CN102448593A - High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes - Google Patents
High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes Download PDFInfo
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- CN102448593A CN102448593A CN2010800229646A CN201080022964A CN102448593A CN 102448593 A CN102448593 A CN 102448593A CN 2010800229646 A CN2010800229646 A CN 2010800229646A CN 201080022964 A CN201080022964 A CN 201080022964A CN 102448593 A CN102448593 A CN 102448593A
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- 229920002577 polybenzoxazole Polymers 0.000 title abstract description 8
- 229920005597 polymer membrane Polymers 0.000 title abstract 4
- 239000007789 gas Substances 0.000 claims abstract description 94
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 229920001721 polyimide Polymers 0.000 claims abstract description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004642 Polyimide Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 230000005855 radiation Effects 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 150000003949 imides Chemical class 0.000 claims abstract description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 238000011282 treatment Methods 0.000 claims abstract description 8
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- 229920006389 polyphenyl polymer Polymers 0.000 claims description 95
- 150000003851 azoles Chemical class 0.000 claims description 94
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 52
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Classifications
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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
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/32—Polythiazoles; Polythiadiazoles
-
- 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
- B01D67/0083—Thermal after-treatment
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
-
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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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
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- 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
- C08G73/22—Polybenzoxazoles
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Abstract
In the present invention high performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes and methods for making and using these membranes have been developed. The cross-linked polybenzoxazole and polybenzothiazole polymer membranes are prepared by: 1) first synthesizing polyimide polymers comprising pendent functional groups (e.g., -OH or -SH) ortho to the heterocyclic imide nitrogen and cross-linkable functional groups in the polymer backbone; 2) fabricating polyimide membranes from these polymers; 3) converting the polyimide membranes to polybenzoxazole or polybenzothiazole membranes by heating under inert atmosphere such as nitrogen or vacuum; and 4) finally converting the membranes to high performance cross-linked polybenzoxazole or polybenzothiazole membranes by a crosslinking treatment, preferably UV radiation.; The membranes can be fabricated into any convenient geometry. The high performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes of the present invention are suitable for a variety of liquid, gas, and vapor separations.
Description
Background of invention
The present invention relates to the also method of
azoles and polybenzothiozole polymer film and preparation and these films of use of high performance crosslinked polyphenyl.
Among the 30-35 in the past, the development of the prior art of polymer film base gas separating method rapidly.Film base technology is compared the advantage with low fund cost and high energy efficiency with conventional separation method.The separation of film gas causes paying special attention to of Petroleum Production person and purifier, chemical company and industrial gasses supplier.Several applications has realized business success, comprises from natural gas with from biogas removing carbon dioxide, has improved oil recovery rate, also has in nitrogen, methane and the argon gas from the ammonia gaseous purge stream to remove hydrogen.The present for example Separex of UOP
TMThe cellulose acetate polymers film is occupied an leading position in the international market of from natural gas, removing carbon dioxide.
The film that in the industrial gasses separating application, the most often uses as polymerization with atresia.Separation is based on dissolving-diffusion mechanism.This mechanism relates to the reciprocation of the molecular scale of infiltration gas and membrane polymer.This mechanism supposition is in the film with two opposed surface, and each component tunicle is adsorbed on a surface, through the gas concentration gradient transmission and in the opposed surface desorb.According to this solubility-diffusion model, this film is separating given gas pairing (CO for example
2/ CH
4, O
2/ N
2, H
2/ CH
4) performance of aspect is by two parameter determining: (hereinafter referred is P to infiltration coefficient
A) and selectivity (α
A/B).P
AFor the product of selective meter's layer thickness of gas flux and film divided by transmembrane pressure.α
A/BBe the ratio (α of two kinds of gas permeability coefficients
A/B=P
A/ P
B), P wherein
ABe the permeability of higher permeability gas, P
BBe permeability than low permeability gas.Gas can have a high infiltration coefficient owing to high solubility factor, high diffusion coefficient or because two kinds of coefficients are all high.Usually along with the increase of gas molecule size, diffusion coefficient reduces and the solubility factor increase.In the high-performance polymer film; High osmosis and high selectivity are all hoped; Because higher permeability has reduced the size of handling the required membrane area of given volume gas, reduced the fund cost of film unit thus, and because the high more purity of product gas that causes of selectivity is high more.
Polymer provides a series of performances, comprises low cost, good penetration property, mechanical stability, and is easy to processability, and this separates gas is important.Preferably has high glass-transition temperature (T
g), the polymeric material of high-melting-point and high-crystallinity.Glassy polymers (promptly is in the T that is lower than them
gThe polymer of temperature) have the hard polymer skeleton, and therefore with have the not too polymer phase ratio of hard frame, make less molecule such as hydrogen and helium through rapider, and it is slower to make big molecule such as hydro carbons pass through glassy polymers.Yet, the polymer of higher permeability usually with the selectivity lower than having than the hypotonicity polymer phase.Between permeability and selectivity, always there be general compromise (restriction of the so-called polymer upper bound).In in the past 30 years, dropped into big quantity research in order to overcome the restriction that this upper bound applies.Used various polymer and technology, but not bigger success.In addition, the conventional polymer film also has the restriction at heat endurance and anti-pollution object space face.
Cellulose acetate (CA) glassy polymers film is widely used in gas to be separated.Present such CA film is used for natural gas and concentrates in industry, comprise and remove carbon dioxide.Although the CA film has many advantages, they comprise that in many performances selectivity, permeability and chemical stability, heat endurance and mechanical stability aspect are restricted.Found that the polymer film performance can reduce fast.The main cause of film properties loss is liquid condensation on the film surface.Can be through providing enough dew point nargin (margin) to prevent condensation for operation based on the dew point that the film product gas calculated.Developed the MemGuard of UOP
TMSystem, a kind of renewable adsorption system of molecular sieve of using is anhydrated and heavy hydrocarbon from natural gas stream, to remove, and therefore reduces the dew point of this materials flow.Remove heavy hydrocarbon through the pretreatment system selectivity and can significantly improve this film properties.Although these pretreatment systems can effectively be realized this function, cost is extremely important.In some versions, depend on feed composition, the 10-40% of cost height to the totle drilling cost of pretreatment system (pretreatment system and film system).Reducing pretreatment system cost or whole removes pretreatment system and will significantly reduce and be used for the film system cost that natural gas concentrates.On the other hand, in recent years, increasing film system applies has been concentrated scheme to big offshore natural gas.For the offshore scheme, the area of coverage (footprint) is a big restriction.Therefore, the reduction area of coverage is extremely important to the offshore scheme.The area of coverage of pretreatment system is also very high, account for the whole film system area of coverage greater than 10% to 50%.From the film system, remove pretreatment system and have great economic impact, especially for the offshore scheme.
Developed high-performance polymer such as polyimides (PI), gather (trimethyl silyl propine) (PTMSP) with polytriazoles to improve film selectivity, permeability and heat endurance.These polymeric film material have demonstrated the divided gas flow pairing like CO
2/ CH
4, O
2/ N
2, H
2/ CH
4And propylene (C
3H
6/ C
3H
8) promising performance.Yet present polymeric film material has reached the limit of their productivity ratio-selectivity trade-off relation.In addition, the permeable molecule such as the CO that be adsorbed by the hard polymer matrix based on the gas separating method that uses glassy state dissolving-diffusion barrier
2Or C
3H
6Plasticizing.When feed gas mixtures contains condensable gases, the polymer plasticizing appears more than plasticizing pressure, and this shows as the infiltrative remarkable increase of all components in membrane structure expansion and the charging.
Aromatics polyphenyl also
azoles (PBO), polybenzothiozole (PBT) and polybenzimidazoles (PBI) is the heat-staple scalariform glassy polymers of height of bar-shaped phenylene heterocycle shape ring element with flat, hard, rigidity.Ring element hard, rigidity in this base polymer effectively wraps up, and stays the very little permeable free volume unit that passes through, and this hopes for the polymer film that has high osmosis and high selectivity simultaneously.Yet these aromatics PBO, PBT and PBI polymer with high thermal stability and chemical stability have poor dissolubility in organic solvent commonly used, make it can not be as the common polymer material for preparing polymer film through the most practical solvent cast method.The solubility aromatic polyimide thermal transition that contains side functional group at the heterocycle acid imide nitrogen ortho position of polymer backbone be the aromatics polyphenyl also
azoles (PBO) or polybenzothiozole (PBT) the replacement method that forms PBO or PBT polymer film can be provided, PBO or PBT polymer film are difficult to or can not be directly obtained through the solvent cast method by PBO or PBT polymer.(Tullos etc., MACROMOLECULES, 32,3598 (1999))
On the other hand, some organic zeolite membrane such as SAPO-34 provide permeability and the selectivity more much higher than polymer film with Carbon Molecular Sieve Membrane in gas separates, but cost is high, has poor mechanical stability and is difficult to mass preparation.Therefore, still highly be desirable to provide the cost effective film that alternative having improves separating property.
At US 5,409, in 524, with many different polymer films through this film heating is handled in this polymer, to discharge excessive free volume.This often reduces the permeability of polymer.This film is heated in 60-300 ℃ temperature range.Then in the presence of oxygen with this film of UV radiation so that partial oxidation should the surface at least.A kind of treated film of reporting is also
azoles film of polyphenyl.Polystyrene and
azole polymer prepared by one-step polycondensation process and will be the polybenzimidazole
azole polymer film prepared at 180 ℃ heat treatment.This film demonstrates permeability and reduces to 9.11Barrer by 12.25Barrer, reduces by 25%, and the oxygen/nitrogen selectivity increases to 6.21 by 5.34, increase by 15%.These conditions have produced to be compared less selectivity with the present invention who uses different material and significantly higher film treatment temperature and increases.
Reported among the publication SCIENCE that publishes recently and be used for also
azoles polymer film (Ho Bum Park etc. of newtype high osmosis polyphenyl that gas separates; SCIENCE 318,254 (2007)).These polyphenyl also
azoles film are reset to contain in the hydroxyl polyimide polymer film of the pendant hydroxyl group at heterocycle acid imide nitrogen ortho position by elevated temperature heat and are prepared.This polyphenyl also
The azoles polymer film demonstrates high CO
2Permeability (＞1000Barrer), it is than 100 times of conventional polymer films, and be similar to some organic zeolite membrane, but CO
2/ CH
4Selectivity is similar to commercially available cellulose acetate membrane.Concerning this film, need improve selectivity to have industrial use.The author attempts through adding little acid adulterant (for example HCl and H
3PO
4) and improve this polyphenyl also
The selectivity of azoles polymer film.Yet this polyphenyl also stability of the little acid adulterant in
azoles polymer film is a key issue as far as commercial Application.
In US 2008/0300336A1, reported that having used the crosslinked certain successful improvement of UV has contained and improve this permeability of the membrane and the performance of the specific blend base film of the molecular sieve of function optionally.Yet, must not only make crosslinked polymer but also add molecular sieve to obtain the wherein performance of the improvement level of report.Highly hope the polymer film be improved, it does not contain molecular sieve not only needing to avoid the dispersing molecule sieve but also eliminate because any problem that the shortage adhesiveness causes between polymer and the molecular sieve.
The present invention through provide the high performance crosslinked polyphenyl of newtype also method with said film of following performance/advantage of
azoles and polybenzothiozole polymer film and preparation overcome the problem of prior art polymer film and organic zeolite membrane: be easy to processability; High selectivity and high seepage velocity or flux; High thermal stability and because anti-solvent swell; Plasticizing and hydrocarbons pollutant and stable in time flux and sustained selectivity.This film provide compare with cross-linked polyimide membranes much better permeability with uncrosslinked polyphenyl also
azoles film compare much better selectivity.
Summary of the invention
The present invention relates to the also method of
azoles and polybenzothiozole polymer film and preparation and these films of use of high performance crosslinked polyphenyl.
High-performance cross-linked polystyrene and
azole and polybenzothiazole polymer film containing the polymer backbone of the UV-crosslinkable functional group and a heterocyclic imide nitrogen in ortho-side functional group (e.g.-OH or a group -SH) of the polyimide polymer crosslinkable by heat and UV radiation conversion thereof.Described in the present invention high performance crosslinked polyphenyl also
azoles and polybenzothiozole polymer film comprises also
azoles or polybenzothiozole polymer segment of polyphenyl, and at least a portion of these polymer segments is cross-linked with each other by possible direct covalent bonds through being exposed to the UV radiation.Polyphenyl is the crosslinked film that film selectivity and the chemical stability and the heat endurance of remarkable improvement are provided of
azoles and polybenzothiozole polymer film also.
Crosslinked polyphenyl also
azoles and polybenzothiozole polymer film has overcome the problem of prior art polymer film and organic zeolite membrane, has the processability of being easy to, high selectivity, high seepage velocity or flux, high thermal stability and because anti-solvent swell, plasticizing and hydrocarbons pollutant and stable in time flux and sustained selectivity.
Production of high-performance cross-linked polystyrene and
azole and polybenzothiazole polymer film comprising: 1) first synthesized imide nitrogen containing heterocyclic ring in the ortho position of the pendant functional groups (e.g.-OH or-SH) and the polymerization skeleton was a UV crosslinkable functional group (e.g. carbonyl) an aromatic polyimide polymer; 2) from step 1) in the synthesis of polyimide polymers of aromatic polyimide film; 3) and an inert atmosphere at 300-600 ℃ such as argon, nitrogen, or by heating under vacuum and the polyimide film and converted to polystyrene
azole or polybenzothiazole film; and 4) Finally, exposure to UV radiation and the polyphenylene and
azole or polybenzothiazole membrane into crosslinked polystyrene and
polybenzothiazole azole or polymer film.In some cases; After being exposed to the UV radiation, can increase the film post-processing step; Wherein with crosslinked polyphenyl also the selective layer surface of
azoles or polybenzothiozole polymer film with the thin layer coating of high osmosis material, but this high osmosis material for example is polysiloxanes, fluoropolymer, thermal curable silicon rubber or UV radiation curing epoxy polysiloxane.
Crosslinked polyphenyl also
azoles and polybenzothiozole polymer film can have atresia symmetry structure or asymmetry structure, and wherein the fine and close selectivity thin layer of atresia is carried on the porous carrier layer.These films can be made into any favourable geometry like dull and stereotyped (or spiral), dish, pipe, doughnut or film composite.
The invention provides a kind of also method of
azoles polymer film or crosslinked polybenzothiozole polymer film separating at least one gas or liquid from gas or liquid mixture of crosslinked polyphenyl of using.The method comprising the steps of: providing at least one gas or liquid permeability was crosslinked polystyrene and
yl or polybenzothiazole polymer film; contact with the gas or liquid mixtures and crosslinked polystyrene
azole or polystyrene benzothiazole one side of the polymer film of at least one gas or liquid penetration over crosslinked polystyrene and
yl or polybenzothiazole polymer film; to and from the opposite side of the membrane to remove the permeate gas or liquid compositions , permeate through the membrane which is at least a part of a gas or liquid.
High performance crosslinked polyphenyl also
Azoles not only is suitable for various liquid, gas and steam with the polybenzothiozole polymer film to be separated as making water through reverse osmosis deaslination; Non-aqueous liquid separates the deep desulfuration like gasoline and diesel fuel; Ethanol/water separates, the pervaporation dehydration of moisture/organic mixture, CO
2/ CH
4, CO
2/ N
2, H
2/ CH
4, O
2/ N
2, H
2S/CH
4, olefin/paraff iotan, isoparaffin/n alkane separate and other light gas mixture separation, also can be used for other and use like catalysis and fuel cells applications.
Detailed Description Of The Invention
In 1999, Tullos etc. reported the synthetic of a series of hydroxyl polyimide polymers that contain the pendant hydroxyl group that is positioned at heterocycle acid imide nitrogen ortho position.Find this quasi-polyimide 350-500 ℃ with nitrogen or vacuum under during heating experience to the also thermal transition of
azoles of polyphenyl.(Tullos etc., MACROMOLECULES, 32,3598 (1999)).Reported further research among the publication SCIENCE that publishes recently, by the polyphenyl of reports such as Tullos also
azoles polymeric material have the free volume unit of adjusting and the form of good connection.These polyphenyl also uncommon micro-structural of
the azoles polymeric material segment that can use heat to drive are reset and symmetry is regulated, and provide preparation to be used for the also method of
azoles polymer film of polyphenyl that gas separates.Referring to Ho Bum Park etc., SCIENCE, 318,254 (2007).These polyphenyl also
The azoles polymer film demonstrates high CO
2Permeability (＞1000Barrer), it is than 100 times of conventional polymer films, and be similar to some organic zeolite membrane, but for CO
2/ CH
4Separate and demonstrate the CO lower than some aperture organic zeolite membrane
2/ CH
4Selectivity.
The crosslinked polyphenyl that the present invention relates to novel high-performance is the method for
azoles and polybenzothiozole polymer film and preparation and these films of use also.
The high performance crosslinked polyphenyl of the present invention through newtype is provided also method with film of following performance/advantage of
azoles and polybenzothiozole polymer film and preparation overcome the problem of prior art polymer film and organic zeolite membrane: be easy to processability; High selectivity and high seepage velocity or flux; High thermal stability and because anti-solvent swell; Plasticizing and be exposed to hydrocarbon pollutant and the deterioration that causes and stable in time flux and sustained selectivity.
Said in the present invention high performance crosslinked polyphenyl also
but azoles and polybenzothiozole polymer film by the UV crosslinking functionality that comprises in the polymer backbone; (for example carbonyl) and be positioned at the side functional group at heterocycle acid imide nitrogen ortho position; (for example group-OH or-SH) crosslinkable polyimide polymer is via thermal transition UV radiation and preparing then.This film comprises also
azoles or polybenzothiozole polymer segment of polyphenyl, and at least a portion of these polymer segments is cross-linked with each other by direct covalent bonds through being exposed to the UV radiation.Polyphenyl is crosslinked film selectivity and the chemical stability and the heat endurance that remarkable improvement is provided for film of
azoles and polybenzothiozole polymer film also.
The present invention provides the steps through the production of these high crosslinked polystyrene and
azole and polybenzothiazole polymer film: 1) first synthesized containing heterocyclic imide nitrogen in ortho side functional groups (for example - OH or-SH) in the polymer backbone and a UV-crosslinkable functional group (e.g. carbonyl) an aromatic polyimide polymer; 2) from step 1) in the aromatic polyimide synthesized polyimide polymers imide film; 3) and an inert atmosphere at 300-600 ℃ such as argon, nitrogen, or by heating under vacuum and the polyimide film and converted to polystyrene
azole or polybenzothiazole film; and 4) Finally, the exposure to UV radiation and the polybenzimidazole
yl or polybenzothiazole film converted to crosslinked polystyrene and
polybenzothiazole azole or polymer film.In some cases; After the UV radiation, can increase the film post-processing step; Wherein with crosslinked polyphenyl also the selective layer surface of
azoles or polybenzothiozole polymer film with the thin layer coating of high osmosis material, but this high osmosis material for example is polysiloxanes, fluoropolymer, thermal curable silicon rubber or UV radiation curing epoxy polysiloxane.
In the present invention for the preparation of crosslinked polystyrene and
azole and polybenzothiazole polybenzoxazole polymer film
azole type and polybenzothiazole type polymer film is made at 300-600 ℃ and inert atmosphere such as argon, nitrogen heating under vacuum or thermal conversion of a polyimide film was prepared.But polyimide film by have the UV crosslinking functionality (for example carbonyl) in polymer backbone and be positioned at heterocycle acid imide nitrogen ortho position side functional group (for example-OH or-SH) soluble polyimide prepares through solution casting or solution spin coating method.Have the side functional group that is positioned at heterocycle acid imide nitrogen ortho position (for example-OH or-thermal transition of SH) polyimides cause through irreversible molecular rearrangement form polyphenyl also
azoles ((, and do not produce other volatile byproducts if side functional group is group-SH) and the loss that is accompanied by carbon dioxide if side functional group is group-OH) or polybenzothiozole.Polyphenyl also
azoles and polybenzothiozole polymer comprises the repetitive of formula (I), and wherein said formula (I) is:
The X of wherein said formula (I) also is S for
azoles for polyphenyl for O or for polybenzothiozole.
Be used in the present invention prepare high performance crosslinked polyphenyl also
but the UV crosslinked polyimide polymer that contains the side functional group that is positioned at heterocycle acid imide nitrogen ortho position of azole type and polybenzothiozole types of membranes comprises first repetitive of a plurality of formulas (II), its Chinese style (II) is:
The X1 of its Chinese style (II) is following group or its mixture:
The X2 of formula (II) is identical with X1 or be selected from following group or its mixture:
Formula (II)-Y-is following group or its mixture:
-Z-,-Z '-with-Z "-be independently-O-or-S-,-R-is following group or its mixture:
In one embodiment of the invention, when the X1 of preferred formula (II) was identical with X2, they were selected from following group or its mixture:
And the Y of formula (II) is selected from following group or its mixture:
In another embodiment of the present invention, the X1 of formula (II) is selected from following group or its mixture:
The X2 of said formula (II) is selected from following group or its mixture:
The Y of formula (II) is selected from following group or its mixture:
Be used in the present invention preparing high performance crosslinked polyphenyl also some of preferred polyimide polymer of
azoles and polybenzothiozole film include, but not limited to gather [3,3 '; 4,4 '-benzophenone tetracarboxylic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (BTDA-APAF)), gather [4,4 '-oxygen di-phthalic anhydride-2; Two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (ODPA-APAF)), gather (3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride-3; 3 '-dihydroxy-4,4 '-benzidine) (gathering (BTDA-HAB)), gather [3,3 ', 4; 4 '-diphenyl sulfone tetraformic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (DSDA-APAF)), gather (3,3 ', 4; 4 '-diphenyl sulfone tetraformic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas-3,3 of 2-'-dihydroxy-4,4 '-benzidine) (gathering (DSDA-APAF-HAB)), gather [2; 2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride-3,3 '; 4,4 '-benzophenone tetracarboxylic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (6FDA-BTDA-APAF)), gather [4; 4 '-oxygen di-phthalic anhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas-3,3 of 2-'-dihydroxy-4; 4 '-benzidine] (gathering (ODPA-APAF-HAB)), gather [3,3 ', 4; 4 '-benzophenone tetracarboxylic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas-3,3 of 2-'-dihydroxy-4; 4 '-benzidine] (gathering (BTDA-APAF-HAB)) and gather (4,4 '-bisphenol-A dianhydride-3,3 '; 4,4 '-benzophenone tetracarboxylic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (BPADA-BTDA-APAF)).
Be used in the present invention to prepare crosslinked polyphenyl also
but azoles and polybenzothiozole film comprise UV crosslinking functionality and the side functional group that is positioned at heterocycle acid imide nitrogen ortho position (for example-OH or-SH) polyimides by diamines and dicarboxylic anhydride at polar solvent such as 1-Methyl-2-Pyrrolidone (NMP) or N; N-dimethylacetylamide (DMAc) synthesize through two-step method, and this two-step method relates to formation and gathers (amic acid) solution imidizate or hot-imide then.Acetic anhydride is used as the imidization catalyst of solution imidization reaction as dehydrating agent and pyridine (or triethylamine).More information about preparing these polymer can be at Tullos etc., and MACROMOLECULES finds in 32,3598 (1999).
In the present invention, for the preparation of high-crosslinked polystyrene and
azole type and membrane type polybenzothiazole polyimide film may be contained in the polymer backbone can be UV crosslinkable functional group and a heterocyclic imides in nitrogen functional groups ortho to a side (e.g.,-OH or-SH) by polyimide polymers were cast on a clean glass plate and the solvent together polyimide solution in the inner plastic cover evaporate slowly at room temperature at least 12 hours symmetry and is made thin nonporous membrane geometry.Then this film is peeled off and at room temperature dry 24 hours from glass plate, then 200 ℃ with vacuum under drying at least 48 hours.
The solvent that is used for dissolving polyimide polymer makes the consoluet ability of this polymer and forms step at film mainly due to them and is easy to remove and desolvates and select.Other considerations in selective solvent comprise hypotoxicity, low corrosion activity, low environment harm trend, availability and cost.The representative solvents of using in the present invention comprises most of amide solvents such as N-methyl pyrrolidone (NMP) and the N that is generally used for forming polymer film; N-dimethylacetylamide (DMAC), carrene, oxolane (THF), acetone, N; Dinethylformamide (DMF), methyl-sulfoxide (DMSO), toluene, two
alkane, 1, other solvents that 3-dioxolanes, its mixture, those skilled in the art are known and composition thereof.
In the present invention, for the preparation of high-crosslinked polystyrene and
azole type and membrane type polybenzothiazole polyimide film but also by the method comprising the steps of manufacturing: the polyimide polymer is dissolved in a solvent to form a solution of a polyimide material; the porous membrane carrier (for example, an inorganic carrier made of a ceramic material) in contact with the solution;, and then the solvent is evaporated to provide the carrier layer on the polyimide-containing polymer thin layer of material selectivity of the material.
Polyimide film can also be through phase inversion then through using at least a drier directly the air drying process asymmetric membrane with tabular or doughnut geometry; This drier is that hydrophobic organic compound such as hydrocarbon or ether are (referring to US 4; 855,048).Polyimide film can also through phase inversion then solvent exchange process asymmetric membrane (referring to US 3,133,132) with tabular or doughnut geometry.
Pass through then at 300-600 ℃; Preferred 400-500 ℃; Most preferably heating and polyimide film is converted into also
azoles or polybenzothiozole polymer film of polyphenyl under 400-450 ℃ and inert atmosphere such as argon gas, nitrogen or the vacuum.Be 30 seconds to 2 hours the heat time heating time of this heating steps.Be 30 seconds to 1 hour preferred heat time heating time.Then through the use of UV light at a predetermined distance and the polyphenylene
yl or polybenzothiazole UV cross-linked polymer film is based on the separation performance of required time selected to form a cross-linked polystyrene and
azole or polybenzothiazole polymer film .Also
azoles or polybenzothiozole polymer film can also
azoles or polybenzothiozole polymer film prepare through being exposed to the UV radiation for example crosslinked polyphenyl by polyphenyl; Wherein use the UV light of the 254nm wavelength that is produced by the UV lamp, this film surface is 1.9cm (0.75 inch) and is being 30 minutes less than 50 ℃ of following radiated times with the distance of UV lamp.UV lamp described herein is the quartzy 12 watts of lamps of low pressure mercury arc immersion UV, and it has 12 watts of power supplys, from Ace Glass Incorporated.This crosslinked polyphenyl also optimization of
azoles and the polybenzothiozole polymer film degree of cross linking should promote to regulate gas and the fluid separation applications that this film is used for wide region with the permeance property improved and environmental stability.This crosslinked polyphenyl also
azoles and the polybenzothiozole polymer film degree of cross linking can be controlled with distance, UV radiated time, UV light wavelength and the intensity etc. on this film surface through regulating the UV lamp.Preferably, the distance on UV lamp and film surface is 0.8-25.4cm (a 0.3-10 inch), and wherein UV light is provided by 12-450 watt of low pressure or middle pressure mercury-arc lamp, and the UV irradiation time is 0.5 minute to 1 hour.More preferably, the distance on UV lamp and film surface is 1.3-5.1cm (a 0.5-2 inch), and wherein UV light is provided by 12-450 watt of low pressure or middle pressure mercury-arc lamp, and the UV irradiation time is 0.5-40 minute.
In some cases; Also can increase the film post-processing step after
azoles or the polybenzothiozole polymer film forming crosslinked polyphenyl; Apply the thin layer of high osmosis material, but this high osmosis material for example is polysiloxanes, fluoropolymer, thermal curable silicon rubber or UV radiation curing epoxy polysiloxane.Coating fills surface pore and the other defect that comprises the space (referring to US 4,230,463; US4,877,528; US 6,368, and 382).
The high performance crosslinked polyphenyl of the present invention also
azoles and polybenzothiozole polymer film can have atresia symmetry structure or asymmetry structure, and wherein the fine and close selectivity thin layer of atresia is carried on the porous carrier layer.Porous carrier can also
azoles or polybenzothiozole polymeric material or the dissimilar organic or inorganic materials with high thermal stability be processed by identical crosslinked polyphenyl.The high performance crosslinked polyphenyl of the present invention also
azoles and polybenzothiozole polymer film can be made into any favourable geometry like dull and stereotyped (or spiral), dish, pipe, doughnut or film composite.
The present invention provides a method of using crosslinked polystyrene and
azole and polybenzothiazole polymer film or a liquid from a gas mixture by at least one gas or liquid, the method comprising the steps of: (a) providing at least a gas or liquid that has a permeability of crosslinked polystyrene and
yl or polybenzothiazole polymer film; (b) contacting said mixture and crosslinked polystyrene
azole or polybenzothiazole of a polymer film side of the at least one gas or liquid permeates said crosslinked polystyrene and
yl or polybenzothiazole polymer film; and (c) and from the opposite side of the membrane permeate removal of the film containing at least one gases or liquids permeate portion of the gas or liquid compositions.
These high performance crosslinked polyphenyl also
azoles especially can be used for purifying, separating or adsorb the individually defined thing class in liquid phase or the gas phase with the polybenzothiozole polymer film.Except the divided gas flow pairing; These high performance crosslinked polyphenyl also
azoles and polybenzothiozole polymer film for example can be used for making water through reverse osmosis deaslination or be used for isolated protein or other thermal instability compounds, for example in medicine and biotechnological industries.High performance crosslinked polyphenyl is
azoles and the polybenzothiozole polymer film also can be used for fermentor and bioreactor migrates out this container to deliver gas in the reaction vessel and with cell culture medium also.Extraly; This high performance crosslinked polyphenyl also
azoles and polybenzothiozole polymer film also can be used for from air or water materials flow, removing microorganism, water purify, continuously ferment/generate ethanol in the film pervaporation system, and detect or remove trace compound or the slaine in air or water materials flow.
The crosslinked polyphenyl of the present invention also
azoles and polybenzothiozole polymer film especially can be used for the gas separating method in air purification, petrochemistry, refining and the gas industry.The instance of such separation comprises separation of VOCs from environmental gas (like toluene, xylenes and acetone), as from air, reclaiming nitrogen or oxygen and nitrogen.Other instances of such separation are separation of C O from natural gas
2Or H
2S, the N from the ammonia gaseous purge stream
2, CH
4With separate H among the Ar
2, in purifier, reclaim H
2, the olefin/paraff iotan separation separates like propylene and separates with the isoparaffin/n alkane.Pairing of any given gas or combination that molecular size is different, for example nitrogen and oxygen, carbon dioxide and methane, hydrogen and methane or carbon monoxide, helium and methane can use crosslinked polyphenyl as herein described also
azoles or polybenzothiozole polymer film separate.Can from the third gas, remove surpassing two kinds of gases.For example, use some gas components that film described herein can selectivity be removed from raw gas to comprise carbon dioxide, oxygen, nitrogen, steam, hydrogen sulfide, helium and other trace gas.Alternative some gas components that keep comprise appropriate hydrocarbon gas.When permeable component is to be selected from the acidic components of carbon dioxide, hydrogen sulfide and its mixture and when hydrocarbon mixture such as natural gas are removed, can use the module of a module or at least two parallel uses, or a series of module to be to remove this acidic components.For example, when using a module, the pressure of feed gas can be 275kPa to 2.6MPa (25-4000psi).Depend on many factors like the certain films of using, the flowing velocity and the compression if desired of inlet materials flow, the availability of the compressor of compression penetrant materials flow, transmembrane pressure can be low to moderate 0.7 crust or high to 145 crust (10psi or high to 2100psi).Pressure reduction greater than 145 crust (2100psi) can make film rupture.Preferably at least 7 the crust (100psi) pressure reduction because lower pressure reduction possibly require the compression of more module, more time and intermediate product materials flow.Depend on the temperature and the ambient temperature conditions of feed steam, the operating temperature of this method can change.Preferably, the valid function temperature of film of the present invention is-50 ℃ to 150 ℃.More preferably, the valid function temperature of film of the present invention is-20 ℃ to 100 ℃, and most preferably, the valid function temperature of film of the present invention is 25-100 ℃.
Crosslinked polyphenyl also
azoles and polybenzothiozole polymer film especially can be used for from gas streams, removing the gases/vapors separating technology in chemistry, petrochemistry, medicine and the associating industry of organic vapor, for example is used for exhaust-gas treatment to reclaim VOC to satisfy the cleaned air regulations or to be used for the process stream of process units so that recyclable valuable compound (for example VCM, propylene).Can use crosslinked polyphenyl also the gases/vapors separating technology of
azoles and polybenzothiozole polymer film other instances in oil and the gas purifier from hydrogen the separate hydrocarbons steam; The hydrocarbon dew pointization (be about to hydrocarbon dew point be reduced to be lower than minimumly maybe the export pipeline temperature make liquid hydrocarbon not separate) that is used for natural gas at pipeline; Be used to control gas engine and gas-turbine methane value, and be used for gasoline and reclaim with fuel gas.Crosslinked polyphenyl also
The thing class that azoles and polybenzothiozole polymer film can mix strong absorption specific gas (for example is used for O
2Cobalt Porphyrin or phthalocyanine or be used for the silver (I) of ethane) carried film to help them.
Crosslinked polyphenyl also
Azoles and polybenzothiozole polymer film can at high temperature be operated and think that the dew point nargin that natural gas concentrates provides enough (for example removes CO from natural gas
2).Crosslinked polyphenyl also
azoles and polybenzothiozole polymer film can be used for natural gas concentrate with single phase film or two stage film system in first and/or second stage film.High performance crosslinked polyphenyl with high selectivity, high osmosis and high thermal stability and chemical stability of the present invention also
azoles and polybenzothiozole polymer film can make this film operate down there not being expensive pretreatment system.Therefore, containing crosslinked polyphenyl also
To not need expensive film pretreatment system such as adsorbent MemGuard in the new technology of azoles or polybenzothiozole polymer film system
TMSystem.Owing to saved pretreatment system and significantly reduced membrane area, new technology can realize significant fund cost saving and reduce the existing film area of coverage.
Crosslinked polyphenyl also
azoles and polybenzothiozole polymer film also can be used for through the pervaporation separation liquid mixture, as is used for removing organic compound (for example alcohol, phenol, chlorinated hydrocabon, pyridine, ketone) from water such as moisture effluent or process fluid.Also
azoles or polybenzothiozole polymer can be used for improving the concentration of alcohol in the rarer ethanolic solution (5-10% ethanol) that obtains through fermentation process to have the optionally crosslinked polyphenyl of ethanol.Another use these crosslinked polyphenyl also the liquid phase separation instance of
azoles and polybenzothiozole polymer film as gasoline and diesel fuel through being similar to US 7; 048; The pervaporation membrane technology deep desulfuration of technology described in 846; With US 7; 048,846 whole contents is incorporated this paper by reference into.Sulfur-containing molecules is optionally crosslinked polyphenyl, and also
azoles and polybenzothiozole polymer film can be used for from fluid catalytic cracking (FCC) and other naphtha hydrocarbon flows selectivity and remove sulfur-containing molecules.Other liquid phase instances comprise the another kind of organic component of separation from a kind of organic component, for example separate the isomers of organic compound.Can use crosslinked polyphenyl also the organic compound mixture that separates of
azoles or polybenzothiozole polymer film comprise: ethyl acetate-ethanol; Diethyl ether-ethanol; Acetate-ethanol; Benzene-ethanol; Chloroform-ethanol; Chloroform-methanol; Acetone-isopropyl ether; Allyl alcohol-allyl ether; Allyl alcohol-cyclohexane; Butanols-butyl acetate; Butanols-1-butyl ether; Ethanol-ethyl-butyl ether; Propyl acetate-propyl alcohol; Isopropyl ether-isopropyl alcohol; Methyl alcohol-ethanol-isopropyl alcohol and ethyl acetate-ethanol-acetate.
Crosslinked polyphenyl also
azoles can be used for from water, separating organic molecule (for example from water, removing ethanol and/or phenol through pervaporation) and removes metal and other organic compounds from water with the polybenzothiozole polymer film.
Crosslinked polyphenyl also
azoles and polybenzothiozole polymer film has the separating gas mixture of being used for, and comprises the direct application of removing carbon dioxide from natural gas.This film can make carbon dioxide to pass through faster than the VELOCITY DIFFUSION of the methane in the natural gas.Carbon dioxide is owing to than highly dissoluble, have the seepage velocity that is higher than methane than high diffusibility or both.Therefore, carbon dioxide is in the permeate side enrichment of this film, and methane is at charging (stopping) lateral enrichment of this film.
Crosslinked polyphenyl also
azoles and polybenzothiozole polymer film also has the direct application that concentrates the alkene that is used for the paraffin/olefin materials flow that cracking of olefins uses.For example crosslinked polyphenyl also
azoles and polybenzothiozole polymer film can be used for propylene and separates with raising and be used for the concentration of effluent of being produced propylene and being produced the catalytic dehydrogenating reaction of isobutene by iso-butane by propane.Therefore, can reduce the number of stages that obtains the required propylene current divider of polymer grade propylene.Crosslinked polyphenyl also
The Another Application of azoles and polybenzothiozole polymer film is for being used to be separated in light paraffins isomerization and MaxEne
TMIn isoparaffin and normal paraffin hydrocarbons, MaxEne
TMBe used for improving the technology of normal paraffin hydrocarbons for a kind of, can be translated into ethene then in the concentration of naphtha cracker raw material.
The crosslinked polyphenyl also additional application of
azoles and polybenzothiozole polymer film is to remove the productive rate that predetermined substance improves equilibrium-limited reaction through selectivity as the separator in the chemical reactor.
In a word, the high performance crosslinked polyphenyl of the present invention also
Azoles is suitable for various liquid, gas and steam with the polybenzothiozole polymer film to be separated, as makes water through reverse osmosis deaslination, and non-aqueous liquid separates the deep desulfuration like gasoline and diesel fuel, and ethanol/water separates, the pervaporation dehydration of moisture/organic mixture, CO
2/ CH
4, CO
2/ N
2, H
2/ CH
4, O
2/ N
2, H
2S/CH
4, olefin/paraff iotan, isoparaffin/n alkane separate and other light gas mixture separation.
Embodiment
Provide the following example so that one or more preferred embodiment of the present invention to be described, but be not restricted embodiment of the present invention.Can make the many variations that fall in the scope of the invention to the following example.
Embodiment 1 synthetic (BTDA-APAF) polyimides that gathers
By 2; Two (3-amino-4-hydroxy phenyl) the HFC-236fa diamines (BTDA) and 3 of 2-; 3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride (APAF) gathers [3 through comprising forming to gather (amic acid) but to contain the crosslinked carbonyl of UV in the synthetic skeleton of the two-step method of solution imidizate technology then with the aromatics that is positioned at the side-OH functional group at heterocycle acid imide nitrogen ortho position in the NMP polar solvent; 3 '; 4,4 '-benzophenone tetracarboxylic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (BTDA-APAF)) polyimides.Acetic anhydride is used as the imidization catalyst of solution imidization reaction as dehydrating agent and with pyridine.For example, 250mL adds 10.0g (27.3mmol) APAF and 40mL NMP in being equipped with three neck round-bottomed flasks of nitrogen inlet and mechanical agitator.In case APAF dissolves fully, just (8.8g, 27.3mmol) solution in 40mL NMP adds in the APAF solution in the flask with BTDA.With this reactant mixture mechanical agitation 24 hours and obtain viscosity and gather (amic acid) solution at ambient temperature.Then, under agitation will slowly add this reactant mixture, in this reactant mixture, be added in the 8.6g pyridine of 10mL NMP then at the 11.1g acetic anhydride among the 10mL NMP.Under 80 ℃ with this reactant mixture again mechanical agitation 1 hour to be gathered (BTDA-APAF) polyimides.(BTDA-APAF) polyimides product that gathers that is the fine fibre form reclaims through this reactant mixture slowly is deposited in a large amount of methyl alcohol.Then, gained is gathered (BTDA-APAF) polyimide fiber thoroughly cleans with methyl alcohol and under 150 ℃ in vacuum drying oven dry 24 hours.
Embodiment 2 synthetic (ODPA-APAF) polyimides that gather
By 4; 4 '-oxygen di-phthalic anhydride (ODPA) and 2; Two (the 3-amino-4-hydroxy phenyl) HFC-236fas (APAF) of 2-gather the aromatics that (amic acid) contain the side-OH functional group that is positioned at heterocycle acid imide nitrogen ortho position then in the synthetic skeleton of two-step method of solution imidizate method and gather [4 through comprising forming in the NMP polar solvent; 4 '-oxygen di-phthalic anhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (ODPA-APAF)) polyimides.Acetic anhydride is used as the imidization catalyst of solution imidization reaction as dehydrating agent and with pyridine.For example, 250mL adds 10.0g (27.3mmol) APAF and 20mL NMP in being equipped with three neck round-bottomed flasks of nitrogen inlet and mechanical agitator.In case APAF dissolves fully, just (8.88g, 27.3mmol) solution in 35mL NMP adds in the APAF solution in the flask with ODPA.With this reactant mixture mechanical agitation 24 hours and obtain viscosity and gather (amic acid) solution at ambient temperature.Then, under agitation will slowly add this reactant mixture, in this reactant mixture, be added in the 8.6g pyridine among the 10mL NMP then at the 11.1g acetic anhydride among the 10mL NMP.Under 80 ℃ with this reactant mixture again mechanical agitation 1 hour to be gathered (ODPA-APAF) polyimides.(ODPA-APAF) polyimides product that gathers that is the fine fibre form reclaims through this reactant mixture slowly is deposited in a large amount of methyl alcohol.Then, gained is gathered (ODPA-APAF) polyimide fiber thoroughly cleans with methyl alcohol and under 150 ℃ in vacuum drying oven dry 24 hours.
Embodiment 3 preparations gather (BTDA-APAF) polymer film
Gather (BTDA-APAF) polymer film according to the following steps preparation: 4.0g synthetic (BTDA-APAF) polyimides that gathers in embodiment 1 is dissolved in 12.0g NMP and 12.0g 1, in the solvent mixture of 3-dioxolanes.With this mixture mechanical agitation 2 hours to form even curtain coating dope.Can make the degassing of spending the night of the even curtain coating dope of gained.On clean glass plate, use scraper preparation to gather (BTDA-APAF) polymer film by still curtain coating dope with 20-mil slit.Then this film is put into vacuum drying oven with glass plate.Slow removing desolvated through the temperature of slow increase vacuum and vacuum drying oven.At last, with this film 200 ℃ with vacuum under drying at least 48 hours form to remove residual solvent fully and gather (BTDA-APAF) polymer film.
Embodiment 4 preparation polyphenyl are
azoles polymer film PBO (BTDA-APAF-450C) (breviary is PBO (BTDA-APAF)) also
Through at N
2(BTDA-APAF) polymer film that gathers that will in embodiment 3, prepare in the stream is heated to 450 ℃ and preparation polyphenyl also with the firing rate of 5 ℃/min from 50 ℃ of heat
Azoles polymer film PBO (BTDA-APAF-450C).This film was kept 1 hour down at 450 ℃, then with the firing rate of 5 ℃/min at N
2Be cooled to 50 ℃ in the stream.
Embodiment 5 prepares also
azoles polymer film (breviary is crosslinked PBO (BTDA-APAF-450C)) of crosslinked PBO (BTDA-APAF-450C) polyphenyl
PBO (BTDA-APAF-450C) polymer film through the crosslinked preparation in embodiment 4 of UV prepares crosslinked PBO (BTDA-APAF-450C) polymer film; This carries out through being exposed to the UV radiation; The 254nm wavelength UV light that is produced by the UV lamp is used in this radiation; This film surface is 1.9cm (0.75 inch) with the distance of UV lamp, and is 20 minutes at 50 ℃ of following radiated times.Used UV lamp is the quartzy 12 watts of lamps of low pressure mercury arc immersion UV, and it has 12 watts of power supplys, from Ace Glass Incorporated.
Embodiment 6 preparations gather (ODPA-APAF) polymer film
Use as embodiment 3 described similar programs preparations gather (ODPA-APAF) polymer film, different is use among this embodiment in embodiment 2, synthesize gather (BTDA-APAF) polyimides.
Embodiment 7 preparation polyphenyl are
azoles polymer film PBO (ODPA-APAF-450C) (breviary is PBO (ODPA-APAF-450C)) also
Use like embodiment 4 described similar programs, (ODPA-APAF) polymer film that gathers that in embodiment 6, prepares through the heat heating prepares also
azoles polymer film PBO (ODPA-APAF-450C) of polyphenyl.
Embodiment 8 preparation polyphenyl are
azoles polymer film PBO (ODPA-APAF-400C) (breviary is PBO (ODPA-APAF-400C)) also
Through at N
2(ODPA-APAF) polymer film that gathers that will in embodiment 6, prepare in the stream is heated to 400 ℃ and preparation polyphenyl also with the firing rate of 5 ℃/min from 50 ℃ of heat
Azoles polymer film PBO (ODPA-APAF-400C).This film was kept 1 hour down at 400 ℃, then with the firing rate of 5 ℃/min at N
2Be cooled to 50 ℃ in the stream.
Embodiment 9 prepares also
azoles polymer film (breviary is crosslinked PBO (ODPA-APAF-450C)) of crosslinked PBO (ODPA-APAF-450C) polyphenyl
PBO (ODPA-APAF-450C) polymer film through the crosslinked preparation in embodiment 7 of UV prepares crosslinked PBO (ODPA-APAF-450C) polymer film; This is exposed to the UV radiation and carries out; The 254nm wavelength UV light that is produced by the UV lamp is used in this radiation; Wherein this film surface is 1.9cm (0.75 inch) with the distance of UV lamp, and is 20 minutes at 50 ℃ of following radiated times.Used UV lamp is the quartzy 12 watts of lamps of low pressure mercury arc immersion UV, and it has 12 watts of power supplys, from Ace Glass Incorporated.
Embodiment 10 prepares also
azoles polymer film (breviary is crosslinked PBO (ODPA-APAF-400C)) of crosslinked PBO (ODPA-APAF-400C) polyphenyl
PBO (ODPA-APAF-400C) polymer film through the crosslinked preparation in embodiment 8 of UV prepares crosslinked PBO (ODPA-APAF-400C) polymer film; This carries out through being exposed to the UV radiation; The 254nm wavelength UV light that is produced by the UV lamp is used in this radiation, and wherein the distance of this film surface and UV lamp is 1.9cm (0.75 inch) and is 20 minutes at 50 ℃ of following radiated times.Used UV lamp is the quartzy 12 watts of lamps of low pressure mercury arc immersion UV, and it has 12 watts of power supplys, from Ace Glass Incorporated.
The CO of embodiment 11PBO (BTDA-APAF-450C) and crosslinked PBO (BTDA-APAF-450C) polymer film
2/ CH
4Separating property
The CO of crosslinked PBO (BTDA-APAF-450C) polymer film that under the probe temperature of 50 ℃ and 100 ℃, prepares among PBO (BTDA-APAF-450C) polymer film of preparation and the embodiment 5 in the test implementation example 4 respectively
2/ CH
4Separate by (table 1).Can find out that by table 1 PBO (BTDA-APAF-450C) polymer film demonstrates high CO
2Permeability (P
CO2=535.9Barrer is under 50 ℃ of probe temperatures) and medium CO
2/ CH
4Selectivity (26.0, under 50 ℃ of probe temperatures).After crosslinked, crosslinked PBO (BTDA-APAF-450C) polymer film 50 ℃ with 100 ℃ of probe temperatures under all demonstrate the CO that compares remarkable increase with PBO (BTDA-APAF-450C) film respectively
2/ CH
4Selectivity (48.4, under 50 ℃ of probe temperatures).
Table 1PBO (BTDA-APAF-450C) and crosslinked PBO (BTDA-APAF-450C) polymer film are to CO
2/ CH
4The pure gas penetration testing result who separates
| Film | P <sub>CO2</sub>(Barrer) | α <sub>CO2/CH4</sub> |
| PBO(BTDA-APAF-450C) <sup>a</sup> | 535.9 | 26.0 |
| PBO(BTDA-APAF-450C) <sup>b</sup> | 477.7 | 12.1 |
| Crosslinked PBO (BTDA-APAF-450C) <sup>a</sup> | 219.5 | 48.4 |
| Crosslinked PBO (BTDA-APAF-450C) <sup>b</sup> | 325.3 | 19.7 |
aP
CO2And P
CH450 ℃ and 690kPa (100psig) test down;
bP
CO2And P
CH4100 ℃ and 690kPa (100psig) test down;
1?Barrer＝10
-10cm
3(STP).cm/cm
2.sec.cmHg。
The H of embodiment 12PBO (BTDA-APAF-450C) and crosslinked PBO (BTDA-APAF-450C) polymer film
2/ CH
4Separating property
The H of crosslinked PBO (BTDA-APAF-450C) polymer film of preparation among PBO (BTDA-APAF-450C) polymer film that under 50 ℃ probe temperature, prepares in the test implementation example 4 and the embodiment 5
2/ CH
4Separate by (table 2).Can find out that by table 2 crosslinked PBO (BTDA-APAF-450C) polymer film demonstrates 133 high H
2/ CH
4Selectivity and be higher than the H of PBO (BTDA-APAF-450C) film
2/ CH
4Optionally three times.This result shows that crosslinked PBO (BTDA-APAF-450C) polymer film is H
2/ CH
4The good candidate of separating.
Table 2PBO (BTDA-APAF-450C) and crosslinked PBO (BTDA-APAF-450C) polymer film are to H
2/ CH
4The pure gas penetration testing result who separates
a
| Film | P <sub>H2</sub>(Barrer) | α <sub>H2/CH4</sub> |
| PBO(BTDA-APAF-450C) | 652.3 | 31.7 |
| Crosslinked PBO (BTDA-APAF-450C) | 604.7 | 133.2 |
aP
H2And P
CH450 ℃ and 690kPa (100psig) test down;
1Barrer＝10
-10cm
3(STP)·cm/cm
2·sec·cmHg。
The propylene separating property of embodiment 13PBO (BTDA-APAF-450C) and crosslinked PBO (BTDA-APAF-450C) polymer film
The propylene of crosslinked PBO (BTDA-APAF-450C) polymer film that under 50 ℃ probe temperature, prepares among PBO (BTDA-APAF-450C) polymer film of preparation and the embodiment 5 in the test implementation example 4 is separated (table 3).The propylene selectivity that can be found out PBO (BTDA-APAF-450C) polymer film by table 3 increases to 19.1 from 12.6 after this film is through the UV crosslinking with radiation.This result shows that crosslinked PBO (BTDA-APAF-450C) polymer film is the good candidate that propylene is separated.
The pure gas penetration testing result that table 3PBO (BTDA-APAF-450C) separates propylene with crosslinked PBO (BTDA-APAF-450C) polymer film
a
| Film | ?P <sub>Propylene</sub>(Barrer) | α <sub>Propylene</sub> |
| PBO(BTDA-APAF-450C) | ?14.1 | 12.6 |
| Crosslinked PBO (BTDA-APAF-450C) | ?3.26 | 19.1 |
aP
PropyleneAnd P
Propane50 ℃ and 207kPa (30psig) test down;
1Barrer＝10
-10cm
3(STP)·cm/cm
2·sec·cmHg。
The CO of embodiment 14PBO (ODPA-APAF-450C) and crosslinked PBO (ODPA-APAF-450C) polymer film
2/ CH
4Separating property
CO at 50 ℃ of PBO (ODPA-APAF-450C) that prepare in the test implementation example 7 and 9 down respectively with 690kPa pure gas pressure and crosslinked PBO (ODPA-APAF-450C) polymer film
2/ CH
4Separate by (table 4).Can find out by gathering (ODPA-APAF) polyimide film by table 4 and to demonstrate CO through PBO (ODPA-APAF-450C) polymer film for preparing 450 ℃ of following heat treatments
2Permeability (P
CO2) be 545Barrer, it is higher than 50 times of conventional cellulose acetate polymers films under the same test condition.Yet, the CO of this PBO (ODPA-APAF-450C) polymer film
2/ CH
4Selectivity (α
CO2/CH4=22) identical with conventional cellulose acetate polymers film.After crosslinked, this crosslinked PBO (ODPA-APAF-450C) polymer film is compared with uncrosslinked PBO (ODPA-APAF-450C) film and is demonstrated double CO
2/ CH
4Selectivity (α
CO2/CH4=45).The CO of this crosslinked PBO (ODPA-APAF-450C) polymer film
2Permeability (P
CO2) still be higher than 15 times of conventional cellulose acetate polymers films.
Table 4 PBO (ODPA-APAF-450C) and crosslinked PBO (ODPA-APAF-450C) polymer film are to CO
2/ CH
4The pure gas penetration testing result who separates
a
| Film | P <sub>CO2</sub>(Barrer) | α <sub>CO2/CH4</sub> |
| PBO(ODPA-APAF-450C) | 544.9 | 22.0 |
| Crosslinked PBO (ODPA-APAF-450C) | 185.8 | 45.0 |
aP
CO2And P
CH450 ℃ and 690kPa (100psig) test down;
1Barrer＝10
-10cm
3(STP)·cm/cm
2·sec·cmHg。
The CO of embodiment 15PBO (ODPA-APAF-400C) and crosslinked PBO (ODPA-APAF-400C) polymer film
2/ CH
4Separating property
CO at 50 ℃ of PBO (ODPA-APAF-400C) that prepare in the test implementation example 8 and 10 down respectively with 690kPa pure gas pressure and crosslinked PBO (ODPA-APAF-400C) polymer film
2/ CH
4Separate by (table 5).Can find out by gathering (ODPA-APAF) polyimide film by table 5 and to demonstrate CO through PBO (ODPA-APAF-400C) polymer film for preparing 400 ℃ of following heat treatments
2Permeability (P
CO2) be 143Barrer, it is higher than 13 times of conventional cellulose acetate polymers films under the same test condition.The CO of this PBO (ODPA-APAF-400C) polymer film
2/ CH
4Selectivity (α
CO2/CH4=32) higher by 45% than conventional cellulose acetate polymers film.After crosslinked, this crosslinked PBO (ODPA-APAF-400C) polymer film is compared the CO that demonstrates further increase with uncrosslinked PBO (ODPA-APAF-400C) film
2/ CH
4Selectivity (α
CO2/CH4=45).The CO of this crosslinked PBO (ODPA-APAF-400C) polymer film
2Permeability (P
CO2) still be higher than 8 times of conventional cellulose acetate polymers films.
Table 5 PBO (ODPA-APAF-400C) and crosslinked PBO (ODPA-APAF-400C) polymer film are to CO
2/ CH
4The pure gas penetration testing result who separates
a
| Film | P <sub>CO2</sub>(Barrer) | α <sub>CO2/CH4</sub> |
| ?PBO(ODPA-APAF-400C) | 143.0 | 31.8 |
| Crosslinked PBO (ODPA-APAF-400C) | 88.2 | 45.0 |
aP
CO2And P
CH450 ℃ and 690kPa (100psig) test down;
1Barrer＝10
-10cm
3(STP)·cm/cm
2·sec·cmHg。
Comparative Examples
For cross-linked benzo
azoles polymer film and commercial membrane, five processing simulation embodiment have been studied than higher gas permeability.Comparative Examples 1 is for using the single-phase system of present commercial membrane.Comparative Examples 2 and 3 is for using the single-phase system of crosslinked PBO (BTDA-APAF-450C) film of high gas permeability listed in the table 1.Comparative Examples 1 and 2 is operated under 50 ℃ feeding temperature.In order to have enough dew point nargin preventing liquid condensation on this film surface in operating process, in these two embodiment, use the MemGuard that is called by the use molecular sieve of UOP LLC exploitation
TMThe renewable adsorption system of preliminary treatment.Because crosslinked polyphenyl also
azoles polymer film has high thermal stability and mechanical stability, Comparative Examples 3 is operated under 100 ℃ high feeding temperature.Owing to through at high temperature operating this film system enough dew point nargin is provided, in Comparative Examples 3, has not needed pretreatment system.
From natural gas stream, to reclaim hydro carbons in order improving, to have studied two stage film system.In Comparative Examples 4, commercial membrane was used for for first and second stages.Comparative Examples 4 needs pretreatment system such as MemGuard
TMIn Comparative Examples 5, crosslinked PBO (BTDA-APAF-450C) film of high gas permeability was used for for first and second stages.5 phase I of Comparative Examples operate at elevated temperatures and think that product gas provides enough dew point nargin.Comparative Examples 5 does not need pretreatment system.Second charging stage of Comparative Examples 5 operates under 50 ℃ feeding temperature to improve this film selectivity, therefore, has reduced the hydrocarbon loss.Because heavy hydrocarbon is difficult to arrive the second stage charging, therefore do not need pretreatment unit such as MemGuard
TM
Comparative Examples 1,2 and 3 supposition natural gas feed have 8%CO
2And the CO of product
2Specification is 2%.In Comparative Examples 1, suppose that commercial membrane is to have the concentrate film of the common performance in the market of present natural gas.In Comparative Examples 2 and 3, it is the film of 200nm that crosslinked PBO (BTDA-APAF-450C) (shown in the table 1) material is used to prepare the thickness that has.Crosslinked PBO (BTDA-APAF-450C) the polymer permeability of the membrane of supposing novel high gas permeability is 0.030m based on the measured permeability of dense film down at 50 ℃
3(STP)/m
2.h.kPa and at 100 ℃ be 0.044m down
3(STP)/m
2.h.kPa and the supposition selectivity be 44 under 50 ℃ and be 15 that it is lower than the selectivity shown in the table 1 under 100 ℃.Comparative Examples 1,2 and 3 is implemented the processing simulation based on above-mentioned performance.The result is presented in the table 6.
Table 6 Comparative Examples 1,2 and 3 analog result
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Incoming flow, m <sup>3</sup>(STP)/h | 5.9×10 <sup>5</sup> | 5.9×10 <sup>5</sup> | 5.9×10 <sup>5</sup> |
| CO in the charging <sub>2</sub>，％ | 8 | 8 | 8 |
| CO in the needed product <sub>2</sub>，％ | 2 | 2 | 2 |
| Whether need MemGuard <sup>TM</sup>Bed | Be | Be | Not |
| The film feeding temperature, ℃ | 50 | 50 | 100 |
| The film feed pressure, kPa | 3792.3 | 3792.3 | 3792.3 |
| Save membrane area, % | - | 59.8 | 82.6 |
| The total hydrocarbon rate of recovery, % | The basis | 7.4 | -2.8 |
Can find out through above embodiment, compare ratio 2 with Comparative Examples 1 and demonstrate the significant cost savings (required membrane area few 59.8%) and the higher hydrocarbon rate of recovery (many 7.4%).Comparative Examples 3 not only can be saved membrane area (82.6%), and can under the hydrocarbon rate of recovery that slightly reduces, save expensive MemGuard
TMPretreatment system.Expect novel high gas permeability and high selectivity crosslinked polyphenyl also
azoles polymer film system can significantly reduce the film system cost and to the big extremely important area of coverage of offshore gas processing scheme.
Through the two stage film system and can improve the hydrocarbon rate of recovery of operation shown in the Comparative Examples 4 and 5.In Comparative Examples 4, two stages are all used commercial membrane, and those are identical in its performance data and the Comparative Examples 1.In Comparative Examples 4, crosslinked PBO (BTDA-APAF-450C) polymer film was used for for first and second stages.Phase I operates to save MemGuard at elevated temperatures
TMSystem.Second stage is operated under lower temperature to improve selectivity.Natural gas feed in the Comparative Examples 3 and 4 becomes 45%CO
2(more meaningful concerning two stage system), and in these two embodiment the CO of product
2Specification is assumed to 8%.Table 7 demonstrates the analog result of Comparative Examples 4 and 5.
Table 7 Comparative Examples 4 and 5 analog result
| Comparative Examples 4 | Comparative Examples 5 | |
| Incoming flow, m <sup>3</sup>(STP)/h | 5.9×10 <sup>5</sup> | 5.9×10 <sup>5</sup> |
| CO in the charging <sub>2</sub>，％ | 45 | 45 |
| CO in the required product <sub>2</sub>，％ | 8 | 8 |
| Whether need preliminary treatment | Be | Not |
| Phase I film feeding temperature, ℃ | 50 | 100 |
| Phase I film feed pressure, kPa | 3792.3 | 3792.3 |
| Second stage film feeding temperature, ℃ | 50 | 50 |
| Second stage film feed pressure, kPa | 3902.6 | 3902.6 |
| The phase I membrane area | The basis | 20.5％ |
| The second stage membrane area | The basis | 40.8％ |
| Total compressor horsepower | The basis | 107.5％ |
| The total hydrocarbon rate of recovery, % | 96.9 | 97.1 |
Can find out that by table 7 Comparative Examples 4 has the similar hydrocarbon rate of recovery with Comparative Examples 5.Because the phase I film is carried out high-temperature operation, Comparative Examples 5 need not preliminary treatment such as MemGuard
TMSystem, it is the 10-40% of Comparative Examples 4 totle drilling costs.Simultaneously, from Comparative Examples 4 to Comparative Examples 5, phase I membrane area reduction by 79.5% and second stage membrane area reduce by 59.2%.Can expect and compare that Comparative Examples 5 has big fund and saves (＞50%) and area of coverage saving (＞50%) with Comparative Examples 4.It is big that only defective is that compressor can slightly become.Table 7 shows that from Comparative Examples 4 to Comparative Examples 5, horsepower increases by 7.5%.
Claims (10)
1. one kind prepares the also method of
azoles and polybenzothiozole polymer film of crosslinked polyphenyl, comprises the steps:
A) at first provide or the synthesis of polyimides polymer, wherein said polyimide polymer contain side group-OH of being arranged in heterocycle acid imide nitrogen ortho position or-SH and at the crosslinkable functionality of polymer backbone;
B) make polyimide film by said polyimide polymer;
C) said polyimide film is converted into also
azoles or polybenzothiozole film of polyphenyl, its be included in 300-600 ℃ with inert atmosphere or vacuum under 30 seconds to 1 hour first step of converting of heating; With
D) also
azoles or polybenzothiozole film are exposed to second step of converting of crosslinking Treatment with said polyphenyl.
2. according to the crosslinked polyphenyl of the preparation of claim 1 method of
azoles and polybenzothiozole polymer film also, wherein said crosslinking Treatment is selected from chemical crosslinking and UV radiation.
3. according to the crosslinked polyphenyl of the preparation of claim 1 method of
azoles and polybenzothiozole polymer film also, its also comprise with said crosslinked polyphenyl also
but the selective layer surface of azoles and polybenzothiozole polymer film apply with the thin layer of the high osmosis material that is selected from polysiloxanes, fluoropolymer, heat-setting silicon rubber and UV radiation curing epoxy polysiloxane.
4. according to the crosslinked polyphenyl of the preparation of claim 1 method of
azoles and polybenzothiozole polymer film also; Wherein said polyimide polymer comprises the repetitive of a plurality of formulas (II), and wherein said formula (II) is:
The X1 of wherein said formula (II) is following group or its mixture:
The X2 of said formula (II) is identical with X1 or be selected from following group or its mixture:
Said formula (II)-Y-is following group or its mixture:
-Z-,-Z '-with-Z "-be independently-O-or-S-,-R-is following group or its mixture:
5. according to the crosslinked polyphenyl of the preparation of claim 1 method of
azoles and polybenzothiozole polymer film also, the said X1 of wherein said formula (II) is identical with X2 and be selected from following group and composition thereof:
And the Y of said formula (II) is selected from following group and composition thereof:
6. according to the crosslinked polyphenyl of the preparation of claim 1 method of
azoles and polybenzothiozole polymer film also, the said X1 of wherein said formula (II) is selected from following group or its mixture:
The X2 of said formula (II) is selected from following group or its mixture:
Said formula (II)-Y-is selected from following group or its mixture:
7. according to the crosslinked polyphenyl of the preparation of claim 1 method of
azoles and polybenzothiozole polymer film also, wherein said polyimide polymer is selected from and gathers [3,3 ', 4; 4 '-benzophenone tetracarboxylic acid dianhydride-2, two (3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (BTDA-APAF)), gather (3,3 ', 4; 4 '-benzophenone tetracarboxylic acid dianhydride-3,3 '-dihydroxy-4,4 '-benzidine) (gathering (BTDA-HAB)), gather [3,3 '; 4,4 '-diphenyl sulfone tetraformic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (DSDA-APAF)), gather (3,3 '; 4,4 '-diphenyl sulfone tetraformic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas-3,3 of 2-'-dihydroxy-4; 4 '-benzidine) (gathering (DSDA-APAF-HAB)), gather [2,2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride-3; 3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride-2; Two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (6FDA-BTDA-APAF)), gather [4,4 '-oxygen di-phthalic anhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (ODPA-APAF)), gather [4; 4 '-oxygen di-phthalic anhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas-3,3 of 2-'-dihydroxy-4; 4 '-benzidine] (gathering (ODPA-APAF-HAB)), gather [3,3 ', 4; 4 '-benzophenone tetracarboxylic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas-3,3 of 2-'-dihydroxy-4; 4 '-benzidine] (gathering (BTDA-APAF-HAB)) and gather (4,4 '-bisphenol-A dianhydride-3,3 '; 4,4 '-benzophenone tetracarboxylic acid dianhydride-2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-] (gathering (BPADA-BTDA-APAF)).
8. one kind is used the also method of
azoles or polybenzothiozole polymer film separating at least one gas or liquid from gas or liquid mixture of crosslinked polyphenyl, and said method comprises the steps:
(a) provide according to the prepared crosslinked polyphenyl of each method among the claim 1-7
azoles or polybenzothiozole polymer film also, wherein said crosslinked polyphenyl also
azoles or polybenzothiozole polymer film is permeability at least a gas or liquid;
(B) contacting the gas or liquid mixture and the cross-linked polystyrene
yl or polybenzothiazole polymer film such that at least one side of a gas or liquid penetration through said crosslinked poly benzo
yl or polybenzothiazole polymer film; and
(c) opposition side from said film removes permeate gas or fluid composition, and it is to penetrate the said at least a gas of said film or the part of liquid.
9. according to Claim 8 separating at least one gas from gas or liquid mixture or the method for liquid, wherein said gas is for being selected from CO
2/ CH
4, CO
2/ N
2, H
2/ CH
4, O
2/ N
2, H
2S/CH
4, olefin/paraff iotan and isoparaffin/n alkane mixture.
10. according to Claim 8 method, wherein said gas or liquid comprise and contain methane and at least a natural gas that is selected from the gas component of carbon dioxide, oxygen, nitrogen, steam, hydrogen sulfide, helium and other trace gas.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/412,629 US8127936B2 (en) | 2009-03-27 | 2009-03-27 | High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes |
| US12/412,629 | 2009-03-27 | ||
| US12/412,633 | 2009-03-27 | ||
| US12/412,633 US8127937B2 (en) | 2009-03-27 | 2009-03-27 | High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes |
| PCT/US2010/024855 WO2010110975A2 (en) | 2009-03-27 | 2010-02-22 | High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102448593A true CN102448593A (en) | 2012-05-09 |
Family
ID=42781743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800229646A Pending CN102448593A (en) | 2009-03-27 | 2010-02-22 | High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP2411130A4 (en) |
| JP (1) | JP5607721B2 (en) |
| KR (1) | KR101392124B1 (en) |
| CN (1) | CN102448593A (en) |
| AU (1) | AU2010229241B2 (en) |
| BR (1) | BRPI1013695A2 (en) |
| CA (1) | CA2755923A1 (en) |
| MY (1) | MY157509A (en) |
| WO (1) | WO2010110975A2 (en) |
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-
2010
- 2010-02-22 AU AU2010229241A patent/AU2010229241B2/en not_active Ceased
- 2010-02-22 BR BRPI1013695A patent/BRPI1013695A2/en not_active IP Right Cessation
- 2010-02-22 KR KR1020117024855A patent/KR101392124B1/en active IP Right Grant
- 2010-02-22 CN CN2010800229646A patent/CN102448593A/en active Pending
- 2010-02-22 JP JP2012502061A patent/JP5607721B2/en not_active Expired - Fee Related
- 2010-02-22 WO PCT/US2010/024855 patent/WO2010110975A2/en active Application Filing
- 2010-02-22 CA CA2755923A patent/CA2755923A1/en not_active Abandoned
- 2010-02-22 MY MYPI2011004425A patent/MY157509A/en unknown
- 2010-02-22 EP EP10756536.8A patent/EP2411130A4/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5409524A (en) * | 1992-12-01 | 1995-04-25 | The Dow Chemical Company | Membranes having improved selectivity and recovery, and process for making same |
| KR100782959B1 (en) * | 2005-01-25 | 2007-12-11 | 한양대학교 산학협력단 | Porous organic polymer, preparation method thereof and gas separation membrane using the same |
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| CN110256671A (en) * | 2013-01-16 | 2019-09-20 | 日产化学工业株式会社 | The manufacturing method and display base plate resin film formation composition of display base plate resin film |
| CN105008028A (en) * | 2013-03-06 | 2015-10-28 | 沙特基础工业公司 | Polymeric membranes |
| CN110694495A (en) * | 2013-09-30 | 2020-01-17 | 佐治亚科技研究公司 | Asymmetric modified carbon molecular sieve hollow fiber membranes with improved permeability |
| CN105848768A (en) * | 2013-11-15 | 2016-08-10 | 汉阳大学校产学协力团 | Flue gas separation membrane comprising thermally rearranged poly(benzoxazole-imide) copolymer having cross-linked structure, and preparation method therefor |
| US9522364B2 (en) | 2013-12-16 | 2016-12-20 | Sabic Global Technologies B.V. | Treated mixed matrix polymeric membranes |
| CN106459403A (en) * | 2014-05-28 | 2017-02-22 | 味之素株式会社 | Polyether ketone compound |
| CN112566714A (en) * | 2018-08-28 | 2021-03-26 | 沙特阿拉伯石油公司 | Fluorinated polytriazole membrane material for gas separation technology |
| CN112566714B (en) * | 2018-08-28 | 2022-11-22 | 沙特阿拉伯石油公司 | Fluorinated polytriazole membrane material for gas separation technology |
| CN112439319A (en) * | 2020-11-16 | 2021-03-05 | 中蓝晨光化工有限公司 | Solvent-resistant PBO nanofiltration membrane and preparation method thereof |
| CN112439319B (en) * | 2020-11-16 | 2022-10-14 | 中蓝晨光化工有限公司 | Solvent-resistant PBO nanofiltration membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| MY157509A (en) | 2016-06-15 |
| JP2012521871A (en) | 2012-09-20 |
| WO2010110975A3 (en) | 2011-02-17 |
| BRPI1013695A2 (en) | 2016-04-26 |
| KR20110130503A (en) | 2011-12-05 |
| AU2010229241A1 (en) | 2011-10-06 |
| WO2010110975A2 (en) | 2010-09-30 |
| EP2411130A2 (en) | 2012-02-01 |
| CA2755923A1 (en) | 2010-09-30 |
| AU2010229241B2 (en) | 2014-09-18 |
| JP5607721B2 (en) | 2014-10-15 |
| EP2411130A4 (en) | 2015-09-02 |
| KR101392124B1 (en) | 2014-05-07 |
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