CN104822444B - Gas separation membrane - Google Patents

Gas separation membrane Download PDF

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Publication number
CN104822444B
CN104822444B CN201380062298.2A CN201380062298A CN104822444B CN 104822444 B CN104822444 B CN 104822444B CN 201380062298 A CN201380062298 A CN 201380062298A CN 104822444 B CN104822444 B CN 104822444B
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base
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divalent organic
hfip
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CN104822444A (en
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山中广
山中一广
须田健资
鱼山大树
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Central Glass Co Ltd
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    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/021—Manufacturing thereof
    • B01D63/022—Encapsulating hollow fibres
    • B01D63/023—Encapsulating materials
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    • B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
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    • B01D65/108—Repairing membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0018—Thermally induced processes [TIPS]
    • 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
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide

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  • Separation Using Semi-Permeable Membranes (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

[problem] is the present invention is intended to provide a kind of excellent gas separation membrane of separating property of gas when being dissolved in that organic solvent, mouldability are excellent, using as gas separation membrane.The gas separation membrane of [solution] present invention has polyimide structures, the polyimide structures have formula (1) (in formula, R1Represent divalent organic group and R2Represent quadrivalent organic radical group.) shown in repetitive, R1Divalent organic group shown in formula (2) or the divalent organic group shown in formula (3).

Description

Gas separation membrane
Technical field
The present invention relates to gas separation membrane.
Background technology
By the use of gas separation membrane gas separation as can make mixed gas keep gaseous state be continuously separated and Technology without the simplicity of phase change is received publicity all the time.The separation of gas is that basis will be through the gas of gas separation membrane Body is (below, sometimes referred to as " gas (gas) ".) species have or not transmission, using penetration speed difference being optionally sequestered The technology of gas.
Material as this gas separation membrane, it is known to the polymer such as cellulose acetate, polysulfones or polyimides.Its In, polyimides as have be suitable for use as gas separation membrane intensity and do not allow cracky, excellent heat resistance and can be in high temperature The lower material for using is known.
With regard to having a lot of reports using the gas separation membrane of polyimides, the structure of monomer is had studied in detail to for separating The impact of the separating property of the gas such as the permeability of the film of object gas and the high selectivity to object gas.
For example, as it is known that including hexafluoroisopropylidenyl (below, sometimes referred to as "-C (CF in repetitive structure3)2- yl ".) poly- Acid imide gas separation membrane has to helium (below, sometimes referred to as " He ".), carbon dioxide (below, sometimes referred to as " CO2”.) High-permeability, and have these gas phases for oxygen (below, sometimes referred to as " O2”.), methane (below, sometimes referred to as “CH4”.) high selectivity.
Additionally, in gas separation membrane, by by-C (CF3)2- base is imported in the repetitive in polyimides, is not only carried High molecule chain rigidity, and reduce intermolecular interaction so that it is saturating that gas separation membrane occurs in the species according to gas The difference that crosses, can take into account high film permeability and high selectivity (with reference to non-patent literature 1 and non-patent literature 2).
But there is problems with, containing-C (CF3)2In the synthesis material of the polyimides of-base, as easily can obtaining The raw material for obtaining, only following diamines and tetracarboxylic dianhydride, exist in terms of chemical constitution when forming polyimide film and limit, therefore When making gas separation membrane, it is difficult to which design considers the chemical constitution of intensity and separating property.
And, also there is a problem of being restricted for the organic solvent for dissolving.
Disclose in patent document 1～3 for aggregate into fluorinated polyimide, with 2- hydroxyl -1,1,1,3,3,3- Fluorine isopropyl (below, sometimes referred to as "-C (CF3)2OH " or " HFIP yl ".) the fluoropolymer monomer of diamines and its preparation side Method.
Additionally, the preparation method of the gas separation membrane formed by polyimides etc. has：In the molten of wet polyimides After liquid, only evaporate solvent and the method for acquisition homogeneous membrane；It is inhomogeneous non-right that acquisition is made up of compacted zone and porous layer The method for claiming film.The method for obtaining anisotropic membrane has following methods：Polymer solution is discharged from outlet, make to be present in surface attached Near solvent is evaporated in the air, forms compacted zone, then impregnates in the coagulating bath for fill solidification liquid, so that shape in solidification layer Become fine porous layer, the solidification liquid is to mix with the solvent of polymer solution but the solvent of insoluble polymer.Patent text Offer in 4, disclose the method for complex reverse osmosis membrane being prepared using the method.
As it was previously stated, including-C (CF for obtaining3)2The diamines of the polyimides of-base and tetracarboxylic dianhydride are limited, and are formed During polyimide film in terms of chemical constitution exist limit, when therefore making gas separation membrane, exist be difficult to design consider plus The problem of the chemical constitution of work, intensity and separating property.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-119503 publication
Patent document 2：Japanese Unexamined Patent Publication 2007-119504 publication
Patent document 3：Japanese Unexamined Patent Publication 2008-150534 publication
Patent document 4：No. 3133132 publications of United States Patent (USP)
Non-patent literature
Non-patent literature 1：This strong first-class, Process Technology of Polymer, volume 41, No. 1, page 16,1992
Non-patent literature 2：S.A.Stern, Journal of Membrane Science, volume 94, page 1,1994
Content of the invention
Problems to be solved by the invention
It is an object of the invention to the problem is solved, provide and be dissolved in that organic solvent, mouldability are excellent, separate as gas The separating property of gas excellent gas separation membrane when film is used.
For solution to problem
The present inventor etc. are by using by and changing as substituent with the HFIP base polar group of-OH base (have) Two-NH in compound2The polyimides that aromatic diamine of the base in asymmetric position relation is obtained so as to dissolve in organic Solvent, especially polar solvent, improve gas separating property when the polyimides is made gas separation membrane, so as to complete The present invention.
That is, the present invention is as described below.
A kind of [invention 1] gas separation membrane, which contains polyimide structures, and the polyimide structures have formula (1) Shown repetitive, R1Divalent organic group shown in formula (2) or the divalent organic group shown in formula (3),
In formula, R1Represent divalent organic group and R2Represent quadrivalent organic radical group,
In formula, RaaFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base, p and q are each independently 0～2 integer, and meet 1≤p+q≤4, intersect with wavy line Line segment represents bonding position,
In formula, RbaFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base, r and s are each independently 0～2 integer, and meet 1≤r+s≤4, intersect with wavy line Line segment represents bonding position.
The gas separation membrane of [invention 2] according to invention 1, wherein, the divalent organic group shown in formula (2) is formula (4)：
In formula, RabFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base, represents bonding position with the line segment that wavy line intersects.
The gas separation membrane of [invention 3] according to invention 1 or 2, wherein, the divalent organic group shown in formula (2) is Any one in formula (4-1) or (4-2)：
In formula, HFIP represents-C (CF3)2OH base, represents bonding position with the line segment that wavy line intersects.
The gas separation membrane of [invention 4] according to invention 1, wherein, the divalent organic group shown in formula (3) is formula (5) any one in the divalent organic group shown in：
In formula, RbbFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base, represents bonding position with the line segment that wavy line intersects.
The gas separation membrane of [invention 5] according to invention 1 or 4, wherein, the divalent organic group shown in formula (3) is Any one in formula (5-1) or (5-2)：
In formula, HFIP represents-C (CF3)2OH base, represents bonding position with the line segment that wavy line intersects.
The gas separation membrane of [invention 6] according to any one of invention 1～5, wherein, R2For formula (6)～the (11) Suo Shi Quadrivalent organic radical group in any one,
In formula, represent bonding position with the line segment that wavy line intersects.
The gas separation membrane of [invention 7] according to any one of invention 1～6, wherein, R1Comprising HFIP base had The hydrogen atom of-OH base replaced by glycidyl.
The gas separation membrane of [invention 8] according to invention 7, wherein, the cyclic ether position open loop crosslinking of glycidyl.
The gas separation membrane of [invention 9] according to any one of invention 1～8, which is mixed with epoxide further Merge heating and obtain.
The gas separation membrane of [invention 10] according to invention 9, wherein, epoxide is represented by formula (12)：
In formula, RfIt is the g valency organic group for sloughing any g hydrogen atom from alkane, aromatic ring or alicyclic ring, permissible in structure Containing oxygen atom, sulphur atom or nitrogen-atoms, a part of hydrogen atom can also be replaced by fluorine atom, chlorine atom, alkyl or fluoroalkyl, G represents 1～4 integer.
The effect of invention
By the present invention with HFIP base as substituent the polyimide gas that obtains of asymmetrical aromatic diamine Body seperation film has the good separating property that HFIP base brings as substituent and unsymmetric structure.As HFIP base has There is-OH base, therefore the gas separation membrane of the present invention dissolves in specific organic solvent, especially polar solvent, also easily prepare Polyimide solution, formable for needed for film shape.
Additionally, with regard to the polyimide gas separation membrane with HFIP base and unsymmetric structure of the present invention, due to holding Easily HFIP base is imported as in the aromatic diamine with unsymmetric structure of raw material, therefore with existing fluorinated polyimide Class gas separation membrane is compared, and can be carried out for making the film physical property such as gas separating property and film-strength or the resistance to swelling in solvent Become excellent structure design.
Additionally, also having-C (CF in addition to HFIP base and unsymmetric structure3)2The gas separation membrane of-base shows better Good gas separating property.
Specific embodiment
Hereinafter, the present invention will be described, but the invention is not restricted to implementation below.
In this specification, sometimes by with HFIP base and the polyimides with unsymmetric structure is expressed as " with HFIP The asymmetric polyimides of base ".Additionally, sometimes by the aromatic diamine compound table with HFIP base and with unsymmetric structure It is shown as " the asymmetric aromatic diamine compound with HFIP base ".
The gas separation membrane of the present invention be obtained in the asymmetric polyimides with HFIP base.As containing HFIP base The monomeric compound of raw material of asymmetric polyimides can enumerate the asymmetric aromatic diamine containing HFIP base and tetracarboxylic acid Acid dianhydride.In order to obtain as intensity during gas separation membrane, it is preferred to use aromatic diamine.By making these monomeric compounds Reaction, is obtained in that the asymmetric polyimides for containing HFIP base.
Except the asymmetric aromatic diamine with HFIP base, in order to adjust as intensity during film, separating property, may be used also To add other diamines.Similarly, in order to adjust as intensity during film, separating property, in addition to tetracarboxylic dianhydride, may be used also To add other dicarboxylic acids and its derivative.
1. the asymmetric aromatic diamine containing HFIP base
Asymmetric aromatic diamine containing HFIP base is represented by formula (2-A) and formula (3-A), used as synthesis in order to make Make the monomeric compound of the asymmetric polyimides containing HFIP base of the gas separation membrane of the present invention,
In formula, RaaFor singly-bound, oxygen atom, sulphur atom ,-SO2- group ,-CH2- group ,-C (=O)-group ,-C (CH2)2- Group ,-C (CH3)(CH2CH3)-group ,-C (CF3)2- group ,-CH (CH3)-group ,-CH (OH)-group or-NH- group, or Person is that the ester ring type hydrocarbon compound of carbon number 3～12, the aromatic hydrocarbon compound of carbon number 6～25 slough any 2 hydrogen atoms and shape The divalent organic group for becoming, HFIP represent-C (CF3)2OH group, p and q are each independently 0～2 integer, and meet 1≤ P+q≤4,
In formula, RbaFor singly-bound, oxygen atom, sulphur atom ,-SO2- group ,-CH2- group ,-C (=O)-group ,-C (CH2)2- Group ,-C (CH3)(CH2CH3)-group ,-C (CF3)2- group ,-CH (CH3)-group ,-CH (OH)-group or-NH- group, or Person is that the ester ring type hydrocarbon compound of carbon number 3～12, the aromatic hydrocarbon compound of carbon number 6～25 slough any 2 hydrogen atoms and shape The divalent organic group for becoming.HFIP represents-C (CF3)2OH group, r and s are each independently 0～2 integer, and meet 1≤ r+s≤4.
[the asymmetric aromatic diamine (2-A) containing HFIP base]
In asymmetric aromatic diamine (2-A) containing HFIP base, the ester ring type hydrocarbon compound as carbon number 3～12 is sloughed The divalent organic group of 2 hydrogen atoms, preferably hexamethylene, bicyclohexane, adamantane or norbornane slough 2 hydrogen atoms Divalent organic group, the aromatic hydrocarbon compound as carbon number 6～25 sloughs the divalent organic base of 2 hydrogen atoms Group, can enumerate the divalent organic group that benzene, biphenyl, naphthalene or fluorenes slough 2 hydrogen atoms.
Compound of the asymmetric aromatic diamine (2-A) containing HFIP base preferably shown in formula (4-A),
In formula, RabFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH2)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base.Specifically, the compound shown in formula (4-1-A)～(4-14-A) can be enumerated,
In formula, HFIP represents-C (CF3)2OH base.Me represents methyl, and Et represents ethyl.Wherein, easily obtain from raw material diamines Property viewpoint consideration, particularly preferred formula (4-1-A) and formula (4-2-A).
[the asymmetric aromatic diamine (3-A) containing HFIP base]
In asymmetric aromatic diamine (3-A) containing HFIP base, the ester ring type hydrocarbon compound as carbon number 3～12 is sloughed The divalent organic group of 2 hydrogen atoms, preferably hexamethylene, bicyclohexane, adamantane or norbornane slough 2 hydrogen atoms Divalent organic group, the aromatic hydrocarbon compound as carbon number 6～25 sloughs the divalent organic base of 2 hydrogen atoms Group, can enumerate the divalent organic group that benzene, biphenyl, naphthalene or fluorenes slough 2 hydrogen atoms.
Compound of the asymmetric aromatic diamine (3-A) containing HFIP base preferably shown in formula (5-A),
In formula, RbbFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH2)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base.Specifically, the compound shown in formula (5-1-A)～(5-14-A) can be enumerated,
In formula, HFIP represents-C (CF3)2OH base, Me represent methyl, and Et represents ethyl.Wherein, easily obtain from raw material diamines Property viewpoint consideration, particularly preferably (5-1-A) and (5-2-A).
These asymmetric aromatic diamines for containing HFIP base can also be used in combination.
The diamines can be by the reaction of the aromatic diamine containing unsymmetric structure and Hexafluoro acetone or Hexafluoro acetone trihydrate And obtain.With regard to its preparation method, the aromatic diamine containing symmetrical structure described in patent document 1 and hexafluoro third can be applied Ketone or the reaction of Hexafluoro acetone trihydrate.
2. other diamines
In order to adjust the film physical property such as the gas separating property of gas separation membrane, the dissolubility to polar solvent, film-strength, In synthesis with HFIP base and the polyimides of unsymmetric structure, except the asymmetric aromatic diamine with HFIP base it Outward, other diamines, dihydroxy amine can also be used.Usage amount is rubbed for 10 moles of %～80 with respect to above-mentioned tetracarboxylic dianhydride You are %, preferably 30 moles %～60 mole %.
As other diamines, can enumerate 3,5- diamido-benzotrifluoride, 2,5- diamido-benzotrifluoride, 3,3 '-bis- three Methyl fluoride -4,4 '-benzidine, 2,2 '-bis trifluoromethyl -4,4 '-benzidine, 3,3 '-bis trifluoromethyl -5,5 ' - Benzidine, double (trifluoromethyls) -4,4 '-benzidine, double (fluorinated alkyls) -4,4 '-benzidine, two chloro- 4, 4 '-benzidine, two bromo- 4,4 '-benzidines, double (fluorination alkoxyls) -4,4 '-benzidine, diphenyl -4, 4 '-benzidine, 4,4 '-bis- (4- amino tetrafluoro phenoxy group) phenyl tetrafluorides, 4,4 '-bis- (4- amino tetrafluoro phenoxy group) octafluoro connection Benzene, 4,4 '-BINAM, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2,4 di amino toluene, 2,5- diaminotoluene, 2,4- Diaminourea dimethylbenzene, 2,4- diaminourea durol, 1,4- xylylene diamine, dimethyl -4,4 '-benzidine, dioxane Base -4,4 '-benzidine, 2,2 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethyl -4,4 '-benzidine, two Methoxyl group -4,4 '-benzidine, diethoxy -4,4 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,4 '-two Aminodiphenylmethane, 2,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-diaminodiphenyl-methane, 3,3 '-diethyl Double (4- aminophenyl) fluorenes of base-diaminodiphenyl-methane, 9,9-, 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 2,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl sulfide, 3,4 '-diaminodiphenyl sulfide, 4,4 '-DADPS, Double (the 3- aminobenzene oxygen of 3,3 '-DADPS, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 1,3- Base) benzene, double (4- amino-benzene oxygen) benzene of 1,3-, double (4- amino-benzene oxygen) benzene of 1,4-, 4,4 '-bis- (4- amino-benzene oxygens) connection Double [4- (the 4- aminobenzene oxygen of benzene, double [4- (3- amino-benzene oxygen) phenyl] sulfones, double [4- (4- amino-benzene oxygen) phenyl] sulfones, 2,2- Base) phenyl] propane, double [4- (4- amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, double [4- (3- amino-benzene oxygen) benzene of 2,2- Base] propane, double [4- (3- amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, the double [4- (4- amino -2- trifluoromethylbenzene oxygen of 2,2- Base) phenyl] HFC-236fa, double [4- (3- amino -5- 4-trifluoromethylphenopendant) phenyl] HFC-236fa of 2,2-, double (the 4- ammonia of 2,2- Base phenyl) HFC-236fa, double (3- aminophenyl) HFC-236fa of 2,2-, double (3- amino-4-hydroxylphenyl) HFC-236fas of 2,2-, 2,2- double (3- amino -4- aminomethyl phenyl) HFC-236fa, 4,4 '-bis- (4- amino-benzene oxygen) octafluorobiphenyl or 4,4 '-diaminourea Benzanilide, can also be by being used in combination in them.Wherein, preferably use and give obtained gas separation Film with high-permeability, by have-C (CF3)2Diamines shown in the following structural formula of-base.
If additionally, illustrating dihydroxy amine, 3 can be enumerated, 3 '-dihydroxybiphenyl amine, 3,3 '-diaminourea -4,4 '-dihydroxy Biphenyl, 4,4 '-diaminourea -3,3 '-dihydroxybiphenyl, 3,3 '-diaminourea -4,4 '-dihydroxydiphenylsulisomer, 4,4 '-diaminourea -3, 3 '-dihydroxydiphenylsulisomer, double-(3- amino-4-hydroxylphenyl) methane, 2,2- be double-(3- amino-4-hydroxylphenyl) propane, 2, 2- pair-(3- amino-4-hydroxylphenyl) HFC-236fa, 2,2- pair-(4- amino-3-hydroxy base) HFC-236fa, double-(4- ammonia Base -3- hydroxy phenyl) methane, 2,2- be double-(4- amino-3-hydroxy base) propane, 4,4 '-diaminourea -3,3 '-dihydroxy hexichol Ketone, 3,3 '-diaminourea -4,4 '-dihydroxy benaophenonel, 4,4 '-diaminourea -3,3 '-dihydroxy diphenyl ether, 3,3 '-diamino Base -4,4 '-dihydroxy diphenyl ether, 1,4- diaminourea -2,5- dihydroxy benzenes, 1,3- diaminourea -2,4- dihydroxy benzenes and 1,3- Diaminourea -4,6- dihydroxy benzenes, can also be by being used in combination in them.Wherein, preferably use imparting to be obtained Gas separation membrane with high-permeability, by have-C (CF3)2Dihydroxy amine shown in the following structural formula of-base.
3. tetracarboxylic dianhydride
The tetracarboxylic dianhydride used for the asymmetric polyimides containing HFIP base for synthesizing the present invention is by formula (12) represent,
In formula, R2Represent quadrivalent organic radical group.
In formula (12), R2The quadrivalent organic radical group of 4 hydrogen atoms is preferably sloughed from alkane, alicyclic ring or aromatic ring, knot Fluorine atom, chlorine atom, oxygen atom, sulphur atom or nitrogen-atoms can be contained in structure, a part of hydrogen atom also can be by alkyl, fluothane Base, carboxyl, hydroxyl or cyano group replace.
As this tetracarboxylic dianhydride, equal benzene tertacarbonic acid's dianhydride can be specifically enumerated (below, sometimes referred to as “PMDA”.), trifluoromethylbenzene tetracarboxylic dianhydride, dual-trifluoromethyl benzene tetracarboxylic dianhydride, difluorobenzene tetracarboxylic dianhydride, naphthalene tetracarboxylic acid Acid dianhydride, biphenyl tetracarboxylic dianhydride are (below, sometimes referred to as " BPDA ".), terphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-hexichol first Below, ketone tetracarboxylic dianhydride is (sometimes referred to as " BTDA ".), the double O-phthalic acid dianhydride of oxygen (below, sometimes referred to as " ODPA ".)、 Bicyclic (2,2,2)-eight -7- alkene -2,3,5,6- tetracarboxylic dianhydrides, double (3,4- dicarboxyphenyi) the hexafluoro propionic acid dianhydride of 2,2- (with Under, sometimes referred to as " 6FDA ".), 2,3,4,5- thiophene tetracarboxylic dianhydride, 2,5,6,2 ', 5 ', 6 '-hexafluoro -3,3 ', 4,4 '-biphenyl Tetracarboxylic dianhydride, double (3,4- dicarboxyphenyi) sulfonic acid dianhydrides are (below, sometimes referred to as " DSDA ".) or 3,4,9,10- tetracarboxylic acid Being used in combination in them can also be not particularly limited when being applied in combination by acid dianhydride.
Wherein, consider that PMDA, BPDA, BTDA, DSDA, ODPA and 6FDA are particularly preferred, get married and start a new life from accessibility Gas separating property (the permeability and selectivity) consideration that gets well, 6FDA is preferred.
4. dicarboxylic acids and dicarboxylic acid derivatives
In order to adjust as the film physical property such as separating property during gas separation membrane and intensity, except above-mentioned tetracarboxylic dianhydride with Outward, dicarboxylic acids that can also be using formula (13) or shown in formula (14) or dicarboxylic acid derivatives,
In formula, R3It is containing the divalent organic group selected from one or more of alicyclic ring, aromatic ring, alkylidene, can contains Oxygen atom, sulphur atom or nitrogen-atoms, the hydrogen atom of any number can be by alkyl, fluorine atom, chlorine atom, fluoroalkyl, carboxyl, hydroxyl Or cyano group replaces, R4Hydrogen atom, the alkyl of carbon number 1～10 or benzyl is each independently, X is each independently chlorine atom, fluorine Atom, bromine atoms or atomic iodine.
It should be noted that after condensation reaction, being formed containing the heterocycle structure described in formula (15) as copolymer composition Construction unit,
In formula, R3It is containing the divalent organic group selected from one or more of alicyclic ring, aromatic ring, alkylidene, can contains Oxygen atom, sulphur atom or nitrogen-atoms, the hydrogen atom of any number can be by alkyl, fluorine atom, chlorine atom, fluoroalkyl, carboxyl, hydroxyl Or cyano group replaces.
Dicarboxylic acids or dicarboxylic acid derivatives shown in formula (13), (14) can be arbitrarily using aliphatic dicarboxylic acid, fragrance Race's dicarboxylic acids or their dicarboxylic acid derivatives.
As aliphatic dicarboxylic acid and its derivative, can for example enumerate oxalic acid, malonic acid, succinic acid, glutaric acid, oneself two Acid, pimelic acid, suberic acid, azelaic acid, the dicarboxylic acid compound of decanedioic acid or these dicarboxylic acid derivatives.
As aromatic dicarboxylic acid and its derivative, such as phthalic acid, M-phthalic acid, terephthaldehyde can be enumerated Acid, 4,4 '-dicarboxylate biphenyl, 3,3 '-dicarboxylate biphenyl, 3,3 '-dicarboxydiphenyl ether, 3,4 '-dicarboxydiphenyl ether, 4,4 '- Dicarboxydiphenyl ether, 3,3 '-dicarboxyl diphenyl methane, 3,4 '-dicarboxyl diphenyl methane, 4,4 '-dicarboxyl diphenylmethyl Alkane, 3,3 '-dicarboxyl diphenyl difluoromethane, 3,4 '-dicarboxyl diphenyl difluoromethane, 4,4 '-dicarboxyl diphenyl difluoro Methane, 3,3 '-Dicarboxy diphenylsulfone, 3,4 '-Dicarboxy diphenylsulfone, 4,4 '-Dicarboxy diphenylsulfone, 3,3 '-dicarboxyl diphenyl sulfide Ether, 3,4 '-dicarboxyl diphenyl sulfide, 4,4 '-dicarboxyl diphenyl sulfide, 3,3 '-dicarboxybenzophenone, 3,4 '-dicarboxyl hexichol Double (3- carboxyl phenyl) propane of ketone, 4,4 '-dicarboxybenzophenone, 2,2-, 2,2- double (3,4 '-dicarboxyphenyi) propane, 2,2- Double (3- carboxyl phenyl) HFC-236fas of double (4- carboxyl phenyl) propane, 2,2-, double (3,4 '-dicarboxyphenyi) hexafluoros third of 2,2- Double (3- carboxyphenoxy) benzene of double (4- carboxyl phenyl) HFC-236fa of alkane, 2,2-, 1,3-, double (3- carboxyphenoxy) benzene of 1,4-, Double (4- carboxyphenoxy) benzene of 1,4-, 3,3 '-(1,4- phenylene is double (1- methyl ethylidene)) double benzoic acid, 3,4 '-(1,4- Asia Phenyl double (1- methyl ethylidene)) double benzoic acid, 4,4 '-(1,4- phenylene is double (1- methyl ethylidene)) double benzoic acid, 2,2- Double (4- (4- carboxyphenoxy) phenyl) propane of double (4- (3- carboxyphenoxy) phenyl) propane, 2,2-, double (4- (the 3- carboxylics of 2,2- Phenoxyl) phenyl) HFC-236fa, 2,2- double (4- (4- carboxyphenoxy) phenyl) HFC-236fa, double (4- (3- carboxyl benzene oxygen Base) phenyl) thioether, double (4- (4- carboxyphenoxy) phenyl) thioethers, double (4- (3- carboxyphenoxy) phenyl) sulfones or double (4- (4- carboxyphenoxy) phenyl) sulfone；Belong to dicarboxylic acids containing perfluorinated nonene epoxide 5- (perfluorinated nonene epoxide) M-phthalic acid, 4- (perfluorinated nonene epoxide) phthalic acid, 2- (perfluorinated nonene epoxide) terephthalic acid (TPA) or 4- methoxyl group -5- (perfluorinated nonene oxygen Base) M-phthalic acid；Belong to 5- (perfluor hexene epoxide) M-phthalic acid, the 4- (perfluor of the dicarboxylic acids of the epoxide of hexene containing perfluor Hexene epoxide) phthalic acid, 2- (perfluor hexene epoxide) terephthalic acid (TPA) or 4- methoxyl group -5- (perfluor hexene epoxide) isophthalic Dioctyl phthalate, 2,2 '-di-trifluoromethyl -4,4 '-dicarboxylate biphenyl or these dicarboxylic acids derivative.Further, it is also possible to by they In be used in combination.
Wherein, because be readily available, polycondensation reaction carry out ease excellent, preferably terephthalic acid (TPA), M-phthalic acid, 4, 4 '-dicarboxylate biphenyl, 2,2 '-two trifluoromethyls -4,4 '-dicarboxylate biphenyl, double (4- carboxyl phenyl) HFC-236fa of 2,2-.
The usage amount of the dicarboxylic acids or the dicarboxylic acid derivatives with respect to above-mentioned tetracarboxylic dianhydride be 10 moles of more than % and 80 moles of below %, preferably 30 moles more than % and 60 mole of below %.In the range of the mol ratio, gas can be adjusted Separating property, the dissolubility to polar solvent, film-strength.
5. the synthesis of the asymmetric polyimides containing HFIP base
The synthetic method of the asymmetric polyimides containing HFIP base used in the gas separation membrane to the present invention is carried out Explanation.
Herein, the situation for being expressed as " dicarboxylic acids (derivative) " refers to " dicarboxylic acids or dicarboxylic acid derivatives ".In specification Same as below.
In order to synthesize the asymmetric polyimides containing HFIP base used in the gas separation membrane of the present invention, can enumerate Following methods：Must there are the above-mentioned asymmetric aromatic diamine containing HFIP base and tetracarboxylic dianhydride, be added as needed on other Diamines and dicarboxylic acids (derivative), then make which mutually melt more than 150 DEG C, in solvent-free lower reaction；In reaction temperature -20 At～80 DEG C, polymerisation is carried out in organic solvent.In the polymerization, due to diamines and tetracarboxylic dianhydride or dicarboxylic acids (derivative) is reacted with 1 to 1 according to the molar ratio, therefore the asymmetric diamines containing HFIP base and other diamines, tetracarboxylic dianhydride And the presence of dicarboxylic acids (derivative) is than being preferably aromatic diamine and other diamines according to the molar ratio：Tetracarboxylic dianhydride and two Carboxylic acid (derivative)=1：1.
As long as can be used for the organic solvent dissolving response matrix of above-mentioned polymerisation, can enumerate that to belong to amide-type molten The N,N-dimethylformamide of agent, DMAC N,N' dimethyl acetamide, HPT or METHYLPYRROLIDONE；Category Benzene, anisole, diphenyl ether, nitrobenzene or benzonitrile in fragrant same clan's solvent；Belong to chloroform, the dichloromethane of halogen based solvents Alkane, 1,2- dichloroethanes or 1,1,2,2- tetrachloroethanes；Belong to the gamma-butyrolacton of lactone, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone or Alpha-Methyl-gamma-butyrolacton；Belong to 2-methyl cellosolve, the 2- ethoxy of alcohols and glycol ethers Base ethanol, butoxy ethanol or n-butanol.Further, it is also possible to make these organic solvents and acid acceptor such as pyridine, triethylamine Coexist, carry out polymerisation.
Carried out by making the polyamic acid with HFIP base and unsymmetric structure obtained in above-mentioned polymerisation further Dehydration closed-loop reaction, cyclisation and imidizate such that it is able to be converted into object with the poly- of HFIP base and unsymmetric structure Acid imide.
Dehydration closed-loop reaction promotes the reaction condition of cyclisation to carry out using heating, using acid catalyst etc..In general, can So that just the polyamic acid solution with HFIP base and unsymmetric structure after polymerisation is more than 150 DEG C and less than 250 DEG C At a high temperature of imidizate, the asymmetric polyimide solution being prepared into containing HFIP base.Now, can also add pyridine, three Ethamine, acetic anhydride etc..The concentration of the asymmetric polyimides containing HFIP base in solution is preferably more than 5 mass % and 50 matter Amount below %.During less than 5 mass %, too dilute industrially impracticable.During more than 50 mass %, it is difficult to dissolve.Further preferably For more than 10 mass % and below 40 mass %.
The weight average molecular weight of the asymmetric polyimides containing HFIP base of the present invention is (below, sometimes referred to as " Mw ".) excellent Elect 10, more than 000, more preferably 20, more than 000 as.The upper limit of the weight average molecular weight be preferably less than 500,000, more preferably For less than 300,000.When weight average molecular weight is less than 10,000, the macromolecule film strength of acquisition is not enough.Weight average molecular weight is more than When 500,000, the viscosity of the Polymer Solution of acquisition is too high and make operation become difficult.The weight average molecular weight of indication is root herein According to gel permeation chromatography (below, sometimes referred to as " GPC ".) analysis, scaled value (this Shen based on polystyrene standard for obtaining Please in same as below.).The labor condition of the analysis will be described in embodiments herein.
6. the preparation of the asymmetric polyimide solution containing HFIP base
The solution of the asymmetric polyimides containing HFIP base being achieved in that can also be directly used in and prepare gas separation Film.Additionally, in order to remove contained residual monomer in the solution of the polyimides containing HFIP base and unsymmetric structure, low point Sub- quantity of material, can be added to the solution of the asymmetric polyimides containing HFIP base in the poor solvents such as water or alcohol, make to contain There is the asymmetric polyimides precipitation of HFIP base and purification is isolated, so which is dissolved in organic solvent and be adjusted to above-mentioned dense again Degree.
As long as spendable asymmetric polyimides of the organic solvent dissolving containing HFIP base is just not particularly limited, such as Can enumerate belong to the N,N-dimethylformamide of amide solvent, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, six Methyl acid phosphate triamide, METHYLPYRROLIDONE, belong to the benzene of fragrant same clan's solvent, anisole, diphenyl ether, nitrobenzene or Benzonitrile, belongs to the chloroform of halogen based solvents, dichloromethane, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes, belongs to lactone Gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone or Alpha-Methyl-gamma-butyrolacton, belong to phenols Phenol, cresols, xylenols, catechol or chlorophenol, belong to 2-methyl cellosolve, the 2- ethyoxyl second of alcohols and glycol ethers Alcohol, butoxy ethanol or n-butanol etc..Further, it is also possible to the mixed solvent using them.
7. the making of gas separation membrane
The gas separation membrane for including the asymmetric polyimides containing HFIP base of the present invention can be by using solvent from In asymmetric polyimide solution containing HFIP base evaporation come make film wet type membrane formation obtain homogeneous membrane or by Any one in the anisotropic membrane containing compacted zone and porous layer that other methods are obtained.
[homogeneous membrane]
Homogeneous membrane can be obtained in the following way：For example using spin coater, applicator etc. in bases such as glass substrates After on body, wet type covers the solution of the above-mentioned asymmetric polyimides containing HFIP base, dry in air, nitrogen or argon gas etc. In gas, heating evaporates solvent, then peels off from glass baseplate and obtains.Additionally, using the asymmetric polyamides containing HFIP base Amino acid solution substitutes the asymmetric polyimide solution containing HFIP base, is covered on matrix according to above-mentioned steps, then Heating makes its imidizate, can also obtain the film of homogeneous.
In order to be used for gas separation membrane, the thickness of homogeneous membrane is preferably more than 5 μm and below 1mm.The film thinner than 5 μm is not only Make difficult and be easily broken.The film thicker than 1mm, gas are difficult to pass through.More preferably 10 μm～200 μm.
[anisotropic membrane]
Anisotropic membrane containing compacted zone and porous layer can carry out film forming in aforementioned manners.Additionally, molten using polyamic acid Liquid substitutes polyimide solution and forms anisotropic membrane, and then hot-imide can also obtain anisotropic membrane.
In anisotropic membrane, the penetration speed of compacted zone is different according to gaseous species and different, with entering for mixed gas The gas separation function of row selection.On the other hand, porous layer has as the effect for keeping the supporter of film shape.
Permissible for anisotropic membrane gas separation membrane, including the asymmetric polyimides containing HFIP base of the present invention It is any one shape in smooth membranaceous, hollow fiber.
The thickness of compacted zone is preferably less than more than 10nm and 10 μm.When thinner than 10nm, it is difficult to film forming, impracticable.Than 10 μ When m is thick, gas cannot easily penetrate.Preferably less than more than 30nm and 1 μm.
When smooth membranaceous, the thickness of porous layer is preferably more than 5 μm and below 2mm.When thinner than 5 μm, it is difficult to film forming, no Practical.When thicker than 2mm, gas cannot easily penetrate.More preferably more than 10 μm and less than 500 μm.During hollow fiber, interior Footpath is more than 10 μm and below 4mm, preferably more than 20 μm and below 1mm, and external diameter is more than 30 μm and below 8mm, preferably More than 50 μm and below 1.5mm.When forming hollow fiber, preferably compacted zone is contained in outside.
As make anisotropic membrane when solidification liquid, can be suitably using water or the mixed solvent of water and organic solvent.Mixing Solvent contains more than 40 mass %, water more than preferably 50 mass %, as organic solvent, can enumerate belong to alcohol methyl alcohol, Ethanol or isopropanol, belong to the acetone of ketone, methyl ethyl ketone, metacetone.Water or during its mixed solvent used in solidification liquid, no Film production equipment need to be made explosion-proof specification, reduce cost.
[solidification liquid]
For the present invention gas separation membrane, containing HFIP base unsymmetric structure polyimides due to polar group HFIP base containing effective, thus be especially soluble in DMA, the N for belonging to amide solvent, N- dimethyl methyl Acid amides or METHYLPYRROLIDONE, belong to gamma-butyrolacton, the gamma-valerolactone of lactone, are also easy to make with required film thickness Homogeneous membrane, also easily make the anisotropic membrane using water paracoagulation liquid.
Especially when anisotropic membrane is made, by changing the distance from outlet to coagulating bath, or, with doughnut When shape is discharged, by discharging dry air, water paracoagulation liquid etc. in the inner side of outlet simultaneously, the densification needed for being formed Layer.By change coagulating bath organic solvent species, can be formed with required aperture, pore-size distribution, thickness porous layer.
The film processed with solidification liquid is used after preferably making its drying using heating.Heat treatment temperature is preferably Do not melted with ensureing which below the vitrification point of polyimides.
[polyorganosiloxane resin coating]
In order to repair the surface defect of made gas separation membrane, it is also possible to be coated with polysiloxanes on separation membrane surface Resin.As coating process, it is possible to use the known rubbing method such as rotary coating, the coating using applicator, dip coated.
As polyorganosiloxane resin, conventional dimethyl silicone polymer, the polysiloxanes containing phenyl can be enumerated, contain ethene The polysiloxanes of base, the polysiloxanes containing Si-H base, containing the polysiloxanes of trifluoro propyl, the polysiloxanes of siliceous silane alcohol base, contain The polysiloxanes of amino, the polysiloxanes containing epoxy radicals, the polysiloxanes containing methylacryloyl, the poly- silica containing acryloyl group Alkane etc..These polyorganosiloxane resins are commercially available, can enumerate Gelest company production DMS series, PDV series, VDT series, FMV series, HMS series, DMS series, HPM series, FMS series, SQO series, AMS series, MCR series, ECMS series, RMS Series etc..
8. being applied in combination of epoxide
For improve mechanical strength or plasticising patience, as the gas separation membrane of invention 7～10, with by above-mentioned formula (1) macromolecular compound of the repetitive shown in can be mixed with epoxide, make which solid by heating or light irradiation etc. Change and form cured film.The cured film applies also for above-mentioned homogeneous membrane and anisotropic membrane.
As epoxide, can enumerate by making phenol resol resins, cresol novolac resin, aromatic series Hydrocarbon formaldehyde resin phenol-formaldehyde resin modified, dicyclopentadiene-modified phenolic resin, phenol aralkyl resin, cresols aralkyl resin, Naphthols aralkyl resin, biphenyl modified phenol aralkyl resin, phenol Pehanorm resin, tetrahydroxy diphenylphosphino ethane tree Fat, naphthol novolac varnish gum, naphthols-phenol cocondensation novolac resin, naphthols-cresols cocondensation novolac resin, biphenyl Phenol-formaldehyde resin modified or amino triazine modified phenolic resin compound are contacted with epichlorohydrin and carry out epoxide modified epoxy compound Thing.
These epoxides are commercially available, can enumerate bisphenol A-type (big Japanese ink Industrial Co., Ltd production, commodity Name, EPICLON840), bisphenol-f type (Asahi Denka Kogyo K. K production, trade name, ADEKA RESIN EP-4901), first Phenol phenolic varnish type (big Japanese ink Industrial Co., Ltd production, trade name, EPICLON N-600 series), dicyclopentadiene Type (big Japanese ink Industrial Co., Ltd production, trade name, EPICLON HP-7200 series), Triazine (Nissan Chemical Industries Co., Ltd. produces, trade name, TEPIC series) etc..
Epoxide shown in formula (12) is synthesized by corresponding alcohol and epichlorohydrin：
In formula (12), RfIt is the g valency organic group for sloughing g hydrogen atom from alkane, aromatic ring or alicyclic ring, in structure Oxygen atom, sulphur atom or nitrogen-atoms can be contained, a part of hydrogen atom can be replaced by fluorine atom, chlorine atom, alkyl or fluoroalkyl. G is 1～4 integer.
As the alcohol, can enumerate Isosorbide-5-Nitrae-cyclohexanediol, 1,3- adamantane glycol, catechol, 1,3- Benzenediol, 2,2 '- Dihydroxybiphenyl, 4,4 '-dihydroxybiphenyl, 2,2 '-methylene diphenol, 4,4 '-methylene diphenol, ethylene glycol, propane diols, 2,2- Double (4- the hydroxy phenyl)-butane of double (4- the hydroxy phenyl) -3- methylpropane of double (4- hydroxy phenyl)-propane, 2,2-, 2,2-, 3, Double (4- the hydroxy phenyl) -4- methylpentanes of double (4- the hydroxy phenyl)-pentane of 3-, 2,2-, double (4- the hydroxy phenyl)-hexanes of 3,3-, Double (3- chloro-4-hydroxyl the phenyl)-propane of 2,2-, double (the chloro- 4- hydroxy phenyl of the 3,5- bis-)-propane of 2,2-, double (the bromo- 4- of 3- of 2,2- Hydroxy phenyl)-propane, double (the bromo- 4- hydroxy phenyl of the 3,5- bis-)-propane of 2,2-, double (the 3- methyl -4- hydroxy phenyls)-the third of 2,2- Alkane, 2,2- double (4- hydroxy phenyl) -1,1,1,3,3,3- HFC-236fa, 2,6- dihydroxy naphthlene, 2,3- dihydroxy naphthlene, 2,7- dihydroxies Base naphthalene, 1,4- dihydroxy naphthlene, 1,5- dihydroxy naphthlene, 2,3- dihydroxy-pyridine, 2,4- dihydroxy-pyridine, 4,4 '-dihydroxy hexichol Ether, 4,4 '-dihydroxy diphenyl sulfide, 4,4 '-dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxydiphenylsulisomer, 4,4 '-dihydroxy two Double (4- the hydroxy-cyclohexyl)-propane of Benzophenone, 1,4- dihydroxy-hexane, 2,2-, 1,1 '-methylene, two-beta naphthal, 4,4 ', 4 '- Trihydroxy triphenyl methane, tri- (4- hydroxy phenyl) ethane of 1,1,1- or α, α, α '-three (4- hydroxy phenyl) -1- ethyl -4- are different Propylbenzene.
As the alcohol, can also be using the alcohol in the HFIP base contained by the repetitive shown in formula (1).
During the gas separation membrane of acquisition invention 7～10, can also be by these epoxides and hardener for epoxy resin It is applied in combination.If the curing agent is illustrated, aminated compounds, anhydrides compound, amides compound, phenol generalization can be enumerated Compound, sulfur alcohol compound, glyoxaline compound, polysulfide resins class compound or phosphorus species.Specifically, permissible Enumerate and belong to the diaminodiphenyl-methane of thermal curing agents, DADPS, diethylenetriamines, trien, poly- Aklylene glycol polyamines, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic acid Acid anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2-methylimidazole, triphenylphosphine, 2-ethyl-4-methylimidazole, BF3- amine complex or guanidine derivatives, belong to ultraviolet curing agent Diphenyl iodine hexafluorophosphate, triphenylsulfonium hexafluorophosphate.
The mixed proportion of the macromolecular compound comprising the repetitive shown in formula (1) and epoxide is in mass ratio It is calculated as macromolecular compound：Epoxide=10：90～98：2, preferably 50：50～95：5.
Epoxide is calculated as 70 in mass ratio with the mixing ratio of hardener for epoxy resin：30～99.5：0.5, preferably For 90：10～99：1.
In the midway operation for preparing above-mentioned gas seperation film, for example, can be coated with glass or silicon substrate, Ran Houtong Cross heating or irradiated using the ultraviolet of ultraviolet (UV) lamp etc. and solidified, so as to form the gas separation membrane of crosslinking curing. As spendable organic solvent, as long as can dissolve with the repetitive shown in formula (1) containing the non-right of HFIP base Claim polyimides and above-mentioned epoxide as the composition of principal component, it is possible to use with being not particularly limited.If concrete Illustrate, then can enumerate and belong to the DMF of amide solvent, DMA, N- methyl formyl Amine, HPT or METHYLPYRROLIDONE and cyclohexanone, propylene glycol methyl ether acetate or γ-Ding Nei Ester.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the invention is not restricted to these embodiments.
[preparation of polyimide film]
Preparation to the asymmetric polyimide film containing HFIP base of gas separation membrane is illustrated.
Add 2.01g (3.78mmol) in possessing the 200mL there-necked flask of nitrogen ingress pipe and reflux cooler following HFA-3,4 '-ODA, 1.68g (3.78mmol) 6FDA, 14gN, N- dimethylacetylamide, in a nitrogen atmosphere, stirs under room temperature 18 hours, then add pyridine, 0.77g (7.56mmol) acetic anhydride of 0.66g (8.32mmol), be stirred at room temperature further 3 hours.Gained reactant liquor is warming up to 200 DEG C, is stirred 6 hours further afterwards, is cooled to room temperature.Obtain being dissolved with polyamides Asia The uniform DMAC N,N' dimethyl acetamide solution of amine 1.The solution by GPC determine (equipment is by Tosoh Corporation system Make, HLC-8320, solvent are tetrahydrofuran, are scaled polystyrene.Same as below.) Mw of polyimides 1 that obtains is 28, 000.
By above-mentioned DMA solution coating on the glass substrate, using spin coater with rotating speed： 1000rpm, retention time：The application conditions of 30 seconds carry out rotary coating.By gained glass substrate in a nitrogen atmosphere, 200 DEG C Under carry out 1 hour heat after, from glass substrate peel off and obtain the film obtained by polyimides 1, that is, obtain with HFIP 1 film of polyimides of base and unsymmetric structure is (below, sometimes referred to as " polyimide film 1 ".).Thickness is determined, is as a result 25 μm.
Then, make a series of following shown diamine compounds containing HFIP base (HFA-3,4 '-MDA, HFA-2,4 '- ODA) react with following tetracarboxylic dianhydrides (PMDA, BPDA, BTDA, DSDA, ODPA, 6FDA), according to method similar to the above, Polyimide film 2～9 is obtained respectively by polyimides 2～9.The respective original of gained polyimide film 2～9 is shown in table 1 Material compound, thickness, illustrate the Mw for determining the polyimides 2～9 that obtains by GPC in table 2.
[table 1]
Polyimide film Diamine compound Tetracarboxylic dianhydride Thickness
Polyimide film 2 HFA-3,4 '-ODA BPDA 35μm
Polyimide film 3 HFA-3,4 '-ODA BTDA 40μm
Polyimide film 4 HFA-3,4 '-ODA ODPA 2Bμm
Polyimide film 5 HFA-3,4 '-MDA PMDA 25μm
Polyimide film 6 HFA-3,4 '-MDA DSDA 32μm
Polyimide film 7 HFA-3,4 '-MDA 6FDA 31μm
Polyimide film 8 HFA-2,4 '-ODA 6FDA 45μm
Polyimide film 9 HFA-2,4 '-ODA ODPA 40μm
[table 2]
Polyimides Mw
Polyimides 2 35,000
Polyimides 3 31,000
Polyimides 4 29,000
Polyimides 5 41,000
Polyimides 6 43,000
Polyimides 7 38,000
Polyimides 8 30,000
Polyimides 9 29,000
Then, by a series of diamine compounds containing HFIP base (HFA-3,4 '-ODA, HFA-3,4 '-MDA) and The DMA solution that serial tetracarboxylic dianhydride (6FDA, BPDA, BTDA, DSDA) group is obtained after merging polymerisation In, add following epoxy resin 1 of ormal weight or epoxy resin 2, the triphenylphosphine as curing agent (with respect to epoxy resin are 1 mass %), respectively obtain polyimides.The polyimides is distinguished masking, obtains polyimide film 10～13.Show in table 3 Go out the respective starting compound of polyimide film 10～13, the thickness of gained.
Epoxy resin 1：Bisphenol A type epoxy resin (Mitsubishi chemical Co., Ltd produces JER828)
Epoxy resin 2：(Aldrich Corporation is produced cresol novolak type epoxy resin, catalog number： 408042)
[table 3]
Polyimide film Diamine compound Tetracarboxylic dianhydride Epoxy resin Thickness
Polyimide film 10 HFA-3,4 '-ODA BTDA Epoxy resin 1 (10) 30μm
Polyimide film 11 HFA-3,4 '-ODA 6FDA Epoxy resin 2 (10) 40μm
Polyimide film 12 HFA-3,4 '-MDA BPDA Epoxy resin 1 (10) 32μm
Polyimide film 13 HFA-3,4 '-MDA 6FDA Epoxy resin 2 (10) 38μm
Annotation：When the gross mass of diamine compound and tetracarboxylic dianhydride is set as 100 by the numeral expression in table bracket Epoxy resin quality.
[evaluation of polyimide film 1]
The measure of air transmission coefficient and the evaluation of separating property are carried out to polyimide film 1.Gas separation membrane described below The assay method of Gas permeability.
It is 7cm by membrane area that air transmission coefficient is2Gas separation membrane configure in stainless steel vessel, based on JIS K7126-1：Pressure differential method described in the 1st of 2006 " plastic film and thin slice-air permeability test methods " is determining.
Specifically, under conditions of 23 DEG C of temperature, using helium (He), carbon dioxide (CO2), oxygen (O2), nitrogen (N2) and methane gas (CH4) as test gas, based on JIS K7126-1：2006 determine the transmission coefficients of each gas and divide From performance (ratio of the transmission coefficient of each gas).
It is shown in Table 4 based on above-mentioned JIS K7126-1：The measurement result of the air transmission coefficient of 2006 polyimide film 1, Table 5 illustrates the evaluation result of separating property.
[table 4]
Transmission coefficient measurement result
[table 5]
Separating property result
The comparison of [comparative example 1] polyimide film 1 and existing resin
Then, by the air transmission coefficient of above-mentioned polyimide film 1 and gas separating property with not within the scope of the invention The air transmission coefficient of the fluorine-containing polyimide film (comparative example 1) without HFIP base of following structural formula and gas separating property are compared Relatively.
Table 6 is the CO of the polyimide film obtained by the fluorinated polyimide of comparative example 12、O2、N2And CH4Ventilative system Several results, table 7 are the results of the separating property of the film.
Comparison sheet 4 and table 6, with the existing fluorinated polyimide described in comparative example 1 not within the scope of the invention The CO of film2、O2、N2And CH4Air transmission coefficient compare, belong to the present invention containing HFIP base asymmetric polyimide film, The CO of the gas separation membrane obtained by the polyimide film 1 of embodiment 12、O2、N2And CH4Air transmission coefficient show bigger Value, and the polyimide film 1 of embodiments of the invention 1 shows more excellent gas permeability.
As shown in table 7, compared with the gas separation membrane of comparative example 1, by the present invention containing HFIP base and unsymmetric structure The gas separation membrane of embodiment 2 that obtains of polyimides in CO2/CH4And CO2/N2Separating property in terms of more excellent.
[table 6]
[table 7]
[evaluation of polyimide film 2～13]
Separating property measure is carried out to polyimide film 2～13 using the evaluation method same with polyimide film 1.From knot Fruit is as can be seen that CO2Transmission coefficient be 30 Palestine and Israels on, show high transmission coefficient, the polyimide film phase with comparative example 1 Than, it is shown that more excellent performance.
Industrial applicability
The penetration speed of the gas separation membrane obtained by the asymmetric polyimide film containing HFIP base of the present invention is (ventilative Coefficient) there is very big difference according to the species of gas, gas separating property is excellent.Therefore, can be suitably used for natural from liquefying Separate in gas etc. and fixing carbon dioxide technology and by fuel with ethanol recovery for the purpose of Separation Membrane for Water and Ethanol etc..

Claims (14)

1. a kind of gas separation membrane, which has polyimide structures, and the polyimide structures have the repetition shown in formula (1) Unit, R1Divalent organic group shown in formula (2) or the divalent organic group shown in formula (3),
In formula (1), R1Represent divalent organic group and R2Represent quadrivalent organic radical group,
In formula (2), RaaFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base, p and q are each independently 0～2 integer, and meet 1≤p+q≤4, intersect with wavy line Line segment represents bonding position,
In formula (3), RbaFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base, r and s are each independently 0～2 integer, and meet 1≤r+s≤4, intersect with wavy line Line segment represents bonding position.
2. gas separation membrane according to claim 1, wherein, the divalent organic group shown in formula (2) is formula (4),
In formula, RabFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3) (CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the ester ring type for carbon number 3～12 The divalent organic group that hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP Represent-C (CF3)2OH base, represents bonding position with the line segment that wavy line intersects.
3. gas separation membrane according to claim 1 and 2, wherein, the divalent organic group shown in formula (2) is formula (4- 1) any one or in (4-2),
In formula, HFIP represents-C (CF3)2OH base, represents bonding position with the line segment that wavy line intersects.
4. gas separation membrane according to claim 1, wherein, the divalent organic group shown in formula (3) is shown in formula (5) Divalent organic group in any one,
In formula, RbbFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3) (CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the ester ring type for carbon number 3～12 The divalent organic group that hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP Represent-C (CF3)2OH base, represents bonding position with the line segment that wavy line intersects.
5. the gas separation membrane according to claim 1 or 4, wherein, the divalent organic group shown in formula (3) is formula (5- 1) any one or in (5-2),
In formula, HFIP represents-C (CF3)2OH base, represents bonding position with the line segment that wavy line intersects.
6. the gas separation membrane according to claim 1,2 or 4, wherein, R2Quadrivalent organic radical shown in formula (6)～(11) Any one in group,
In formula, represent bonding position with the line segment that wavy line intersects.
7. the gas separation membrane according to claim 1,2 or 4, wherein, R1Comprising the hydrogen of-OH base that has of HFIP base Atom is replaced by glycidyl.
8. gas separation membrane according to claim 7, wherein, the cyclic ether position open loop crosslinking of glycidyl.
9. the gas separation membrane according to claim 1,2,4 or 8, which is further will be with by the formula (1) Suo Shi Macromolecular compound and the epoxide of repetitive be mixed and heated and obtain.
10. gas separation membrane according to claim 9, wherein, epoxide is represented by formula (12)：
In formula, RfBe the g valency organic group that any g hydrogen atom is sloughed from alkane, aromatic ring or alicyclic ring, optionally contain in structure Oxygen atom, sulphur atom or nitrogen-atoms, a part of hydrogen atom are optionally replaced by fluorine atom, chlorine atom, alkyl or fluoroalkyl, and g represents 1 ～4 integer.
A kind of 11. polyimides, its have the repetitive shown in formula (1), R1Divalent organic group shown in formula (2) Or the divalent organic group shown in formula (3),
In formula (1), R1Represent divalent organic group and R2Represent quadrivalent organic radical group,
In formula (2), RaaFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base, p and q are each independently 0～2 integer, and meet 1≤p+q≤4, intersect with wavy line Line segment represents bonding position,
In formula (3), RbaFor singly-bound, oxygen atom, sulphur atom ,-SO2- base ,-CH2- base ,-C (=O)-base ,-C (CH3)2- base ,-C (CH3)(CH2CH3)-base ,-C (CF3)2- base ,-CH (CH3)-base ,-CH (OH)-base or-NH- base, or the fat for carbon number 3～12 The divalent organic group that ring type hydrocarbon compound, the aromatic hydrocarbon compound of carbon number 6～25 are sloughed any 2 hydrogen atoms and formed, HFIP represents-C (CF3)2OH base, r and s are each independently 0～2 integer, and meet 1≤r+s≤4, intersect with wavy line Line segment represents bonding position,
R1Comprising the hydrogen atom of-OH base that has of HFIP base replaced by glycidyl.
A kind of 12. cured film, its are formed by the polyimides described in claim 11, the contracting that the polyimides has The glyceryl cyclic ether position open loop crosslinking of water.
A kind of 13. cured film, its are to be mixed and heated the polyimides described in claim 11 with epoxide and obtain 's.
14. cured film according to claim 13, wherein, epoxide is represented by formula (12)：
In formula, RfBe the g valency organic group that any g hydrogen atom is sloughed from alkane, aromatic ring or alicyclic ring, optionally contain in structure Oxygen atom, sulphur atom or nitrogen-atoms, a part of hydrogen atom are optionally replaced by fluorine atom, chlorine atom, alkyl or fluoroalkyl, and g represents 1 ～4 integer.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5690870A (en) * 1994-10-26 1997-11-25 Nitto Denko Corporation Method of manufacturing a polyimide-type gas permeation membrane including fluorine
CN101573396A (en) * 2006-12-19 2009-11-04 中央硝子株式会社 Fluorinated diamine and polymer formed therefrom

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266100A (en) * 1992-09-02 1993-11-30 E. I. Du Pont De Nemours And Company Alkyl substituted polyimide, polyamide and polyamide-imide gas separation membranes
US5320650A (en) * 1993-05-04 1994-06-14 E. I. Du Pont De Nemours And Company Fluorinated aromatic polyimide, polyamide and polyamide-imide gas separation membranes
JPH08173778A (en) * 1994-10-26 1996-07-09 Nitto Denko Corp Manufacture of fluorine containing polyimide gas separating membrane
JP2001040089A (en) * 1999-07-27 2001-02-13 Nitto Denko Corp Polyimide resin, its production and gas separation membrane composed thereof
EP1783158B1 (en) * 2004-10-13 2013-12-11 Central Glass Company, Limited Fluorine-containing polymerizable monomer and polymer compound using same
US20100216967A1 (en) * 2009-02-20 2010-08-26 International Business Machines Corporation Interfacial polymerization methods for making fluoroalcohol-containing polyamides
JP5359914B2 (en) * 2010-02-12 2013-12-04 宇部興産株式会社 Polyimide gas separation membrane and gas separation method
JP5915376B2 (en) * 2011-05-30 2016-05-11 セントラル硝子株式会社 Gas separation membrane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5690870A (en) * 1994-10-26 1997-11-25 Nitto Denko Corporation Method of manufacturing a polyimide-type gas permeation membrane including fluorine
CN101573396A (en) * 2006-12-19 2009-11-04 中央硝子株式会社 Fluorinated diamine and polymer formed therefrom

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