WO2014084187A1 - Membrane de séparation de gaz - Google Patents
Membrane de séparation de gaz Download PDFInfo
- Publication number
- WO2014084187A1 WO2014084187A1 PCT/JP2013/081700 JP2013081700W WO2014084187A1 WO 2014084187 A1 WO2014084187 A1 WO 2014084187A1 JP 2013081700 W JP2013081700 W JP 2013081700W WO 2014084187 A1 WO2014084187 A1 WO 2014084187A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- gas separation
- separation membrane
- represented
- hfip
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 110
- 238000000926 separation method Methods 0.000 title claims abstract description 99
- 229920001721 polyimide Polymers 0.000 claims abstract description 81
- 239000004642 Polyimide Substances 0.000 claims abstract description 67
- 125000000962 organic group Chemical group 0.000 claims abstract description 51
- 239000007789 gas Substances 0.000 claims description 111
- -1 alicyclic hydrocarbon compound Chemical class 0.000 claims description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 125000004434 sulfur atom Chemical group 0.000 claims description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 14
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
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- GGOZGYRTNQBSSA-UHFFFAOYSA-N pyridine-2,3-diol Chemical compound OC1=CC=CN=C1O GGOZGYRTNQBSSA-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KCNSDMPZCKLTQP-UHFFFAOYSA-N tetraphenylen-1-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC=C2C2=C1C=CC=C2O KCNSDMPZCKLTQP-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- 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
- B01D67/0016—Coagulation
- B01D67/00165—Composition of the coagulation baths
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1046—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
- B01D65/106—Repairing membrane apparatus or modules
- 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
Definitions
- the present invention relates to a gas separation membrane.
- Gas separation by a gas separation membrane has long been attracting attention as a simple technique that can continuously separate a mixed gas in a gaseous state and does not involve phase change.
- Gas separation is a technique for selectively separating gas by utilizing the difference in permeation speed and the presence or absence of permeation depending on the type of gas that permeates the gas separation membrane (hereinafter, sometimes referred to as “gas”).
- polymers such as cellulose acetate, polysulfone or polyimide are known.
- polyimide is known as a material that has strength suitable for use as a gas separation membrane, is not easily damaged, has excellent heat resistance, and can be used at high temperatures.
- a polyimide gas separation membrane containing a hexafluoroisopropylidene group (hereinafter sometimes referred to as “—C (CF 3 ) 2 —group”) in the repeating structure is represented by helium (hereinafter referred to as “He”). ), Carbon dioxide (hereinafter sometimes referred to as “CO 2 ”), high permeability to these gases, oxygen of these gases (hereinafter sometimes referred to as “O 2 ”), methane (Hereinafter, sometimes referred to as “CH 4 ”) is known to have high selectivity.
- He helium
- CO 2 Carbon dioxide
- O 2 oxygen of these gases
- CH 4 methane
- Patent Documents 1 to 3 2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group (hereinafter “—C (CF 3 ) 2 OH” or “A fluorine-containing polymerizable monomer, which is a diamine having “HFIP group” in some cases, and a method for producing the same are disclosed.
- a method for producing a gas separation membrane made of polyimide or the like includes a method in which a polyimide solution is wet-coated and then a solvent is simply evaporated to obtain a homogeneous membrane, and a heterogeneous asymmetric membrane consisting of a dense layer and a porous layer. There is a way to get it.
- a method of obtaining an asymmetric membrane is a method in which a polymer solution is discharged from a discharge port, a solvent existing in the vicinity of the surface is evaporated in the air to form a dense layer, and then a solvent that is compatible with the solvent of the polymer solution but does not dissolve the polymer.
- Patent Document 4 discloses a method for producing a composite reverse osmosis membrane by this method.
- the diamine and tetracarboxylic dianhydride for obtaining a polyimide containing a —C (CF 3 ) 2 — group are limited, and the chemical structure is limited when forming a polyimide film.
- a gas separation membrane is used, there is a problem that it is difficult to design a chemical structure considering workability, strength, and separation performance.
- An object of the present invention is to solve such problems, and to provide a gas separation membrane that dissolves in an organic solvent, has excellent moldability, and has excellent gas separation performance when used as a gas separation membrane.
- the present inventors have prepared a polyimide obtained from an aromatic diamine having an HFIP group, which is a polar group having an —OH group, as a substituent, and two —NH 2 groups in the compound being in an asymmetric positional relationship. By using it, it was made soluble in an organic solvent, particularly a polar solvent, and the polyimide was used as a gas separation membrane, thereby improving gas separation performance and completing the present invention.
- the present invention is as follows.
- R 1 represents a divalent organic group
- R 2 represents a tetravalent organic group.
- R 1 is represented by the general formula (2) (Wherein R aa is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 3 ) 2 — group, —C ( CH 3 ) (CH 2 CH 3 ) — group, —C (CF 3 ) 2 — group, —CH (CH 3 ) — group, —CH (OH) — group or —NH— group, or carbon number
- This is a divalent organic group formed by removing any two hydrogen atoms from an alicyclic hydrocarbon compound having 3 to 12 carbon atoms and an aromatic hydrocarbon compound having 6 to 25 carbon atoms.
- HFIP is —C (CF 3 ) 2 represents an OH group, where p and q are each independently an integer of 0 to
- R ba is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 3 ) 2 — group, —C ( CH 3 ) (CH 2 CH 3 ) — group, —C (CF 3 ) 2 — group, —CH (CH 3) — group, —CH (OH) — group or —NH— group, or 3 carbon atoms
- HFIP is —C (CF 3 ) 2 Represents an OH group, r and s are each independently an integer of 0 to 2, and satisfy 1 ⁇ r + s ⁇ 4.
- a line segment intersecting with a wavy line represents a bonding position.
- the divalent organic group represented by the general formula (2) is represented by the general formula (4).
- R ab is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 3 ) 2 — group, —C ( CH 3 ) (CH 2 CH 3 ) — group, —C (CF 3 ) 2 — group, —CH (CH 3 ) — group, —CH (OH) — group or —NH— group, or carbon number
- This is a divalent organic group formed by removing any two hydrogen atoms from an alicyclic hydrocarbon compound having 3 to 12 carbon atoms and an aromatic hydrocarbon compound having 6 to 25 carbon atoms.
- HFIP is —C (CF 3 ) 2 Represents an OH group (the line that intersects the wavy line represents the bond position)
- the gas separation membrane according to invention 1 wherein
- the divalent organic group represented by the general formula (2) is represented by the formula (4-1) or (4-2) (In the formula, HFIP represents a —C (CF 3 ) 2 OH group. A line segment intersecting with a wavy line represents a bonding position.)
- the divalent organic group represented by the general formula (3) is represented by the formula (5).
- R bb is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 3 ) 2 — group, —C ( CH 3 ) (CH 2 CH 3 ) — group, —C (CF 3 ) 2 — group, —CH (CH 3 ) — group, —CH (OH) — group or —NH— group, or carbon number
- This is a divalent organic group formed by removing any two hydrogen atoms from an alicyclic hydrocarbon compound having 3 to 12 carbon atoms and an aromatic hydrocarbon compound having 6 to 25 carbon atoms.
- HFIP is —C (CF 3 ) 2 Represents an OH group (the line that intersects the wavy line represents the bond position)
- the gas separation membrane of invention 1 which is any one of divalent organic groups represented by:
- the divalent organic group represented by the general formula (3) is represented by the formula (5-1) or (5-2) (In the formula, HFIP represents a —C (CF 3 ) 2 OH group. A line segment intersecting with a wavy line represents a bonding position.)
- the gas separation membrane of invention 1 or 4 which is any one of the above.
- R 2 represents the formulas (6) to (11) (In the formula, the line that intersects the wavy line represents the coupling position.)
- invention 7 The gas separation membrane according to any one of inventions 1 to 6, wherein a hydrogen atom of an —OH group of the HFIP group contained in R 1 is substituted with a glycidyl group.
- invention 9 Furthermore, the gas separation membrane according to any one of inventions 1 to 8, obtained by mixing with an epoxy compound and heating.
- the epoxy compound has the general formula (12) (In the formula, R f is a g-valent organic group in which an arbitrary number of hydrogen atoms have been removed from an alkane, aromatic ring or alicyclic ring, and the structure may contain an oxygen atom, a sulfur atom or a nitrogen atom, (Part of the hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, an alkyl group or a fluoroalkyl group, and g represents an integer of 1 to 4).
- the gas separation membrane of the invention 9 represented by these.
- the polyimide-based gas separation membrane obtained from an asymmetric aromatic diamine having a HFIP group as a substituent of the present invention has good separation performance due to having an HFIP group as a substituent and an asymmetric structure. Since the HFIP group has an —OH group, the gas separation membrane according to the present invention is soluble in a specific organic solvent, particularly a polar solvent, and it is easy to prepare a polyimide solution, which is molded into a desired membrane shape. Is possible.
- the polyimide gas separation membrane having an asymmetric structure with the HFIP group of the present invention it is easy to introduce the HFIP group into the aromatic diamine having an asymmetric structure as a raw material. Compared to a separation membrane, in addition to high gas separation performance, it is possible to design a structure for improving membrane properties such as membrane strength or resistance to swelling in a solvent.
- a gas separation membrane having a —C (CF 3 ) 2 — group in addition to an HFIP group and an asymmetric structure exhibits even better gas separation performance.
- a polyimide having an HFIP group and having an asymmetric structure may be referred to as “HFIP group-containing asymmetric polyimide”.
- an aromatic diamine compound having an HFIP group and an asymmetric structure may be referred to as an “HFIP group-containing asymmetric aromatic diamine compound”.
- the gas separation membrane of the present invention is made from an HFIP group-containing asymmetric polyimide.
- the monomer compound used as a raw material for the HFIP group-containing asymmetric polyimide include HFIP group-containing asymmetric aromatic diamine and tetracarboxylic dianhydride. It is preferable to employ an aromatic diamine for its strength when it is used as a gas separation membrane.
- the HFIP group-containing asymmetric polyimide is obtained by reacting these monomer compounds.
- asymmetric aromatic diamine having an HFIP group may be added to adjust the strength and separation performance of the membrane.
- other dicarboxylic acids and derivatives thereof may be added in addition to tetracarboxylic dianhydride in order to adjust the strength and separation performance of the membrane.
- the HFIP group-containing asymmetric aromatic diamine As a monomer compound for synthesizing the HFIP group-containing asymmetric polyimide for producing the gas separation membrane of the present invention, the HFIP group-containing asymmetric aromatic diamine has the formula (2-A) (Wherein R aa is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 2 ) 2 — group, —C ( CH 3 ) (CH 2 CH 3 ) — group, —C (CF 3 ) 2 — group, —CH (CH 3 ) — group, —CH (OH) — group or —NH— group, or carbon number
- R aa is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 2 ) 2 — group, —
- R ba is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 2 ) 2 — group, —C ( CH 3 ) (CH 2 CH 3 ) — group, —C (CF 3 ) 2 — group, —CH (CH 3 ) — group, —CH (OH) — group or —NH— group, or carbon number
- HFIP is —C (CF 3 ) 2 represents an OH group, where r and s are each independently an integer of 0 to 2 and satisfy 1 ⁇ r + s ⁇ 4. It is represented by
- HFIP group-containing asymmetric aromatic diamine (2-A) examples of the divalent organic group formed by removing two hydrogen atoms from an alicyclic hydrocarbon compound having 3 to 12 carbon atoms include cyclohexane, bicyclohexane, and adamantane.
- a divalent organic group formed by removing two hydrogen atoms of norbornane is preferable, and the divalent organic group formed by removing two hydrogen atoms of an aromatic hydrocarbon compound having 6 to 25 carbon atoms is benzene.
- the HFIP group-containing asymmetric aromatic diamine (2-A) has the formula (4-A) Wherein R ab is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 2 ) 2 — group, —C ( CH 3 ) (CH 2 CH 3 ) — group, —C (CF 3 ) 2 — group, —CH (CH 3 ) — group, —CH (OH) — group or —NH— group, or carbon number
- This is a divalent organic group formed by removing any two hydrogen atoms from an alicyclic hydrocarbon compound having 3 to 12 carbon atoms and an aromatic hydrocarbon compound having 6 to 25 carbon atoms.
- HFIP is —C (CF 3 ) 2 represents an OH group.) The compound represented by these is preferable.
- HFIP represents a —C (CF 3 ) 2 OH group.
- Me represents a methyl group.
- Et represents an ethyl group.
- the compound represented by these is mentioned.
- the formulas (4-1-A) and (4-2-A) are particularly preferable because of easy availability of the raw material diamine.
- the divalent organic group formed by removing two hydrogen atoms from the alicyclic hydrocarbon compound having 3 to 12 carbon atoms includes cyclohexane, bicyclohexane, and adamantane.
- a divalent organic group formed by removing two hydrogen atoms of norbornane is preferable, and the divalent organic group formed by removing two hydrogen atoms of an aromatic hydrocarbon compound having 6 to 25 carbon atoms is benzene.
- the HFIP group-containing asymmetric aromatic diamine (3-A) has the formula (5-A) Wherein R bb is a single bond, oxygen atom, sulfur atom, —SO 2 — group, —CH 2 — group, —C ( ⁇ O) — group, —C (CH 2 ) 2 — group, —C ( CH 3 ) (CH 2 CH 3 ) — group, —C (CF 3 ) 2 — group, —CH (CH 3 ) — group, —CH (OH) — group or —NH— group, or carbon number
- This is a divalent organic group formed by removing any two hydrogen atoms from an alicyclic hydrocarbon compound having 3 to 12 carbon atoms and an aromatic hydrocarbon compound having 6 to 25 carbon atoms.
- HFIP is —C (CF 3 ) 2 represents an OH group.) The compound represented by these is preferable.
- HFIP represents a —C (CF 3 ) 2 OH group.
- Me represents a methyl group.
- Et represents an ethyl group.
- the compound represented by these is mentioned.
- (5-1-A) and (5-2-A) are particularly preferred because of the availability of raw material diamines.
- HFIP group-containing asymmetric aromatic diamines may be used in combination of two or more.
- the diamine can be obtained by reacting an asymmetric structure-containing aromatic diamine with hexafluoroacetone or hexafluoroacetone trihydrate.
- reaction with the symmetrical structure containing aromatic diamine of patent document 1 and hexafluoroacetone or hexafluoroacetone trihydrate is applicable.
- diamines Asymmetric aromatic diamines with HFIP groups in the synthesis of polyimides with HFIP groups and asymmetric structures for the adjustment of membrane properties such as gas separation performance, solubility in polar solvents, membrane strength, etc.
- other diamines and dihydroxyamines may be used.
- the amount used is 10 mol% to 80 mol%, preferably 30 mol% to 60 mol%, based on the tetracarboxylic dianhydride.
- diamines include 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, 3,3′-bistrifluoromethyl-4,4′-diaminobiphenyl, 2,2′-bistrifluoromethyl- 4,4'-diaminobiphenyl, 3,3'-bistrifluoromethyl-5,5'-diaminobiphenyl, bis (trifluoromethyl) -4,4'-diaminobiphenyl, bis (fluorinated alkyl) -4,4 '-Diaminobiphenyl, dichloro-4,4'-diaminobiphenyl, dibromo-4,4'-diaminobiphenyl, bis (fluorinated alkoxy) -4,4'-diaminobiphenyl, diphenyl-4,4'-diaminobiphenyl, 4,4′-bis (4-aminotetrafluorophenoxy) tetrafluorobenz
- dihydroxyamines examples include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoro Propane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) Lopan, 4,4′-diamino-3,3′-
- Tetracarboxylic dianhydride used for synthesizing the HFIP group-containing asymmetric polyimide according to the present invention has the general formula (12). (In the formula, R 2 represents a tetravalent organic group.) It is represented by
- R 2 is preferably a tetravalent organic group in which four hydrogen atoms are removed from an alkane, alicyclic ring or aromatic ring, and has a fluorine atom, chlorine atom, oxygen atom, sulfur in the structure.
- An atom or a nitrogen atom may be contained, and a part of the hydrogen atom may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group.
- tetracarboxylic dianhydrides include pyromellitic dianhydride (hereinafter sometimes referred to as “PMDA”), trifluoromethylbenzenetetracarboxylic dianhydride, bistrifluoro.
- PMDA pyromellitic dianhydride
- trifluoromethylbenzenetetracarboxylic dianhydride bistrifluoro.
- PMDA, BPDA, BTDA, DSDA, ODPA and 6FDA are particularly preferable from the viewpoint of availability, and 6FDA is more preferable from the viewpoint of good gas separation performance (permeability and selectivity).
- R 3 is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring and an alkylene group, and may contain an oxygen atom, a sulfur atom or a nitrogen atom,
- R 4 may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group, or a cyano group
- R 4 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- each X is independently a chlorine atom, a fluorine atom, a bromine atom or an iodine atom.
- R 3 is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring and an alkylene group, and may contain an oxygen atom, a sulfur atom or a nitrogen atom, The hydrogen atom may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group.
- the dicarboxylic acid or dicarboxylic acid derivative represented by the general formulas (13) and (14) any of aliphatic dicarboxylic acid, aromatic dicarboxylic acid, or these dicarboxylic acid derivatives may be used.
- Examples of the aliphatic dicarboxylic acid and derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dicarboxylic acid compounds of sebacic acid or their dicarboxylic acid derivatives. It is done.
- aromatic dicarboxylic acids and derivatives thereof include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-dicarboxybiphenyl, 3,3′-dicarboxybiphenyl, 3,3′-dicarboxyldiphenyl ether, 3, 4'-dicarboxyldiphenyl ether, 4,4'-dicarboxyldiphenyl ether, 3,3'-dicarboxyldiphenylmethane, 3,4'-dicarboxyldiphenylmethane, 4,4'-dicarboxyldiphenylmethane, 4,4'-dicarboxyldiphenylmethane, 3,3'-dicarboxyl Diphenyldifluoromethane, 3,4'-dicarboxyldiphenyldifluoromethane, 4,4'-dicarboxyldiphenyldifluoromethane, 3,3'-dicarboxyldiphenylsulfone
- terephthalic acid isophthalic acid, 4,4'-dicarboxybiphenyl, 2,2'-ditrifluoromethyl-4,4'-dicarboxybiphenyl because of its ease of availability and ease of condensation polymerization.
- 2,2-bis (4-carboxyphenyl) hexafluoropropane is preferred.
- the amount of the dicarboxylic acid or the dicarboxylic acid derivative used is 10 mol% or more and 80 mol% or less, preferably 30 mol% or more and 60 mol% or less with respect to the tetracarboxylic dianhydride. Within the range of the molar ratio, gas separation performance, solubility in polar solvents, and membrane strength can be adjusted.
- dicarboxylic acid (derivative) means “dicarboxylic acid or dicarboxylic acid derivative”. The same applies hereinafter in the description.
- the above-mentioned HFIP group-containing asymmetric aromatic diamine and tetracarboxylic dianhydride are essential, and if necessary, other diamines and dicarboxylic acids.
- examples thereof include a method in which an acid (derivative) is added and then melted at 150 ° C. or higher and reacted without solvent, and a method in which a polymerization reaction is carried out in an organic solvent at a reaction temperature of ⁇ 20 to 80 ° C.
- diamine and carboxylic dianhydride or dicarboxylic acid (derivative) react with each other in a one-to-one molar ratio, so that HFIP group-containing asymmetric diamine and other diamines and tetracarboxylic acids.
- the organic solvent that can be used in the polymerization reaction is only required to dissolve the reaction substrate.
- the polymerization reaction may be carried out in the presence of these organic solvents and an acid acceptor such as pyridine or triethylamine.
- the polyamic acid having an asymmetric structure with the HFIP group obtained by the polymerization reaction can be further converted to a polyimide having an asymmetric structure with the HFIP group, which is the target product, by immobilization by cyclization by dehydration ring closure reaction. .
- the dehydration ring closure reaction is performed under conditions that promote cyclization, such as heating and use of an acid catalyst.
- a polyamic acid solution having an asymmetric structure with an HFIP group immediately after the polymerization reaction can be imidized at a high temperature of 150 ° C. or more and 250 ° C. or less to prepare an HFIP group-containing asymmetric polyimide solution.
- pyridine, triethylamine, acetic anhydride or the like may be added.
- the concentration of the HFIP group-containing asymmetric polyimide in the solution is preferably 5% by mass or more and 50% by mass or less. If it is less than 5% by mass, it is too thin to be industrially practical. If it exceeds 50% by mass, it is difficult to dissolve. Furthermore, it is preferably 10% by mass or more and 40% by mass or less.
- the weight average molecular weight (hereinafter sometimes referred to as “Mw”) of the HFIP group-containing asymmetric polyimide according to the present invention is preferably 10,000 or more, and more preferably 20,000 or more.
- the upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less.
- the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor.
- the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult.
- the weight average molecular weight here is determined as a converted value based on standard polystyrene by gel permeation chromatography (hereinafter sometimes referred to as “GPC”) analysis (the same applies hereinafter). Detailed analysis conditions for the analysis are described in the examples of the present application.
- GPC gel permeation chromatography
- HFIP group-containing asymmetric polyimide solution Preparation of HFIP group-containing asymmetric polyimide solution
- the HFIP group-containing asymmetric polyimide solution thus obtained can be used as it is for gas separation membrane production.
- a solution of an HFIP group-containing asymmetric polyimide is added to a poor solvent such as water or alcohol to add an HFIP group.
- a poor solvent such as water or alcohol
- the organic solvent that can be used is not particularly limited as long as the HFIP group-containing asymmetric polyimide is dissolved.
- the gas separation membrane containing the HFIP group-containing asymmetric polyimide of the present invention is a homogeneous membrane obtained by a wet film formation method for producing a thin film by utilizing the evaporation of the solvent from the HFIP group-containing asymmetric polyimide solution, Alternatively, it may be any one of an asymmetric membrane having a dense layer and a porous layer obtained by other methods.
- the homogenous film is, for example, wet-coated with a spin coater, applicator or the like on the above-mentioned HFIP group-containing asymmetric polyimide solution on a substrate such as a glass substrate, and then heated in a dry gas such as air, nitrogen or argon, After evaporating the solvent, it is obtained by peeling from the glass substrate.
- a HFIP group-containing asymmetric polyamic acid solution is used to coat the substrate by the above procedure, and then heated to imidize to obtain a homogeneous film.
- the thickness of the homogeneous membrane is preferably 5 ⁇ m or more and 1 mm or less.
- a film thinner than 5 ⁇ m is difficult to manufacture and easily broken.
- a film thicker than 1 mm is difficult for gas to permeate. More preferably, it is 10 ⁇ m to 200 ⁇ m.
- An asymmetric film having a dense layer and a porous layer can be formed by the method described above. Moreover, after forming an asymmetric film using a polyamic acid solution instead of a polyimide solution, the asymmetric film can also be obtained by thermal imidization.
- the dense layer has different permeation speeds depending on the gas type, and has a gas separation function to be selected for the mixed gas.
- the porous layer has a role as a support for maintaining the membrane shape.
- the asymmetric membrane including the HFIP group-containing asymmetric polyimide used for the gas separation membrane of the present invention may be either a flat membrane shape or a hollow fiber shape.
- the thickness of the dense layer is preferably 10 nm or more and 10 ⁇ m or less. If it is thinner than 10 nm, it is difficult to form a film and it is not practical. If it is thicker than 10 ⁇ m, it is difficult for gas to permeate. Preferably they are 30 nm or more and 1 micrometer or less.
- the thickness of the porous layer is preferably 5 ⁇ m or more and 2 mm or less for a flat film. If it is thinner than 5 ⁇ m, it is difficult to form a film and it is not practical. If it is thicker than 2 mm, it is difficult for gas to permeate. More preferably, they are 10 micrometers or more and 500 micrometers or less.
- the inner diameter is 10 ⁇ m or more and 4 mm or less, preferably 20 ⁇ m or more and 1 mm or less, and the outer diameter is 30 ⁇ m or more and 8 mm or less, preferably 50 ⁇ m or more and 1.5 mm or less. In the case of a hollow fiber shape, it is preferable to have a dense layer on the outside.
- the coagulation liquid for producing the asymmetric membrane water or a mixed solvent of water and an organic solvent is preferably used.
- the mixed solvent contains 40% by mass or more, preferably 50% by mass or more of water, and examples of the organic solvent include alcohols such as methanol, ethanol or isopropanol, and ketones such as acetone, methyl ethyl ketone, and diethyl ketone.
- alcohols such as methanol, ethanol or isopropanol
- ketones such as acetone, methyl ethyl ketone, and diethyl ketone.
- the HFIP group-containing asymmetric structure polyimide used for the gas separation membrane of the present invention is an amide solvent N, N-dimethylacetamide, N, N-dimethylformamide or N- It is particularly easy to dissolve in methyl-2-pyrrolidone, lactones ⁇ -butyrolactone and ⁇ -valerolactone, it is easy to produce a homogeneous film having a desired film thickness, and an asymmetric film using an aqueous coagulant is used. It is also easy to produce.
- both dry air, aqueous coagulation liquid, etc. are discharged inside the discharge port.
- a desired dense layer can be formed.
- a porous layer having a desired pore size, pore size distribution, and thickness can be formed by changing the organic solvent species of the coagulation bath.
- the film treated with the coagulating liquid is preferably used after being dried by heat treatment.
- the heat treatment temperature is preferably not higher than the glass transition temperature of polyimide so as not to melt.
- silicone resin coating For the purpose of repairing the surface defect of the produced gas separation membrane, a silicone resin may be coated on the surface of the separation membrane.
- a coating method a known coating method such as spin coating, coating with an applicator, or dip coating can be used.
- Silicone resins include general dimethyl silicone, phenyl group-containing silicone, vinyl group-containing silicone, Si-H group-containing silicone, trifluoropropyl group-containing silicone, silanol group-containing silicone, amino group-containing silicone, epoxy group-containing silicone, A methacryl group containing silicone, an acryl group containing silicone, etc. are mentioned. These are commercially available, such as 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 manufactured by Gelest. Is mentioned.
- the polymer compound having a repeating unit represented by the general formula (1) is mixed with an epoxy compound as in the gas separation membranes of Inventions 7 to 10 for the purpose of improving mechanical strength or plastic resistance. And cured by heating or light irradiation to form a cured film. The cured film can also be applied to the homogeneous film and the asymmetric film.
- Epoxy compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol aralkyl resin, phenol triol.
- Rf is a g-valent organic group in which g hydrogen atoms have been removed from an alkane, aromatic ring or alicyclic ring, and the structure may contain an oxygen atom, a sulfur atom or a nitrogen atom, (Part of the hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, an alkyl group, or a fluoroalkyl group.
- G is an integer of 1 to 4.
- Examples of the alcohol include 1,4-cyclohexanediol, 1,3-adamantanediol, catechol, 1,3-benzenediol, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl, and 2,2′-methylene.
- these epoxy compounds and epoxy resin curing agents may be used in combination.
- the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, mercaptan compounds, imidazole compounds, polysulfide resin compounds, and phosphorus compounds.
- thermosetting agents diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, triethylenetetramine, polyalkylene glycol polyamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride Methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2-methylimidazole, triphenylphosphine, 2-ethyl-4-methylimidazole, BF 3 -amine complex or Examples thereof include guanidine derivatives, ultraviolet curing agents such as diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate.
- ultraviolet curing agents such as diphenyliodonium hexafluorophosphate
- the mixing ratio of the epoxy compound and the curing agent for the epoxy resin is 70:30 to 99.5: 0.5, preferably 90:10 to 99: 1, expressed as a mass ratio.
- the gas separation membrane In the middle step of manufacturing the gas separation membrane, for example, it is applied to a glass or silicon substrate, and then cured by heating or ultraviolet irradiation with an ultraviolet (UV) lamp or the like to form a crosslinked and cured gas separation membrane.
- UV ultraviolet
- the organic solvent that can be used is not particularly limited as long as it can dissolve the HFIP group-containing asymmetric polyimide having the repeating unit represented by the general formula (1) and the composition mainly composed of the epoxy compound. can do.
- N, N-dimethylacetamide solution in which polyimide 1 was dissolved was obtained.
- the Mw of polyimide 1 determined by GPC measurement of the solution (the device is HLC-8320 manufactured by Tosoh Corporation, the solvent is tetrahydrofuran, converted to polystyrene, and the same shall apply hereinafter) was 28,000.
- the above N, N-dimethylacetamide solution was applied on a glass substrate, and using a spin coater, the rotation speed: 1000 rpm, the retention time: 30 sec.
- Spin coating was performed under the following coating conditions.
- the obtained glass substrate is heated at 200 ° C. for 1 hour in a nitrogen atmosphere, and then peeled off from the glass substrate, that is, a film obtained from polyimide 1, that is, a polyimide 1 film having an asymmetric structure with an HFIP group (hereinafter, “ May be referred to as “polyimide film 1”).
- the film thickness was measured and found to be 25 ⁇ m.
- polyimide films 2 to 9 were obtained from polyimides 2 to 9, respectively, in the same manner as described above.
- raw material compounds and film thicknesses are shown in Table 1, and Mw of polyimides 2 to 9 obtained by GPC measurement are shown in Table 2.
- Epoxy resin 1 bisphenol A type epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation)
- Epoxy resin 2 Cresol novolac type epoxy resin (manufactured by Aldrich, catalog No. 408042)
- the polyimide membrane 1 was measured for gas permeability coefficient and evaluated for separation performance. The measurement method of the gas permeation performance of the gas separation membrane is shown below.
- the gas permeability coefficient is the same as the differential pressure method described in Part 1 of JIS K7126-1: 2006 “Plastics—Films and Sheets—Gas Permeability Test Method” by placing a gas separation membrane with a membrane area of 7 cm 2 in a stainless steel cell. Measured in conformity.
- helium (He), carbon dioxide gas (CO 2 ), oxygen gas (O 2 ), nitrogen gas (N 2 ) and methane gas (CH 4 ) are used as test gases under the condition of a temperature of 23 ° C.
- helium (He) carbon dioxide gas (CO 2 ), oxygen gas (O 2 ), nitrogen gas (N 2 ) and methane gas (CH 4 ) are used as test gases under the condition of a temperature of 23 ° C.
- the permeability coefficient and separation performance of each gas were measured.
- Comparative Example 1 Comparison of Polyimide Membrane 1 and Conventional Resin Next, the gas permeation coefficient and gas separation performance of the polyimide membrane 1 described above, and a fluorine-containing polyimide having no HFIP group of the following structural formula not within the scope of the present invention The gas permeability coefficient and gas separation performance of the membrane (Comparative Example 1) were compared.
- Table 6 shows the results of gas permeability coefficients of CO 2 , O 2 , N 2 and CH 4 of the polyimide membrane obtained from the fluorine-containing polyimide of Comparative Example 1, and Table 7 shows the results of the separation performance of the membrane.
- the gas permeation coefficients of CO 2 , O 2 , N 2 and CH 4 of the gas separation membrane obtained from the polyimide membrane 1 of Example 1 which is the HFIP group-containing asymmetric polyimide membrane of the present invention Shows a value larger than the gas permeability coefficient of CO 2 , O 2 , N 2 and CH 4 of the conventional fluorine-containing polyimide film described in Comparative Example 1 which is not in the category of the present invention.
- the polyimide membrane 1 exhibited better gas separation properties.
- the gas separation membrane of Example 2 obtained from the polyimide having an HFIP group and an asymmetric structure of the present invention is more CO 2 / CH 4 and CO 2 than the gas separation membrane of Comparative Example 1.
- the separation performance of / N 2 was excellent.
- the gas separation membrane obtained from the HFIP group-containing asymmetric polyimide membrane of the present invention has a large difference in permeation rate (gas permeation coefficient) depending on the type of gas, and is excellent in gas separation performance. Therefore, it can be suitably used for a separation / fixation technique of carbon dioxide from liquefied natural gas or the like, and a water-ethanol separation membrane for the purpose of recovering ethanol for fuel.
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Abstract
Le problème selon l'invention consiste à proposer une membrane de séparation de gaz qui se dissout dans un solvant organique, présente une très bonne formabilité et se caractérise par de remarquables performances en matière de séparation de gaz quand elle est utilisée en tant que membrane de séparation de gaz. La solution selon l'invention consiste en une membrane de séparation de gaz à structure polyimide comportant un motif répété représenté par la formule générale (1) (dans la formule, R1 représente un groupe organique bivalent et R2 représente un groupe organique tétravalent), R1 étant un groupe organique bivalent représenté par la formule générale (2) ou un groupe organique bivalent représenté par la formule générale (3).
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JP6547503B2 (ja) * | 2014-09-12 | 2019-07-24 | セントラル硝子株式会社 | 気体分離膜 |
JP2016137484A (ja) * | 2015-01-26 | 2016-08-04 | セントラル硝子株式会社 | 気体分離膜 |
CN105289337B (zh) * | 2015-11-04 | 2017-07-28 | 中国科学院山西煤炭化学研究所 | 一种可交联聚酰亚胺气体分离膜及制备方法 |
TWI641654B (zh) * | 2016-04-08 | 2018-11-21 | Taiwan Textile Research Institute | 聚醯亞胺組成物以及分離膜的製備方法 |
TWI629095B (zh) * | 2016-04-08 | 2018-07-11 | 財團法人紡織產業綜合研究所 | 聚醯亞胺組成物以及分離膜的製備方法 |
CN107138056B (zh) * | 2017-05-12 | 2020-04-14 | 天津工业大学 | 一种用于n2/ch4分离的气体分离膜 |
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JP2001040089A (ja) * | 1999-07-27 | 2001-02-13 | Nitto Denko Corp | ポリイミド樹脂、その製造法及びこれからなる気体分離膜 |
KR100877270B1 (ko) * | 2004-10-13 | 2009-01-07 | 샌트랄 글래스 컴퍼니 리미티드 | 불소 함유 중합성 단량체 및 그것을 이용한 고분자 화합물 |
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- 2013-11-14 JP JP2013236336A patent/JP6194774B2/ja active Active
- 2013-11-26 WO PCT/JP2013/081700 patent/WO2014084187A1/fr active Application Filing
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JP2014128788A (ja) | 2014-07-10 |
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CN104822444A (zh) | 2015-08-05 |
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