFIG. 6 . - A sample of LEL [37-28-37] was compression molded at 160° C. SAXS analysis (
FIGS. 8( a)-(c)) at 160° C. showed a broad signal with a maximum at 0.06 nm−1 (d=105 nm) with no discernable higher-order reflections consistent with a microphase separated structure lacking long range order. The high degree of incompatibility between LPE and PLA, combined with low entanglement molecular weight for LPE, hinder the adoption of a well-organized mesophase. Annealing the samples up to 72 h at 160° C. did not appreciably increase the level of organization. Cooling from the melt to ambient temperature results in crystallization of the LPE phase (FIGS. 7( a)-7(c)). SAXS analysis for either sample at 25° C. (FIGS. 8( a)-(c)) gave virtually indistinguishable profiles compared to the 160° C. data, which is indicative of confined LPE crystallization and consistent with behavior of other block polymers of polyethylene (i.e., hPB) and a highly incompatible component. - Exposure of molded LEL [37-28-37] samples to a 0.5 M solution of NaOH selectively removed the PLA, as confirmed gravimetrically and by IR spectroscopy (
FIGS. 9( a)-(b)). An interconnected LPE scaffold with a disorganized pore structure was observed by scanning electron microscopy (SEM) (FIGS. 10-11) . Etched LEL [14-28-14] samples show a similarly disordered bicontinuous morphology (FIG. 12 ) after PLA removal despite containing significantly less PLA as compared to LEL [37-28-27]. - Nitrogen adsorption analysis of nanoporous membranes derived from both samples showed type IV adsorption/desorption isotherms indicative of mesoporosity (
FIGS. 13( a) and (b)). Narrow pore-size distributions (BJH method; desorption isotherms) peaked at 24 nm and 38 nm for nanoporous membranes from LEL [14-28-14] and LEL [37-28-37], respectively, with calculated peak widths at half height equal to 3.5 nm and 11.1 nm (FIGS. 14 and 15) . Specific surface areas calculated for LEL [14-28-14] and LEL [37-28-37] derived membranes were 70 and 96 m2 g−1, respectively. - Thin (˜150 μm) films of the LEL samples were cast at 140° C. from tetralin for tensile testing evaluation as described above. These solvent cast films adopted the same disordered bicontinuous morphologies as the molded samples, as determined by SEM (
FIGS. 16( a) and (b)). From the stress-strain curves of these samples (FIGS. 17( a) and (b)) the tensile toughness values were determined to be 1.54 and 4.91 MJ m−3 for nanoporous versions of LEL [37-28-37] and LEL [14-28-14], respectively. - Temperature-induced pore collapse is an important attribute in battery separators for preventing thermal runaway and minimizing the potential for ignition upon fortuitous anode/cathode contact. The DSC analysis of the nanoporous LPE membranes (
FIGS. 2 and 7( a)-(c)) gave high melting temperatures (Tm,PE≈130° C.) and levels of crystallinity (˜60%) as compared to typical values for hPB. Annealing the nanoporous LPE membranes at 150° C. for 5 min causes pore collapse, as confirmed by SEM analysis (FIGS. 18( a) and (b)). - Chemical resistance to strong acids was evaluated by submerging sections of the LEL [37-28-37] derived nanoporous samples into concentrated sulfuric (@ RT), hydrochloric (@ 50° C.) and nitric (@ RT) acids for 24 h. After rinsing and drying, >95% of the mass was retained in all cases. By SEM, there was little difference in the pore structure at the exposed surface (
FIGS. 19( a)-(d)) in both the sulfuric and nitric acid cases. After the HCl treatment the porosity and pore size distribution were minimally affected according to nitrogen adsorption analysis (FIG. 20) . - A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
Claims (10)
1-10. (canceled)
11. A composition comprising a block copolymer that includes at least one polyester block and at least one linear polyolefin block, wherein the composition is in the form of a nano-structured, bicontinuous composite that includes a continuous matrix phase and a second continuous phase, wherein the continuous matrix phase comprises the linear polyolefin block of the block copolymer, and the second continuous phase comprises the polyester block of the block copolymer.
12. A composition according to claim 11 , wherein the polyolefin is polyethylene and the polyester is polylactide.
13. A composition comprising a nano-structured, bicontinuous composite that includes a continuous matrix phase comprising a linear polyolefin and a second continuous phase comprising a plurality of nano-pores.
14. A composition according to claim 13 , wherein the pores have an average pore diameter of about 1 to about 500 nanometers.
15. A composition according to claim 13 , wherein the pores have an average pore diameter of about 10 to about 50 nanometers.
16. A composition according to claim 13 , wherein the composition is in the form of a nano-porous membrane.
17. A composition according to claim 16 , wherein the membrane is a battery separator.
18. A composition according to claim 16 , wherein the membrane is a water purification membrane.
19. A composition according to claim 13 , wherein the polyolefin is polyethylene.
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CN103374142B (en) * | 2012-04-16 | 2015-07-01 | 苏州安安新材料有限公司 | Method for preparing porous diaphragm from (AB) n type block copolymer |
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US9469733B2 (en) | 2014-05-30 | 2016-10-18 | Pall Corporation | Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (IVa) |
US9604181B2 (en) | 2014-05-30 | 2017-03-28 | Pall Corporation | Membrane comprising self-assembled block copolymer and process for producing the same by spray coating (IIc) |
US9592477B2 (en) | 2014-05-30 | 2017-03-14 | Pall Corporation | Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (Ib) |
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US9441078B2 (en) | 2014-05-30 | 2016-09-13 | Pall Corporation | Self-assembling polymers—I |
US9592476B2 (en) | 2014-05-30 | 2017-03-14 | Pall Corporation | Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (IIb) |
US9593219B2 (en) | 2014-05-30 | 2017-03-14 | Pall Corporation | Membrane comprising self-assembled block copolymer and process for producing the same by spin coating (IIa) |
US9193835B1 (en) | 2014-05-30 | 2015-11-24 | Pall Corporation | Self-assembling polymers—IV |
US9169361B1 (en) | 2014-05-30 | 2015-10-27 | Pall Corporation | Self-assembling polymers—VI |
US9598543B2 (en) | 2014-05-30 | 2017-03-21 | Pall Corporation | Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (VIa) |
US9593218B2 (en) | 2014-05-30 | 2017-03-14 | Pall Corporation | Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (IIIa) |
US9616395B2 (en) | 2014-05-30 | 2017-04-11 | Pall Corportaion | Membrane comprising self-assembled block copolymer and process for producing the same by spray coating (Ic) |
US9163122B1 (en) | 2014-05-30 | 2015-10-20 | Pall Corporation | Self-assembling polymers—II |
US9593217B2 (en) | 2014-05-30 | 2017-03-14 | Pall Corporation | Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (Va) |
US9765171B2 (en) | 2014-05-30 | 2017-09-19 | Pall Corporation | Self-assembling polymers—V |
US9962662B2 (en) | 2014-06-30 | 2018-05-08 | Pall Corporation | Fluorinated polymer and use thereof in the preparation of hydrophilic membranes (vi) |
US9303133B2 (en) | 2014-06-30 | 2016-04-05 | Pall Corporation | Hydrophilic membranes and method of preparation thereof (IV) |
US9309367B2 (en) | 2014-06-30 | 2016-04-12 | Pall Corporation | Membranes comprising cellulosic material and hydrophilic block copolymer (V) |
US9718924B2 (en) | 2014-06-30 | 2017-08-01 | Pall Corporation | Hydrophilic block copolymers and membranes prepared therefrom (II) |
US9260569B2 (en) | 2014-06-30 | 2016-02-16 | Pall Corporation | Hydrophilic block copolymers and method of preparation thereof (III) |
US9394407B2 (en) | 2014-06-30 | 2016-07-19 | Pall Corporation | Hydrophilic block copolymers and membranes prepared therefrom (I) |
US9254466B2 (en) | 2014-06-30 | 2016-02-09 | Pall Corporation | Crosslinked cellulosic membranes |
EP3034547B1 (en) | 2014-12-17 | 2019-10-09 | SABIC Global Technologies B.V. | A process for the preparation of a block copolymer comprising a first polyolefin block and a second polymer block |
EP3034545B1 (en) | 2014-12-17 | 2020-11-04 | SABIC Global Technologies B.V. | A process for the preparation of a graft copolymer comprising a polyolefin main chain and one or a multiple polymer side chains and the products obtained therefrom |
EP3034544B1 (en) | 2014-12-17 | 2019-10-16 | SABIC Global Technologies B.V. | A process for the preparation of a graft copolymer comprising a polyolefin main chain and one or a multiple polymer side chains |
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WO2017097569A1 (en) * | 2015-12-09 | 2017-06-15 | Sabic Global Technologies B.V. | Process for the preparation of polyolefin-based graft copolymers comprising a first functionalized short chain branched polyolefin block and one or multiple polymer side chains |
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