US20160089639A1 - High permeability polyimide membranes: gas selectivity enhancement through uv treatment - Google Patents
High permeability polyimide membranes: gas selectivity enhancement through uv treatment Download PDFInfo
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- US20160089639A1 US20160089639A1 US14/497,354 US201414497354A US2016089639A1 US 20160089639 A1 US20160089639 A1 US 20160089639A1 US 201414497354 A US201414497354 A US 201414497354A US 2016089639 A1 US2016089639 A1 US 2016089639A1
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 72
- 229920001721 polyimide Polymers 0.000 title claims abstract description 71
- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 230000035699 permeability Effects 0.000 title abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims description 21
- 229920005597 polymer membrane Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002798 polar solvent Substances 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 claims description 4
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000001294 propane Substances 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- KHSJPILTPYIYOH-UHFFFAOYSA-N CC1=CC(CC2=CC(C)=C(N3C(=O)C4=CC5=C(C=C4C3=O)C(=O)N(C3=C(C)C(N4C(=O)C6=CC7=C(C=C6C4=O)C(=O)N(C)C7=O)=C(C)C=C3C)C5=O)C(C)=C2)=CC(C)=C1C Chemical compound CC1=CC(CC2=CC(C)=C(N3C(=O)C4=CC5=C(C=C4C3=O)C(=O)N(C3=C(C)C(N4C(=O)C6=CC7=C(C=C6C4=O)C(=O)N(C)C7=O)=C(C)C=C3C)C5=O)C(C)=C2)=CC(C)=C1C KHSJPILTPYIYOH-UHFFFAOYSA-N 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- -1 3 equiv) Chemical compound 0.000 description 1
- YYAVXASAKUOZJJ-UHFFFAOYSA-N 4-(4-butylcyclohexyl)benzonitrile Chemical compound C1CC(CCCC)CCC1C1=CC=C(C#N)C=C1 YYAVXASAKUOZJJ-UHFFFAOYSA-N 0.000 description 1
- QUACYTKJOFAODG-UHFFFAOYSA-N 4-[(4-amino-2,6-dimethylphenyl)methyl]-3,5-dimethylaniline Chemical compound CC1=CC(N)=CC(C)=C1CC1=C(C)C=C(N)C=C1C QUACYTKJOFAODG-UHFFFAOYSA-N 0.000 description 1
- RBRRXTGETWLBQG-UHFFFAOYSA-N CC1=CC(C)=C(C)C(C)=C1N1C(=O)C2=C/C3=C(\C=C/2C1=O)C(=O)N(C)C3=O.CC1=CC(C)=C(N)C(C)=C1N.CC1=CC(CC2=CC(C)=C(N)C(C)=C2)=CC(C)=C1N.CC1=CC(CC2=CC(C)=C(N3C(=O)C4=C/C5=C(\C=C/4C3=O)C(=O)N(C)C5=O)C(C)=C2)=CC(C)=C1C.O=C1OC(=O)C2=CC3=C(C=C12)C(=O)OC3=O Chemical compound CC1=CC(C)=C(C)C(C)=C1N1C(=O)C2=C/C3=C(\C=C/2C1=O)C(=O)N(C)C3=O.CC1=CC(C)=C(N)C(C)=C1N.CC1=CC(CC2=CC(C)=C(N)C(C)=C2)=CC(C)=C1N.CC1=CC(CC2=CC(C)=C(N3C(=O)C4=C/C5=C(\C=C/4C3=O)C(=O)N(C)C5=O)C(C)=C2)=CC(C)=C1C.O=C1OC(=O)C2=CC3=C(C=C12)C(=O)OC3=O RBRRXTGETWLBQG-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D63/00—Apparatus in general for separation processes using semi-permeable 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
- B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
Abstract
Description
- The membranes most commonly used in commercial gas separation applications are asymmetric polymeric membranes and have a thin nonporous selective skin layer that performs the separation. Separation is based on a solution-diffusion mechanism. This mechanism involves molecular-scale interactions of the permeating gas with the membrane polymer. According to this solution/diffusion model, the membrane performance in separating a given pair of gases is determined by two parameters: the permeability coefficient (PA) and the selectivity (αA/B). The PA is the product of the gas flux and the selective skin layer thickness of the membrane, divided by the pressure difference across the membrane. The αA/B is the ratio of the permeability coefficients of the two gases (αA/B=PA/PB) where PA is the permeability of the more permeable gas and PB is the permeability of the less permeable gas. Gases can have high permeability coefficients because of a high solubility coefficient, a high diffusion coefficient, or because both coefficients are high. In general, the diffusion coefficient decreases while the solubility coefficient increases with an increase in the molecular size of the gas. In high performance polymer membranes, both high permeability and selectivity are desirable because higher permeability decreases the size of the membrane area required to treat a given volume of gas, thereby decreasing capital cost of membrane units, and because higher selectivity results in a higher purity product gas. These new membranes have high permeability and the selectivity of some of these membranes can be tuned via cross-linking in the presence of UV light.
- The invention provides a polyimide polymer and a polyimide membrane having a formula
- where m and n are independent integers from 10 to 500 and are in a ratio from 1:10 to 10:1
- In some embodiments of the invention, this polyimide membrane is UV treated.
- The invention further provides a process for separating at least one gas from a mixture of gases comprising providing a UV treated polyimide polymer membrane having a formula
- where m and n are independent integers from 10 to 500 and are in a ratio from 1:10 to 10:1; contacting the mixture of gases to one side of the UV treated aromatic polyimide membrane to cause at least one gas to permeate said membrane; and removing from an opposite side of the polyimide membrane a permeate gas composition comprising a portion of said at least one gas that permeated said membrane.
- This invention relates to polyimide gas separation membranes and more particularly to a new class of polyimide membranes with high permeability. Specifically, an improved polyimide membrane with more than 430 Barrer CO2 and H2 permeabilities greatly exceeding the intrinsic permeability of commercial polyimide membranes is disclosed. The permeability is similar to heat-treated polyimides disclosed in U.S. Pat. No. 8,613,362 B2. However, in this case heat treatment, which can be problematic in the preparation of membranes, is not required to achieve such high permeabilities.
- Although the selectivity for gas separations is low with these highly permeable polyimides described in the present invention, it can be increased significantly with UV treatment. In fact, both high permeability and selectivity can be achieved for CO2/CH4 separation with UV treatment, as demonstrated by pure gas tests for membrane dense films of these polyimides. This sensitivity to UV light is also present in thin-film composite membranes where the disclosed polyimide is the selective layer. U.S. Pat. No. 4,717,393 by Hayes and U.S. Pat. No. 7,485,173 by Liu, et. al., disclosed photochemically cross-linked aromatic polyimides. In these cases, a functional group that is cross-linkable to UV light is required, such as a carbonyl or sulfonyl group. However, the high permeability polyimides described in the present invention do not comprise functional groups that are cross-linkable to UV light.
- The polyimides disclosed in the present invention do not contain these carbonyl or sulfonyl functional groups. U.S. Pat. No. 5,409,524 reported a method for the improvement in selectivity of polymeric membranes, such as polysulfone, polycarbonate and polystyrene membranes, without carbonyl or sulfonyl groups through UV treatment, but heating the membranes to a temperature in the range of 60-300° C. is required. Furthermore, the UV and heat treatment of polyimides were not disclosed in this patent. However, heating is not required during the UV treatment to achieve high selectivity for the polyimides described in the present invention. US 2006/0177740 A1 disclosed a polymer derived from pyromellitic dianhydride (PMDA) and 3,3′,5,5′-tetramethyl-4,4′-methylene dianiline (TMMDA) monomers. This disclosure did not include polymers containing 2,4,6-trimethyl-mphenylenediamine (TMPDA). Also, this polymer was used for polyimide matrix electrolytes for battery applications and was not considered for use as a polymeric membrane.
- The membranes made in accordance with the present invention have the formula shown below.
- where m and n are independent integers from 10 to 500 and are in a ratio from 1:10 to 10:1.
- The invention involves the condensation reaction of pyrometallic dianhydride (PMDA) with a mixture of 2,4,6-trimethyl-1,3-phenylenediamine (TMPDA) and 4,4′-methylene bis(2,6-dimethylaniline) (TMMDA) in a polar solvent such as dimethylacetamide (DMAc) or (NMP) solvent to form the polyimide described in the present invention. The condensation reaction described in the current invention is a two-step process involving the formation of the poly(amic acid) followed by a solution chemical imidization process. Acetic anhydride is used as the dehydrating agent and pyridine is used as the imidization catalyst for the solution chemical imidization reaction. Typical reaction times are about 20 hours at about 22° C. In a second step, acetic anhydride is added, followed by pyridine and the mixture is heated to about 95° C. for 2 hours and then allowed to cool to room temperature. The resulting mixture is then used to make a polyimide membrane which is then treated with UV radiation to produce a polyimide membrane with improved properties.
- An aromatic poly(pyrometallic dianhydride-2,4,6-trimethyl-1,3-phenylenediamine-4,4′-methylene bis(2,6-dimethylaniline))polyimide (poly(PMDA-TMPDA-TMMDA)) was synthesized from pyrometallic dianhydride (PMDA, 3 equiv), 2,4,6-trimethyl-1,3-phenylenediamine (TMPDA, 2 equiv), and 4,4′-methylene bis(2,6-dimethylaniline) (TMMDA, 1 equiv) in N,N-dimethylacetamide (DMAc) polar solvent by a two-step process involving the formation of a polyamic acid followed by a solution chemical imidization process. Acetic acid was used as the dehydrating reagent and pyridine was used as the imidization catalyst for the solution chemical imidization reaction.
- For example, a dry 2 L three-necked round-bottom flask attached to a mechanical stirrer and a reflux condenser with a nitrogen inlet was charged with TMPDA (17.0 g, 2.00 equiv), TMMDA(20.0 g, 1.00 equiv), and anhydrous DMAc (380 g) and the solution was vigorously stirred. The dianhydride, PMDA (44.9 g, 3.00 equiv), was added. Additional DMAc (130 g) was added slowly. The reaction vessel was sealed with a septum and stirred at 22° C. for 20 hours. Acetic anhydride (43.2 g) was added to the viscous reaction mixture slowly over 5 minutes, followed by pyridine (66.5 g) all at once. The reaction is heated to 95° C. for 2.5 hours and then allowed to cool to room temperature. The reaction mixture precipitated into a solution of isopropanol:acetone (1:1) to form white thin fibers. The white solid was heated in the vacuum oven for two days at 100° C. The polymer was isolated in nearly quantitative yield.
- An aromatic poly(pyrometallic dianhydride-2,4,6-trimethyl-1,3-phenylenediamine-4,4′-methylene bis(2,6-dimethylaniline))polyimide (poly(PMDA-TMPDA-TMMDA)) was synthesized from PMDA (2 equiv), TMPDA (1 equiv), and TMMDA (1 equiv) in DMAc polar solvent by a two-step process involving the formation of the polyamic acid followed by a solution chemical imidization process. Acetic acid was used as the dehydrating reagent and pyridine was used as the imidization catalyst for the solution chemical imidization reaction.
- For example, a dry 2 L three-necked round-bottom flask attached to a mechanical stirrer and a reflux condenser with a nitrogen inlet was charged with TMPDA (30.0 g, 1.00 equiv), TMMDA (50.8 g, 1.00 equiv), and anhydrous DMAc (775 g) and the solution was vigorously stirred. The dianhydridePMDA (89.8 g, 2.00 equiv) was added. Additional DMAc (130 g) was added slowly. The reaction was sealed with a septum and stirred at 22° C. for 20 hours. Acetic anhydride (86.4 g) was added to the viscous reaction mixture slowly over 5 minutes, followed by pyridine (133 g) all at once. The reaction is heated to 95° C. for 2.5 hours and then allowed to cool to room temperature. The reaction mixture precipitated into a solution of isopropanol:acetone (1:1) to form white thin fibers. The white solid was heated in the vacuum oven for two days at 100° C. The polymer was isolated in nearly quantitative yield.
- The polyimide membrane dense films were prepared as follows: The aromatic poly(PMDA-TMPDA-TMMDA) polyimide, was dissolved in N-methyl pyrrolidone (NMP, 18% polymer). The polyimide dope was filtered, allowed to degas overnight and cast onto a clean glass plate with a doctor knife with a 20-mil knife gap. The film on the glass plate was heated to 60° C. for 6 hours and dried in the vacuum oven at 180° C. for 48 hours. The film was tested for CO2/CH4 and H2/CH4 separations at 50° C. under 689 kPa (100 psig) pure gas feed pressure. The films were also submitted to UV treatment at 254 nm at 2 cm for 10 minutes at 50° C. and subsequently tested again under pure gas pressures. The results are shown in Table 1.
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TABLE 1 Pure gas permeation test results of poly(PMDA-TMPDA-TMMDA) membranes for CO2/CH4 and H2/CH4 separationsa PCO2 Membraneb (Barrer) PH2 (Barrer) αCO2/CH4 αH2/CH4 Polyimide-1 434.6 434.7 11.8 11.8 Polyimide-1-UV 10 min 114.6 342.8 33.7 100.8 Polyimide-2 436.3 483.0 10.4 11.5 Polyimide-2-UV 10 min 117.7 365.0 45.3 140.4 aPCO2, PCH4, and PH2 were tested at 50° C. and 690 kPa (100 psig); 1 Barrer = 10−10 cm3(STP) · cm/cm2 · sec · cmHg bPolyimide 1: PMDA:TMPDA:TMMDA (3:2:1); Polyimide 2: PMDA-TMPDA:TMMDA (2:1:1). - A 2 wt % Polyimide 1 polymer solution was prepared by dissolving 0.8 g of Polyimide 1 polymer synthesized in Example 1 in a solvent mixture consisting of 19.6 g of 1,2,3-trichloro-propane and 19.6 g of dichloromethane. The solution was filtered using a 1 micron-sized filter to remove any insoluble impurities and allowed to degas overnight. One drop of Polyimide 1 polymer solution was introduced to the surface of a pure water bath. The Polyimide 1 solution spread on the surface of water with simultaneous solvent evaporation to form a thin polymer film on the surface of water. The thin polymer film on the surface of water was then laminated onto the surface of a low selectivity, high permeance porous poly(ether sulfone) support membrane. The resulting TFC membrane was dried at 70° C. for 1 hour in a conventional oven.
- The UV-treated TFC Polyimide 1 polymer membranes were prepared by submitting the membrane to a UV lamp from a certain distance and for a period of time selected based upon the separation properties sought. For example, one UV treated TFC Polyimide 1 membrane was prepared from TFC Polyimide 1 membrane obtained in Example 3 by exposure to UV radiation using 254 nm wavelength UV light generated from a UV lamp with 10 cm (3.94 inches) distance from the membrane surface to the UV lamp and an radiation time of 10 minutes. The surface of the Polyimide 1 layer of the TFC Polyimide 1 membrane was dip coated with a RTV615A/615B silicone rubber solution. The coated membrane was dried inside a hood at room temperature for 30 minutes and then dried at 70° C. for 1 hour in a conventional oven.
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TABLE 2 Mixed gas permeation test results of Polyimide 1 TFC membranes for CO2/CH4 Membrane PCO2/L (GPU) αCO2/CH4 Polyimide 1-TFC 178 7.0 Polyimide 1-TFC-UV10 min-2% RTV 13.4 15.8 Conditions: Tested at 50° C., 6895 kPa (1000 psig), 10% CO2/90% CH4; - While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
- A first embodiment of the invention is a polyimide polymer having a formula
- where m and n are independent integers from 10 to 500 and are in a ratio from 1:10 to 10:1. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the ratio of m to n is in a range from 1:5 to 5:1. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein a polyimide membrane comprises a polyimide polymer having the above formula. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the polyimide polymer is UV treated.
- A second embodiment of the invention is a process for separating at least one gas from a mixture of gases comprising providing a UV treated polyimide polymer membrane having a polyimide polymer with a formula
- where m and n are independent integers from 10 to 500 and are in a ratio from 1:10 to 10:1; contacting the mixture of gases to one side of the UV treated polyimide polymer membrane to cause at least one gas to permeate the membrane; and removing from an opposite side of the UV treated polyimide polymer membrane a permeate gas composition comprising a portion of the at least one gas that permeated the membrane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of gases comprises a mixture of carbon dioxide and methane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of gases comprises a mixture of hydrogen and methane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of gases comprises a mixture of helium and methane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of gases comprises a mixture of at least one volatile organic compound and at least one atmospheric gas. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of gases comprises nitrogen and hydrogen. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of gases comprises a mixture of carbon dioxide, oxygen, nitrogen, water vapor, hydrogen sulfide, helium and methane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the UV treated polyimide polymer membrane comprises a species that adsorbs strongly to at least one gas. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of gases comprises a mixture of paraffins and olefins.
- A third embodiment of the invention is a method of preparing a polyimide polymer membrane comprising a condensation reaction of pyrometallic dianhydride (PMDA) with a mixture of 2,4,6-trimethyl-1,3-phenylenediamine (TMPDA) and 4,4′-methylene bis(2,6-dimethylaniline) (TMMDA) in a polar solvent to produce a polyimide polymer; then making a polyimide polymer membrane from the polyimide polymer and treating the polyimide polymer membrane with UV radiation. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the polar solvent comprises dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP) solvent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the condensation reaction is a two-step process involving a formation of a poly(amic acid) followed by a solution chemical imidization reaction. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein acetic anhydride is used as a dehydrating agent and pyridine is used as an imidization catalyst for the solution chemical imidization reaction.
- Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
- In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
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