CN107759720A - 氟聚合物和包含氟聚合物的膜(i) - Google Patents

氟聚合物和包含氟聚合物的膜(i) Download PDF

Info

Publication number
CN107759720A
CN107759720A CN201710694153.4A CN201710694153A CN107759720A CN 107759720 A CN107759720 A CN 107759720A CN 201710694153 A CN201710694153 A CN 201710694153A CN 107759720 A CN107759720 A CN 107759720A
Authority
CN
China
Prior art keywords
copolymer
perforated membrane
monomeric unit
acid
carbon atom
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.)
Granted
Application number
CN201710694153.4A
Other languages
English (en)
Other versions
CN107759720B (zh
Inventor
F·O·奥耶莫娃
H·艾特-哈杜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Situofan Usa Ltd
Original Assignee
Pall Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Pall Corp filed Critical Pall Corp
Publication of CN107759720A publication Critical patent/CN107759720A/zh
Application granted granted Critical
Publication of CN107759720B publication Critical patent/CN107759720B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • 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
    • B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
    • 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
    • B01D67/0093—Chemical modification
    • 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
    • B01D67/0093—Chemical modification
    • B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/28—Polymers of vinyl aromatic compounds
    • 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
    • B01D71/28—Polymers of vinyl aromatic compounds
    • B01D71/281—Polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/16—Halogens
    • C08F12/18—Chlorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/16—Halogens
    • C08F12/20—Fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/30—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/18—Chlorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/20—Fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/30—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/184—Monomers containing fluorine with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/20—Vinyl fluoride
    • C08F214/202—Vinyl fluoride with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • 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
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • 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
    • C08J5/2287—After-treatment
    • C08J5/2293—After-treatment of fluorine-containing membranes
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • 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
    • C08J9/36—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/02—Hydrophilization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/36—Introduction of specific chemical groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/08—Homopolymers or copolymers of vinylidene chloride
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18—Homopolymers or copolymers of nitriles
    • C08J2333/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Transplantation (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明涉及氟聚合物和包含氟聚合物的膜。披露了共聚物，由所述共聚物制成的多孔膜，和使用所述多孔膜处理流体以例如从产生自微电子工业的流体除去金属离子的方法，其中所述共聚物包含聚合的单体单元I和II，其中单体单元I具有式A‑X‑CH2‑B，其中A为Rf‑(CH2)n，Rf为式CF3‑(CF2)x‑的全氟烷基基团，其中x为3‑12，n为1‑6，X为O或S，且B为乙烯基苯基，单体单元II为卤代烷基苯乙烯，并且任选地其中卤代烷基中的卤代基团被任选的取代基，例如，乙二胺四乙酸、亚氨基二乙酸或亚氨基二琥珀酸替换。

Description

氟聚合物和包含氟聚合物的膜(I)
发明背景
包含氟聚合物的膜被考虑用于过滤许多流体，例如，以从微电子流体除去痕量金属杂质。这些膜中的一些特征在于低表面能值或临界润湿表面张力(CWST)值和/或对有机溶剂和侵蚀性化学品的高耐受性。尽管这些膜有一种或多种优点，仍然需要具有改进的性能比如低CWST值和/或提高的对有机溶剂和/或侵蚀性化学品的耐受性的氟聚合物和包含这样的氟聚合物的膜。
发明概述
本发明提供了具有低CWST值的氟聚合物和由该氟聚合物制成的膜。在一种实施方案中，本发明提供了包含聚合的单体单元I和II的共聚物，
其中单体单元I具有式：A-X-CH2-B，
其中A为Rf-(CH2)n，Rf为式CF3-(CF2)x-的全氟烷基基团，
x为3-12，n为1-6，X为O或S，且B为乙烯基苯基，以及
单体单元II为卤代烷基苯乙烯，并且任选地
其中卤代烷基苯乙烯的卤素基团被选自以下的取代基替换：烷氧基，烷基羰基，羟基烷基，酸基团，碱基团，阳离子，阴离子，两性离子，羟基，酰氧基，烷硫基，醛基，酰氨基，氨甲酰基，脲基，氰基，硝基，乙二胺四乙酸，亚氨基二乙酸，和亚氨基二琥珀酸。
该共聚物为超疏水性聚合物并且可以用于赋予材料表面以疏油性能，即，表面张力低于25达因/cm。本发明还提供了制备包含置于多孔载体上的所述共聚物的多孔膜的方法。本发明进一步提供了过滤流体，特别是微电子流体至浓度低于1ppb，优选低于0.005ppb或低于大多数仪器的保留极限的方法。
附图说明
图1展示了依照本发明的一种实施方案制备多孔膜的方法，其中颗粒比如NaHCO3用于产生孔。
图2A描绘了依照本发明的实施方案制备的平片膜横截面的SEM显微照片。
图2B描绘了该平片膜一侧的SEM显微照片。
图2C描绘了该平片膜另一侧的SEM显微照片。
图3描绘了依照本发明的另一实施方案制备的多孔膜横截面的SEM显微照片。
图4展示了改性根据一种实施方案的多孔膜以在表面上包括官能团的方法。
图5描绘了依照本发明的实施方案制备的膜的金属去除功效。
发明详述
依照一种实施方案，本发明提供了包含聚合的单体单元I和II的共聚物，
其中单体单元I具有式：A-X-CH2-B，
其中A为Rf-(CH2)n，Rf为全氟烷基基团式的CF3-(CF2)x-，
x为3-12，n为1-6，X为O或S，且B为乙烯基苯基，以及
单体单元II为卤代烷基苯乙烯，并且任选地
其中卤代烷基苯乙烯的卤素基团被选自以下的取代基替换：烷氧基，烷基羰基，羟基烷基。酸基团，碱基团，阳离子，阴离子，两性离子，羟基，酰氧基，烷硫基，醛基，酰氨基，氨甲酰基，脲基，氰基，硝基，乙二胺四乙酸，亚氨基二乙酸，和亚氨基二琥珀酸。
在所述共聚物的一种实施方案中，n＝2、3或4，特别是2。
在任意上述实施方案中，x＝4、5、6、7或8，特别是6。
在任意上述实施方案中，单体单元II为氯烷基苯乙烯，特别是氯甲基苯乙烯。卤代烷基或氯烷基可以在间位或对位取代在苯乙烯上，或单体II可以为间位和对位取代的卤代烷基苯乙烯的混合物。
全氟烷基基团可以存在于苯环B上的任何合适的位置，邻位、间位或对位，优选间位或对位位置，或可以使用o、m和/或对位异构体的混合物。这里，“p/m”代表对位和间位异构体的混合物。
在任意上述实施方案中，所述共聚物为嵌段共聚物，例如，二嵌段、三嵌段或多嵌段共聚物，或无规共聚物。
“烷基”基团可为直链或支化的。依照一种实施方案，烷基基团优选为C1-C22烷基。烷基基团的实例包括甲基，乙基，正丙基，异丙基，正丁基，仲丁基，异丁基，叔丁基，正戊基，异戊基，正己基，十六烷基等。这样的定义也适用于“烷基”出现的任何地方，比如在羟基烷基、单卤代烷基、二卤代烷基和三卤代烷基中。C1-C22烷基基团还可以进一步被环烷基基团，例如C3-C11环烷基基团取代。
依照一种实施方案，“烷氧基”基团优选为C1-C22烷氧基。烷氧基基团的实例包括甲氧基，乙氧基，正丙氧基，异丙氧基，正丁氧基，仲丁氧基，异丁氧基，叔丁氧基，正戊氧基，异戊氧基，正己氧基，十六烷氧基等。
术语“卤代”是指选自氟、氯、溴和碘的卤素，优选氯。
不论在结构中原子数范围被在何时被指出(例如C1-22，C1-12，C1-8，C1-6或C1-4烷基，烷氧基等)，都具体地设想到了也可以使用落入所指出的范围内的任碳原子的何子范围或单个数字。因此，例如，关于本文提到的任何化学基团(例如烷基，烷氧基等)所使用的1-22个碳原子(例如C1-C22)，1-20个碳原子(例如C1-C20)，1-18个碳原子(例如C1-C20)，1-16个碳原子(例如C1-C16)，1-14个碳原子(例如C1-C14)，1-12个碳原子(例如C1-C12)，1-10个碳原子(例如C1-C10)，1-8个碳原子(例如C1-C8)，1-6个碳原子(例如C1-C6)，1-4个碳原子(例如C1-C4)，1-3个碳原子(例如C1-C3)或2-8个碳原子(例如C2-C8)范围的引述都合适地涵盖并具体地描述了1，2，3，4，5，6，7，8，9，10，11，12，13，14，15，16，17，18，19，20，21或22个碳原子以及其任何子范围，合适地例如1-2个碳原子，1-3个碳原子，1-4个碳原子，1-5个碳原子，1-6个碳原子，1-7个碳原子，1-8个碳原子，1-9个碳原子，1-10个碳原子，1-11个碳原子，1-12个碳原子，1-13个碳原子，1-14个碳原子，1-15个碳原子，1-16个碳原子，1-17个碳原子，1-18个碳原子，1-19个碳原子，1-20个碳原子，1-21个碳原子和1-22个碳原子，以及其间的任何范围，比如2-3个碳原子，2-4个碳原子，2-5个碳原子，2-6个碳原子，2-7个碳原子，2-8个碳原子，2-9个碳原子，2-10个碳原子，2-11个碳原子，2-12个碳原子，2-12个碳原子，2-13个碳原子，2-14个碳原子，2-15个碳原子，2-16个碳原子，2-17个碳原子，2-18个碳原子，2-19个碳原子，2-20个碳原子，2-21个碳原子和2-22个碳原子，3-4个碳原子，3-5个碳原子，3-6个碳原子，3-7个碳原子，3-8个碳原子，3-9个碳原子，3-10个碳原子，3-11个碳原子，3-12个碳原子，3-13个碳原子，3-14个碳原子，3-15个碳原子，3-16个碳原子，3-17个碳原子，3-18个碳原子，3-19个碳原子，3-20个碳原子，3-21个碳原子，和3-22个碳原子，和4-5个碳原子，4-6个碳原子，4-7个碳原子，4-8个碳原子，4-9个碳原子，4-10个碳原子，4-11个碳原子，4-12个碳原子，4-13个碳原子，4-14个碳原子，4-15个碳原子，4-16个碳原子，4-17个碳原子，4-18个碳原子，4-19个碳原子，4-20个碳原子，4-21个碳原子，4-22个碳原子等。
在一种实施方案中，所述共聚物选自对位和/或间位取代的[[(全氟己基亚乙基)氧基]甲基]-苯乙烯和卤代烷基苯乙烯单体的共聚物；对位和/或间位取代的[[(全氟己基亚乙基)硫基]甲基]-苯乙烯和卤代烷基苯乙烯单体的共聚物；聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯和聚[氯甲基苯乙烯]的共聚物；聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯和聚[氯甲基苯乙烯]和聚[氯甲基苯乙烯]的共聚物。
依照本发明的实施方案，链段A包含选自以下的单体：2-(全氟己基)乙醇，2-(全氟辛基)乙硫醇，2-(全氟辛基)乙醇，2-(全氟己基)乙硫醇，对位和/或间位取代的[[(全氟己基亚乙基)氧基]甲基]-苯乙烯，和对位和/或间位取代的[[(全氟己基亚乙基)硫基]甲基]-苯乙烯。不希望受任何特定理论或机理的束缚，全氟烃提供了疏油性能和改进的对基材的粘附性。
在一种实施方案中，链段B包含苯乙烯和卤素基团，其中卤素基团为氯。在另一实施方案中，链段B包含选自4-乙烯基苄基氯、3-乙烯基苄基氯、3,4-乙烯基苄基氯的单体。苯乙烯基团中的双键使得与其它聚合物的聚合更容易，并且由于卤素基团(其可以被其它官能团替代)，苯乙烯可以容易地用许多官能团中的一种或多种、包括带正电和/或负电的基团改性。
所述共聚物可以通过任何合适的技术制备。例如，嵌段共聚物可以如方案1中所示制备，而无规共聚物可以如方案2中所示制备。
在一种实施方案中，无规共聚物可以通过将1.4当量的4-对位或3,4-对位-间位-氯甲基苯乙烯与1当量的对位或p，m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯在甲苯中在合适的浓度(例如66wt.％的p，m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯)混合来合成。然后将3mol％的偶氮二异丁腈(AIBN)加入，并将混合物脱气20分钟，之后，将反应混合物在合适的温度，例如60摄氏度搅拌合适的时间，例如14小时。将反应混合物冷却并用丙酮稀释。将获得的产物在甲醇中沉淀并混合2小时。将溶剂倾析并将沉淀再溶于丙酮。将丙酮中的产物在新鲜甲醇中再沉淀并使用粗多孔漏斗过滤，用甲醇洗涤，和在真空炉中干燥过夜。
在一种实施方案中，无规共聚物的数均分子量为约1KDa-约500KDa，例如10KDa-约50KDa，和特别是约20KDa。在一种实施方案中，数均分子量为398KDa。数均分子量通过使用GPC测定。
嵌段共聚物可以任何合适的方法合成，包括例如原子转移自由基聚合(ATRP)、碘转移聚合(ITP)、阴离子聚合和其它形式的氮化物介导的自由基聚合(NMP)。
嵌段共聚物的数均分子量为约1KDa-约9000KDa，特别是10KDa-约50KDa，和更特别是约20KDa。虽然嵌段共聚物的分子量会取决于聚合时长，嵌段的平均分子量对于86小时运行来说为大约8178KDa。
本发明进一步提供了包含置于多孔载体、例如多孔聚合物载体上的任何上述共聚物的多孔膜。在一种实施方案中，多孔聚合物载体选自PVC/PAN，聚砜，聚醚砜，HDPE，PET，PPS，PPSU(聚苯基砜)，PTFE，PVDF，PVF(聚氟乙烯)，PCTFE(聚氯三氟乙烯)，FEP(氟化乙烯-丙烯)，ETFE(聚乙烯四氟乙烯)，ECTFE(聚乙烯氯三氟乙烯)，PFPE(全氟聚醚)，PFSA(全氟磺酸)，和全氟聚环氧丙烷。
本发明进一步提供了制备包含上述共聚物的多孔膜的方法，该方法在一种实施方案中包括：
(i)将所述共聚物溶解在溶剂中以获得包含所述共聚物的溶液；
(ii)流延来自(i)的溶液以获得涂层；
(iii)从所述涂层蒸发溶剂；任选地
(iv)洗涤所述涂层以获得所述多孔膜；和
(v)任选地用选自以下的取代基替换所述卤代烷基的卤代基团中的一个或多个：烷氧基，烷基羰基，羟基烷基，酸基团，碱基团，阳离子，阴离子，两性离子，羟基，酰氧基，烷硫基，醛基，酰氨基，氨甲酰基，脲基，氰基，硝基，乙二胺四乙酸，亚氨基二乙酸，和亚氨基二琥珀酸。
当卤代基团任选地如上所述被取代基替换时，所得共聚物具有更高的表面张力值，例如，至多约45达因/cm，特别是约40-约45达因/cm。
任选的替换可以通过任何合适的方法进行。例如，可以将步骤(iv)结束时获得的多孔膜在改性剂(例如亚氨基二琥珀酸(IDSA))在水、NaOH和DMF的混合物中的溶液中浸泡合适的时间段。可以将该溶液加热至80℃。然后用水和异丙醇(IPA)洗涤该膜并干燥。然后将该膜浸泡在HCl中，用IPA漂洗，并干燥。
在一种实施方案中，将IDSA(15g)溶于水(18g)，8M NaOH(10g)和DMF(45g)的混合物。将混合物倾倒在培养皿中用DMF预润湿的膜上。将膜加热至80℃过夜，用大量水漂洗，然后用IPA漂洗。然后将膜在80℃下干燥1小时。将膜在3％HCl中浸泡2小时，用水和IPA漂洗1小时，再在80℃干燥45分钟。该膜的表面张力范围在40-45达因/cm。
在另一实施方案中，将亚氨基二乙酸(IDA)(60g)溶于水(120g)、8M NaOH(140g)和DMF(160g)的混合物中。然后将混合物倾倒在培养皿中用DMF预润湿的膜上。将膜加热至80℃过夜，用大量水漂洗，然后用IPA漂洗。然后将膜在80℃下干燥1小时。将膜在3％HCl中浸泡2小时，用水和IPA漂洗，再在80℃干燥45分钟。所得膜的表面张力范围在45-48达因/cm。
在再另一实施方案中，将在水(50mL)中的三乙胺(TEA)33％与IPA(50mL)混合，和CWST为23达因/cm的聚(PFOTMS-ran-CMS)涂覆的0.2μm PTFE在室温浸渍在该溶液中过夜。之后，将该膜用大量水漂洗，然后浸泡在IPA中过夜。将膜在80℃干燥30分钟，并测量表面张力。CWST为38达因/cm
在另一实施方案中，本发明提供了制备包含上述共聚物的多孔膜的方法，该方法包括：
(i)将所述共聚物和第二聚合物溶于溶剂中以获得包含所述共聚物和该第二聚合物的溶液；
(ii)将来自(i)的溶液与成孔粉末混合以获得混合物；
(iii)流延来自(ii)的混合物以获得涂层；
(iv)从所述涂层蒸发溶剂；
(v)洗涤所述涂层以除去所述成孔粉末；和
(vi)干燥所得膜；和
(v)任选地用选自以下的取代基替换所述卤代烷基的卤代基团中的一个或多个：烷氧基，烷基羰基，羟基烷基。酸基团，碱基团，阳离子，阴离子，两性离子，羟基，酰氧基，烷硫基，醛基，酰氨基，氨甲酰基，脲基，氰基，硝基，乙二胺四乙酸，亚氨基二乙酸，和亚氨基二琥珀酸。
多孔膜可以是疏油的，特别是CWST为约23达因/cm或更低，例如22或21达因/cm的疏油膜。多孔膜可以是例如制成就能用的(functionally-as-made)膜，其包含所述共聚物膜或纤维，但没有多孔载体；或它可以为涂覆有所述共聚物的多孔载体。
CWST可以通过合适的方法测量。在一种实施方案中，所述方法依赖于一组特定组成的溶液。每种溶液具有特定表面张力。溶液表面张力范围在15至92达因/cm，以小的非相等量递增。为了测量膜表面张力，将其放在白光桌子上，将一滴某表面张力的溶液施加到所述多孔膜表面，记录液滴穿透所述多孔膜并作为光穿过所述多孔膜的指示的变成亮白色的时间。当液滴穿透所述多孔膜的时间为≤10秒时，认为是立即润湿。如果时间>10秒，则认为溶液部分润湿所述多孔膜。
依照本发明的实施方案，所述多孔膜为这样的多孔膜，例如纳米多孔膜，例如，孔直径为1nm至100nm的多孔膜，或孔直径为1μm至10μm的微米多孔膜。
所述多孔膜还可为包含在所述共聚物上的一种或多种加入的官能团的官能化的膜。该多孔膜可以为，例如带电膜。所述共聚物膜的官能化可以使CWST为至多约50达因/cm。官能基团包括，例如阳离子、阴离子或极性基团。
依照本发明的实施方案，所述多孔膜可以具有许多构型，包括平面的、平片、褶皱的、管形的、螺旋的和中空纤维。在一种实施方案中，所述多孔膜为中空纤维膜。
根据本发明的实施方案的多孔膜典型地被置于外壳中，该外壳包含至少一个入口和至少一个出口，并限定该入口和该出口之间的至少一个流体流路，其中至少一个本发明的膜或包括至少一个本发明的膜的过滤器穿过该流体流路，以提供过滤器器件或过滤器模块。在一种实施方案中，过滤器器件提供为包含外壳，该外壳包含入口和第一出口，并限定该入口和该第一出口之间的第一流体流路；和至少一个本发明的膜或包含至少一个本发明的膜的过滤器，本发明的膜或包含至少一个本发明的膜的过滤器置于外壳中穿过该第一流体流路。
优选地，对于交叉流应用来说，至少一个本发明的膜或包含至少一个本发明的膜的过滤器置于外壳中，该外壳包含至少一个入口和至少两个出口，并限定至少在该入口和该第一出口之间的第一流体流路，和在该入口和该第二出口之间的第二流体流路，其中本发明的膜或包含至少一个本发明的膜的过滤器穿过该第一流体流路以提供过滤器器件或过滤器模块。在说明性的实施方案中，过滤器器件包含交叉流过滤器模块，外壳包含入口，包含浓液出口的第一出口，和包含渗透物出口的第二出口，和限定该入口和该第一出口之间的第一流体流路，和该入口和该第二出口之间的第二流体流路，其中至少一个本发明的膜或包含至少一个本发明的膜的过滤器设置穿过该第一流体流路。
过滤器器件或模块可为能消毒的。可采用具有合适的形状并提供入口和一个或多个出口的任何外壳。
外壳可以由任何合适的刚性不能渗透的材料制造，包括与被处理的流体相容的任何不能渗透的热塑性材料。例如，外壳可以由金属，比如不锈钢制造，或由聚合物，例如透明的或半透明的聚合物，比如丙烯酸类、聚丙烯、聚苯乙烯或聚碳酸酯树脂制造。
所述多孔膜可以为制成就能用的膜(“FAM膜”)，其可以例如如图1中所示制备，将聚(PFTOMS-ran-CMS)与第二聚合物，例如PVC-AN在THF中共混并以600rpm搅拌60分钟，然后将达到所需的孔径的可溶性颗粒，比如NaHCO3颗粒，加入溶液，并以1500rpm搅拌120分钟。然后将该混合物流延在在玻璃板上的PET基材上。在室温下慢慢蒸发THF后，将膜浸泡在稀HCl溶液中过夜以除去颗粒。将所得膜在烤箱中或在室温下在合适的温度下干燥例如40℃至100℃，特别是80℃(取决于溶剂的沸点)合适的时间例如60min以除去溶剂。
合适的第二聚合物包括PVC-AN，HDPE，PET，PPS，PPSU(聚苯基砜)，PTFE，PVDF，PVF(聚氟乙烯)，PCTFE(聚氯三氟乙烯)，FEP(氟化乙烯-丙烯)，ETFE(聚乙烯四氟乙烯)，ECTFE(聚乙烯氯三氟乙烯)，PFPE(全氟聚醚)，PFSA(全氟磺酸)，和全氟聚环氧丙烷。
可以用于上述方法的其它可溶的或可去除的颗粒包括碳酸钾，沸石，纤维素，可溶性纤维，二氧化硅颗粒和纳米颗粒；例如氧化锌。所述多孔膜可以以多种方式之一包含所述共聚物。例如，所述多孔膜可包括包含所述共聚物的涂层。涂覆的膜可以例如通过膜涂覆制造，其通过以下方式进行：将2％共聚物溶解在丙酮中，并将膜浸泡在聚合物溶液中2秒。将所得膜在合适的温度例如80℃干燥约20分钟，和将所述多孔膜浸泡在IPA中约2小时，在80℃在烘箱中干燥30分钟，测量表面张力和重量增加。膜的实例的SEM显微图示于图2。
所述多孔膜可以被改性以包括一种或多种官能基团。构建官能化的膜的总体方案示于图4中。所述多孔膜可以被带电基团官能化。例如，在一种实施方案中，所述多孔膜被阴离子基团官能化。阴离子膜的制备包括，例如溶于在水(100g)、8M NaOH(100g)和DMF(200g)的混合物中的EDTA(40g)中。然后将混合物倾倒在培养皿中用DMF预润湿的膜上。将膜加热至80℃过夜，用大量水漂洗，然后用IPA漂洗。然后将膜在80℃下干燥1小时并在3％HCl中浸泡2小时，用水和IPA漂洗1小时，再在80℃干燥45分钟。用水和IPA漂洗1小时，再在80℃干燥45-50达因/cm。在这样的方法中获得的膜从异丙醇中除去99％的痕量金属。
氟化链必须以聚合物的至少35体积％存在以赋予所述多孔膜疏水性。
另外，无规共聚物中全氟苯乙烯嵌段的体积比不得大于50％，以使所述聚合物可溶于非氟化溶剂中。
在另一实施方案中，所述多孔膜被阳离子基团官能化，其可以例如通过如下方式制备：将水(50mL)中的三乙胺33％与IPA(50mL)混合，和将多孔膜，例如PTFE在该混合物中在室温浸渍过夜。之后，将膜用水漂洗并浸泡在IPA中过夜。将膜在80℃干燥30分钟，并测量表面张力。CWST为38达因/cm。
本发明包括以下实施方案，但不限于：
1)包含链段A和链段A的无规共聚物，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；和链段B为氯甲基苯乙烯；
2)包含链段A和链段B的嵌段共聚物，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；和链段B为氯甲基苯乙烯；
3)可官能化的无规共聚物和官能团，该无规共聚物包含链段A和链段B，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；链段B为氯甲基苯乙烯；和该官能团包括亲水性的、疏水性的、带正电或带负电的官能团；
4)可官能化的嵌段共聚物和官能团，该嵌段共聚物包含链段A和链段B，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；链段B为氯甲基苯乙烯；和该官能团包括亲水性的、疏水性的、带正电或带负电的官能团；
5)包含亲水性的、疏水性的或带电膜和涂层的多孔膜，该涂层包含含有链段A和链段B的无规共聚物，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；和链段B为氯甲基苯乙烯；其中，当涂覆有所述共聚物时，所述多孔膜为表面张力为23达因/cm或更低的疏油膜；
6)包含亲水性的、疏水性的或带电膜和涂层的官能化的膜，该涂层包含无规共聚物和官能团，该无规共聚物包含链段A、链段B和官能团，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；链段B为氯甲基苯乙烯；该官能团为带电基团或亲水性的基团；其中，当涂覆时，所述多孔膜的表面张力为23达因/cm或更低；
7)包含亲水性的、疏水性的或带电膜和涂层的多孔膜，该涂层包含包含链段A和链段B的嵌段共聚物，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；和链段B为氯甲基苯乙烯；其中，当用所述共聚物涂覆时，所述多孔膜为表面张力为23达因/cm或更低的疏油膜；
8)包含亲水性的、疏水性的或带电膜和涂层的带电膜，该涂层包含无规共聚物和官能团，该无规共聚物包含链段A和链段B，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；链段B为氯甲基苯乙烯；该官能团包含乙二胺四乙酸、亚氨基二乙酸或亚氨基二琥珀酸；其中，当用所述共聚物涂覆时，所述多孔膜的表面张力为至多50达因/cm，其可以用于从微电子流体和水去除痕量金属离子；
9)疏油的、制成就能用的膜，其包含第一聚合物和无规共聚物的共混物，该无规共聚物包含链段A和链段B，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；链段B为氯甲基苯乙烯；其中所述多孔膜的表面张力为23达因/cm或更低；
10)表面张力为23达因或更低的疏油的中空纤维膜，所述多孔膜包含用于所述多孔膜的聚合物(比如，例如PES，PTFE，PVDF PVC/AN，PP，PE，HDPE，PET，PPS和PPSU)和包含链段A和链段B的无规或嵌段共聚物，其中链段A为聚[p/m-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯或聚[p/m-[[(全氟己基亚乙基)氧基]甲基]-苯乙烯；和链段B为氯甲基苯乙烯。
根据本发明的实施方案的多孔膜可以用于许多应用，包括，例如，诊断应用(包括，例如，样品制备和/或诊断横向流动器件)，喷墨应用，光刻，例如作为HD/UHMW PE基介质的替代品，用于制药工业的过滤流体，金属去除，生产超纯水，工业和地表水处理，用于医疗应用的过滤流体(包括家庭和/或患者使用，例如静脉应用，也包括例如过滤生物流体比如血液(例如病毒去除))，用于电子工业的过滤流体(例如用微电子工业和热SPM中的过滤光刻胶流体)，用于食品和饮料行业的过滤流体，啤酒过滤，澄清，过滤抗体和/或含蛋白质的流体，过滤含有核酸的流体，细胞检测(包括原位)，细胞收获和/或过滤细胞培养流体。或者或另外，根据本发明的实施方案的多孔膜可以用于过滤空气和/或气体和/或可以用于排气应用(例如允许空气和/或气体，但不是液体通过)。根据本发明的实施方案的多孔膜可以用于许多器件，包括外科器件和产品，比如，例如，眼外科产品。
本发明进一步提供了过滤流体的方法，该方法包括使流体通过任何上述多孔膜。例如，痕量金属杂质在下一代半导体和微电子材料的制造中仍旧存在问题。本发明的一种实施方案包含从流体，特别是微电子流体除去金属的方法，其通过使含金属的流体穿过包含所述共聚物的多孔膜和从所述流体除去所述金属。在一种实施方案中，本发明的方法包括使含金属的流体穿过包括所述共聚物和官能团的官能化的多孔膜，以及从所述流体除去所述金属。所述官能化的膜可以从所述流体去除约99％的大多数痕量金属。
痕量金属的实例包括Li，Na，K(以及其它第1族金属)；Mg，Ca(以及其它第2族金属)；Al(以及其它第3族金属)，Pb(以及其它第4族金属)，Sb，Bi(以及其它第5族金属)，和Cd，Cr，Mo，Pd，Ag，W，V，Mn，Fe，Ni，Cu，Zn(以及其它过渡金属)。
有利地，所述共聚物可以赋予材料，比如，例如多孔膜疏油性能，为该材料提供23达因或更低的表面张力，无需后处理。包括所述共聚物的多孔膜在高温下在酸、碱、有机溶剂、氧化剂中稳定，并强抗γ辐射。可以在所述多孔膜中实现高的水突破压力和空气流速，并且所述膜可以被容易地官能化，比如，例如用阳离子和阴离子基团。
所述多孔膜可以用于在许多应用中，比如微电子工业中从水和有机流体除去痕量金属，例如，使得滤液的浓度为0.005ppb或低于仪器的检测极限。在一种实施方案中，被处理的流体包含1ppb或更多的痕量金属，而滤液的痕量金属浓度为0.005ppb。
以下实施例进一步说明本发明，但当日不应解释为以任何方式限制其范围。
实施例1
本实施例展示了依照本发明的实施方案的无规共聚物p-[[(全氟己基亚乙基)硫基]甲基]-苯乙烯和氯甲基苯乙烯或聚(PFOTMS-ran-CMS)的制备。在250mL干燥的圆底烧瓶中混合全氟己基乙基硫基甲基苯乙烯(60.3g，121.6mmol)，4-氯甲基苯乙烯(26g，171mmol，1.4当量)，甲苯(20mL)和AIBN(838mg，5mmol，3mol％)。将反应混合物在0℃用氮气脱气45分钟，在60℃搅拌14小时，然后将反应混合物冷却并加入30mL丙酮。将共聚物产物在甲醇(1L)中沉淀并混合2小时。将溶剂倾析并将沉淀再溶于丙酮(200mL)。将丙酮中的产物再沉淀于新鲜甲醇(2L)中，过滤，用甲醇洗涤(500mL)，和在真空炉中干燥过夜。所得共聚物重58g。1HNMR谱证实了共聚物的结构：
无规的共聚物p-[[(全氟辛基亚乙基)硫基]甲基]-苯乙烯和氯甲基苯乙烯，((聚(PFDTMS-ran-CMS))也使用相同的工序制备。
实施例2
本实施例展示了依照本发明的实施方案由聚(PFOTMS-ran-CMS)的膜的制备。无规共聚物溶解于丙酮，并流延在多孔载体上。由此，制备在丙酮中2％的共聚物溶液，并将多孔载体(PTFE或PES)浸渍在所述共聚物溶液中2秒。将所得涂覆的载体在80℃在烘箱中干燥20分钟，并在IPA中浸泡2小时，在80℃在烘箱中干燥30分钟，并且测量表面张力和增重。获得的增重和表面张力结果在表1-2中给出。
表1.PTFE上涂覆的聚(PFOTMS-ran-CMS)的增重结果
表2.涂覆的膜的表面张力测量；空气流动/水穿透表征
实施例3
本实施例展示了依照本发明的实施方案的嵌段共聚物全氟己基乙硫醇和氯甲基苯乙烯，聚(PFOTMS-b-CMS)的制备。聚(PFOTMS-嵌段-CMS)通过氯甲基苯乙烯及之后的全氟己基乙基硫基甲基苯乙烯的顺序聚合来合成，全氟己基乙基硫基甲基苯乙烯在40小时后加入。氯甲基苯乙烯(14.5ml，100mmol，在6.5mL氯苯中)、重结晶的过氧化苯甲酰(BPO)(0.242g，1mmol)和TEMPO(0.2g，1.3mmol)的溶液加入圆底烧瓶。在冰水浴中脱气20分钟后，将反应混合物在95℃加热3小时以完全分解BPO，并在125℃下加热40小时，以使聚合物进行。将反应混合物冷却到室温，用3mL氯苯稀释，并加入PFOTMS(31.18g，62.9mmol，在6mL氯苯中)。混合物如前所述脱气。反应在130℃进行24小时。用氯仿(100mL)稀释后，从甲醇中沉淀得到嵌段共聚物，干燥以从单体得到88％。NMR结果显示CMS/PFOTMS比为1/0.62。DSC结果表面该嵌段共聚物具有两个Tg(53℃和79℃)。该嵌段共聚物的1H NMR谱证实了共聚物的结构。表3显示了该嵌段共聚物的一些性能，例如Tg。嵌段共聚物p-[[(全氟辛基亚乙基)硫基]甲基]-苯乙烯和氯甲基苯乙烯，聚(PFDTMS-b-CMS)也使用相同的工序合成。
表3.GPC测量的无规和嵌段共聚物的分子量
实施例4
本实施例展示了依照本发明的实施方案由共聚物制备多孔膜的方法。
将p-[[(全氟辛基亚乙基)硫基]甲基]-苯乙烯和氯甲基苯乙烯(聚(PFDTMS-ran-CMS))和聚氯乙烯/丙烯腈(PVC-AN)按如下共混。聚(PFDTMS-ran-CMS)和PVC-AN在THF中混合并以600rpm搅拌60分钟。将具有1.79μm的平均粒度的NaHCO3颗粒加入溶液中并以1500rpm搅拌120分钟。然后将聚合物共混物流延到用PEG 400涂覆的玻璃板上。或者，将聚合物共混物流延到安装在玻璃板上的PET基材上。在室温下慢慢蒸发THF后，将所得膜在稀HCl溶液中浸泡并蚀刻过夜，除去颗粒，并在80℃烘箱中干燥60分钟。
表4.疏油PVC/AN膜流延后的空气流动、水穿透压力和表面张力表征
性能 表现
CWST 21.62达因/cm
AFR(SLPM@5psi) 49
WBT(psi) 2.02
表5.疏油PVC/AN膜流延后的空气流动速率和表面张力表征
性能 表现
CWST 21.62达因/cm
AFR(SLPM@5psi) 22.85
所得膜通过经EDTA、亚氨基二琥珀酸(IDSA)、三乙胺(TEA)或亚氨基二乙酸(IDA)处理来进行带电改性。表6列出了由IDA、EDTA和TEA改性的多孔膜的电荷密度值。
表6.元素分析得到的阴离子和阳离子膜的电荷密度
实施例5
本实施例展示了使用实施例4的EDTA或IDA改性膜从微电子流体、特别是水和异丙醇除去痕量金属离子的方法。
依照本发明的实施方案的多孔膜金属离子去除功效通过用改性膜过滤掺有1ppb的几种金属的异丙苯进行测试。在测试之前，将所有测试设备浸泡在3％HCl中24小时，并在去离子水(DIW)中冲洗。从三个不同的平片介质样品中切出三个47mm的圆盘。将每个盘放在外壳中以挑战。每个样品依次用100mL的IPA，然后用100mL的5％HCl，最后200mL的DIW冲洗。将20mL IPA冲洗通过所述多孔膜，最后10mL作为介质空白收集。每个样品用掺有1ppb金属的IPA进行挑战。建立了7mL/min的流出物流速。弃去初始的10mL流出液。将接下来的10mL流出物收集到PFA瓶中。收集流入物和所有流出物样品以进行ICP-MS分析。图5显示了滤液中金属的浓度。本发明的膜的金属去除率优于普通膜的金属去除率。
所引用的所有参考文献，专利申请和专利在此通过引用并入本文，其程度如同每个参考文献被单独地和具体地指出通过引用并入，并且在这里被全部阐述。
在本发明(特别是在以下权利要求的上下文中)中使用术语“一”和“一(a)”和“一(an)”和“至少一个”以及类似的指示物应被解释为涵盖单数和复数，除非另有说明这里或明显与上下文相矛盾。使用术语“至少一个”后跟一种或多种项目的列表(例如，“至少一个A和B”)被认为是指从列出的项目(A或B)或列出的项目(A和B)中的两个或更多的任何组合，除非另有说明，这里或明确地与上下文相矛盾。术语“包含”、“具有”、“包括”和“包含”应被视为开放式术语(即，“包括但不限于”)，除非其明确指出。值的范围的引用仅用于作为简单地将每个单独的值引用到范围内的简写方法，除非另有说明，并将每个单独的值并入规范中，如同单独列举的那样。这里描述的所有方法可以以任何合适的顺序执行，除非本文明确指出或明确地与上下文相矛盾。提供这种使用任何和所有实施例或示范性语言(例如“比如”)，只是为了更好地阐明本发明，并不对本发明的范围构成限制，除非另有声明。说明书中的语言不应被解释为表明任何未要求保护的要素对本发明的实践至关重要。
本发明的优选实施方案描述在本文中，包括本发明人已知的用于实施本发明的最佳方式。这些优选实施方案的变化在阅读前面的描述后可以对本领域普通技术人员而言变得显而易见。发明人期望本领域技术人员适当地使用这种变化，并且本发明人打算以不同于本文具体描述的方式实施本发明。因此，本发明包括根据适用法律允许的所附权利要求中所述的所有修改和等同的主题。此外，上述要素在其所有可能的变体中的任何组合都包含在本发明中，除非本文明确地指出或上下文明显有矛盾。

Claims (14)

1.包含聚合的单体单元I和II的共聚物，其中：
单体单元I具有式A-X-CH2-B，其中A为Rf-(CH2)n，Rf为式CF3-(CF2)x-的全氟烷基基团，其中x为3-12，n为1-6，X为O或S，且B为乙烯基苯基，
单体单元II为卤代烷基苯乙烯，和
任选地其中卤代烷基的卤代基团被选自以下的取代基替换：烷氧基，烷基羰基，羟基烷基，酸基团，碱基团，阳离子，阴离子，两性离子，羟基，酰氧基，烷硫基，醛基，酰氨基，氨甲酰基，脲基，氰基，硝基，乙二胺四乙酸，亚氨基二乙酸，和亚氨基二琥珀酸。
2.权利要求1所述的共聚物，其中n＝2。
3.所述的共聚物权利要求1或2，其中x＝4-8。
4.权利要求1-3中任一项所述的共聚物，其中单体单元II为氯烷基苯乙烯。
5.权利要求1-4中任一项所述的共聚物，其中所述卤代烷基为氯甲基。
6.权利要求1-5中任一项所述的共聚物，其为嵌段共聚物。
7.权利要求1-5中任一项所述的共聚物，其为无规共聚物。
8.多孔膜，其包含置于多孔载体上的权利要求1-7中任一项所述的共聚物。
9.权利要求8所述的多孔膜，其中所述多孔载体为多孔聚合物载体。
10.权利要求9所述的多孔膜，其中所述多孔聚合物载体选自PVC/PAN，聚砜，聚醚砜，HDPE，PET，PPS，PPSU(聚苯基砜)，PTFE，PVDF，PVF(聚氟乙烯)，PCTFE(聚氯三氟乙烯)，FEP(氟化乙烯-丙烯)，ETFE(聚乙烯四氟乙烯)，ECTFE(聚乙烯氯三氟乙烯)，PFPE(全氟聚醚)，PFSA(全氟磺酸)，和全氟聚环氧丙烷。
11.制备包含共聚物的多孔膜的方法，
其中所述共聚物包含聚合的单体单元I和II，其中：
单体单元I具有式A-X-CH2-B，其中A为Rf-(CH2)n，Rf为式CF3-(CF2)x-的全氟烷基基团，其中x为3-12，n为1-6，X为O或S，且B为乙烯基苯基，以及
单体单元II为卤代烷基苯乙烯；
所述方法包括：
(i)将所述共聚物溶于溶剂中以获得包含所述共聚物的溶液；
(ii)流延来自(i)的溶液以获得涂层；
(iii)从所述涂层蒸发溶剂；任选地
(iv)洗涤所述涂层以获得所述多孔膜；和
(v)任选地用选自以下的取代基替换所述卤代烷基的卤代基团中的一个或多个：烷氧基，烷基羰基，羟基烷基。酸基团，碱基团，阳离子，阴离子，两性离子，羟基，酰氧基，烷硫基，醛基，酰氨基，氨甲酰基，脲基，氰基，硝基，乙二胺四乙酸，亚氨基二乙酸，和亚氨基二琥珀酸。
12.制备包含共聚物的多孔膜的方法，
其中所述共聚物包含聚合的单体单元I和II，其中：
单体单元I具有式A-X-CH2-B，其中A为Rf-(CH2)n，Rf为式CF3-(CF2)x-的全氟烷基基团，其中x为3-12，n为1-6，X为O或S，且B为乙烯基苯基，以及
单体单元II为卤代烷基苯乙烯；
所述方法包括：
(i)将所述共聚物和第二聚合物溶于溶剂中以获得包含所述共聚物和该第二聚合物的溶液；
(ii)将来自(i)的溶液与成孔粉末混合以获得混合物；
(iii)流延来自(ii)的混合物以获得涂层；
(iv)从所述涂层蒸发溶剂；
(v)洗涤所述涂层以除去所述成孔粉末；和
(vi)干燥所得膜；和
(v)任选地用选自以下的取代基替换所述卤代烷基的卤代基团中的一个或多个：烷氧基，烷基羰基，羟基烷基，酸基团，碱基团，阳离子，阴离子，两性离子，羟基，酰氧基，烷硫基，醛基，酰氨基，氨甲酰基，脲基，氰基，硝基，乙二胺四乙酸，亚氨基二乙酸，和亚氨基二琥珀酸。
13.多孔膜，其是通过权利要求11或12的方法制备的。
14.过滤流体的方法，所述方法包括使流体穿过权利要求8-10中任一项所述的多孔膜或权利要求13的多孔膜。
CN201710694153.4A 2016-08-15 2017-08-15 氟聚合物和包含氟聚合物的膜(i) Active CN107759720B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15/237,172 2016-08-15
US15/237,172 US10471396B2 (en) 2016-08-15 2016-08-15 Fluoropolymers and membranes comprising fluoropolymers (I)

Publications (2)

Publication Number Publication Date
CN107759720A true CN107759720A (zh) 2018-03-06
CN107759720B CN107759720B (zh) 2021-05-28

Family

ID=59649481

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710694153.4A Active CN107759720B (zh) 2016-08-15 2017-08-15 氟聚合物和包含氟聚合物的膜(i)

Country Status (10)

Country Link
US (1) US10471396B2 (zh)
EP (1) EP3284759A1 (zh)
JP (1) JP6458960B2 (zh)
KR (2) KR20180019060A (zh)
CN (1) CN107759720B (zh)
AU (1) AU2017213595B2 (zh)
BR (1) BR102017017509B1 (zh)
CA (1) CA2976504C (zh)
SG (1) SG10201706490UA (zh)
TW (1) TWI648296B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111393546A (zh) * 2020-03-31 2020-07-10 浙江康特生物科技有限公司 一种螯合树脂的制备及去除试剂盒纯化水中钴离子的应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10130918B2 (en) * 2016-09-16 2018-11-20 Pall Corporation Fluoropolymers and membranes comprising fluoropolymers (III)
KR102455810B1 (ko) * 2018-03-15 2022-10-18 엔테그리스, 아이엔씨. 플루오르화 필터 막, 필터, 및 방법
US11465104B2 (en) 2019-02-08 2022-10-11 Entegris, Inc. Ligand-modified filter and methods for reducing metals from liquid compositions
US11574805B2 (en) 2019-09-12 2023-02-07 Brewer Science, Inc. Selective liquiphobic surface modification of substrates

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1255876A (zh) * 1997-05-01 2000-06-07 米利波尔公司 表面改性多孔膜及其制造方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5232600A (en) 1989-05-15 1993-08-03 Pall Corporation Hydrophobic membranes
US4954256A (en) 1989-05-15 1990-09-04 Pall Corporation Hydrophobic membranes
JPH0774290B2 (ja) 1990-05-18 1995-08-09 ジャパンゴアテックス株式会社 親水性多孔質フッ素樹脂材料
JP2002540928A (ja) 1999-04-14 2002-12-03 ポール・コーポレーション 多孔質膜
JP2007009163A (ja) * 2005-07-04 2007-01-18 National Institute Of Advanced Industrial & Technology 含フッ素スチレン誘導体及びその重合体
US20090277837A1 (en) 2008-05-06 2009-11-12 Chunqing Liu Fluoropolymer Coated Membranes
WO2012000851A1 (en) * 2010-07-01 2012-01-05 Solvay Solexis S.P.A. Process for the treatment of sulfonyl fluoride polymers
JP4979824B1 (ja) 2011-03-29 2012-07-18 株式会社アストム イオン交換膜
KR101334888B1 (ko) 2012-03-16 2013-11-29 강원대학교산학협력단 리튬 이차전지용 분리막 및 그 제조방법
US9776142B2 (en) 2014-02-28 2017-10-03 Pall Corporation Porous polymeric membrane with high void volume
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)
US9718924B2 (en) * 2014-06-30 2017-08-01 Pall Corporation Hydrophilic block copolymers and membranes prepared therefrom (II)
JP2016137455A (ja) 2015-01-28 2016-08-04 富士フイルム株式会社 複合イオン交換膜及びその製造方法、イオン交換膜モジュール、並びに、イオン交換装置
US9649603B2 (en) * 2015-03-31 2017-05-16 Pall Corporation Hydrophilically modified fluorinated membrane (III)
JP7074290B2 (ja) * 2018-01-23 2022-05-24 株式会社ミヤデン 誘導加熱用の出力変成器

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1255876A (zh) * 1997-05-01 2000-06-07 米利波尔公司 表面改性多孔膜及其制造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DAVID VALADE等: "Random and Block Styrenic Copolymers Bearing Both Ammonium and Fluorinated Side-Groups", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 *
梁梦兰等: "《表面活性剂与洗涤剂——制备 性质 应用》", 31 May 1992, 科学技术文献出版社 *
石影等: "《定量化学分离方法》", 31 December 2001, 中国矿业大学出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111393546A (zh) * 2020-03-31 2020-07-10 浙江康特生物科技有限公司 一种螯合树脂的制备及去除试剂盒纯化水中钴离子的应用
CN111393546B (zh) * 2020-03-31 2021-08-03 浙江康特生物科技有限公司 一种螯合树脂的制备及去除试剂盒纯化水中钴离子的应用

Also Published As

Publication number Publication date
TW201815841A (zh) 2018-05-01
AU2017213595A1 (en) 2018-03-01
JP2018076479A (ja) 2018-05-17
EP3284759A1 (en) 2018-02-21
US10471396B2 (en) 2019-11-12
BR102017017509B1 (pt) 2022-11-29
AU2017213595B2 (en) 2021-07-08
US20180043313A1 (en) 2018-02-15
BR102017017509A2 (pt) 2018-03-13
KR20180136921A (ko) 2018-12-26
KR102028584B1 (ko) 2019-11-04
TWI648296B (zh) 2019-01-21
SG10201706490UA (en) 2018-03-28
CA2976504C (en) 2019-07-23
KR20180019060A (ko) 2018-02-23
JP6458960B2 (ja) 2019-01-30
CN107759720B (zh) 2021-05-28
CA2976504A1 (en) 2018-02-15

Similar Documents

Publication Publication Date Title
CN107759720A (zh) 氟聚合物和包含氟聚合物的膜(i)
AU2017213592B2 (en) Fluoropolymers and membranes comprising fluoropolymers (II)
KR101785184B1 (ko) 다공질막용 수지 조성물, 제막 원액, 다공질막, 상기 다공질막을 사용한 중공사막, 수처리 장치, 전해질 지지체 및 세퍼레이터
JP6548173B2 (ja) フルオロポリマー及びフルオロポリマーを含む膜（ｉｉｉ）

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20240406

Address after: U.S.A.

Patentee after: Situofan USA Ltd.

Country or region after: U.S.A.

Address before: USA New York

Patentee before: PALL CORP

Country or region before: U.S.A.

TR01 Transfer of patent right