Patent US4840646A successfully refreshed from Google Patents.
US4840646A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Tetrabromo bisphenol based polyestercarbonate membranes and method of using
Assignee: MG Generon Inc
•
Filing: 1988-07-19
•
Granted: 1989-06-20
•
Expires: 2008-07-19
Abstract
Abstract The invention is a membrane comprising a dense skin of a polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, wherein the membrane has a separation factor for oxygen and nitrogen of 6.5 or greater at about 24° C. In another aspect, the invention is a method of separating oxygen from a mixture of gases comprising nitrogen and oxygen, wherein the method comprises (a) contacting the gas mixture with a thin, non-porous membrane comprising a polyestercarbonate described hereinbefore under conditions such that the oxygen selectively permeates through the membrane to the other side of the membrane; and (b) removing the permeated oxygen from the other side of the membrane, wherein separation factor for the oxygen and nitrogen is 6.5 or greater at about 24° C. The membranes of this invention demonstrate surprisingly high separation factors for oxygen and nitrogen separations. The membranes of this invention have good mechanical properties and therefore are useful under more extreme conditions, for example temperature and pressure, than many commercially used membranes.
Inventors
- 👤 Joginder N. Anand
- 👤 Stephen E. Bales
- 👤 Darrell C. Feay
- 👤 Thomas O. Jeanes
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 12:13
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/68; C08G63/682; B; B01; B01D; B01D53/00; B01D53/22; B01D71/00; B01D71/06; B01D71/48; B01D71/50
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
109 words
A method of separating oxygen from a mixture of gases comprising nitrogen and oxygen wherein the method comprises a. contacting the gas mixture with a membrane comprising a thin, discriminating layer of polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, under conditions such that the oxygen selectively permeates through the membrane to the other side of the membrane; and b. removing the permeated gas from the other side of the membrane; wherein the separation factor for oxygen and nitrogen is 6.5 or greater at about 24° C. and a reduced flux of 1.25×10 -8 cc/cm 2 -sec cmHg or greater oxygen.
Claim 2
Independent Claim
109 words
A method of separating oxygen from a mixture of gases comprising nitrogen and oxygen wherein the method comprises a. contacting the gas mixture with a membrane comprising a thin, discriminating layer of polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, under conditions such that the oxygen selectively permeates through the membrane to the other side of the membrane; and b. removing the permeated gas from the other side of the membrane; wherein the separation factor for oxygen and nitrogen is 6.5 or greater at about 24° C. and a reduced flux of 1.25×10 -8 cc/cm 2 -sec cmHg or greater oxygen.
Claim 3
Dependent Claim
50 words
The method of claim 1 wherein a pressure differential is maintained across the membrane between the side of the membrane in contact with the gas mixture and the other side of the membrane, the higher pressure is maintained on the side of the membrane in contact with the gas mixture.
Claim 4
Dependent Claim
121 words
The method of claim 2 wherein the polyestercarbonate corresponds to the formula ##STR8## wherein R 1 is separately in each instance a direct bond, ##STR9## a C 1-6 divalent hydrocarbon, a C 1-6 divalent fluorocarbon, or an inertly substituted C 1-6 divalent hydrocarbon radical; R 2 is separately in each instance a C 1-20 divalent hydrocarbon, or a C 1-20 divalent hydrocarbon substituted with one or more halo moieties; W is the residue of a monofunctional compound which is reactive with a chloroformate functionality; x is 0 or 1; y is 0 or 1; n is 50 or greater; with the proviso that the ratio of units wherein x=1 to units wherein y=1 is between about 99:1 to about 1:99, inclusive.
Claim 5
Dependent Claim
33 words
The method of claim 3 which has a separation factor for oxygen and nitrogen of 7.0 or greater and a reduced flux of 7.56×10 -8 cc/cm 2 -sec cmHg or greater for oxygen.
Claim 6
Dependent Claim
83 words
The method of claim 4 wherein R 1 is separately in each occurrence a direct bond, a C 1-6 divalent hydrocarbon, a C 1-6 divalent fluorocarbon, or an inertly substituted divalent C 1-6 hydrocarbon; R 2 is separately in each occurrence a divalent C 1-20 aliphatic, C 5-20 cycloaliphatic, C 6-20 aromatic, a halo-substituted C 6-20 aromatic, a halo-substituted C 1-20 aliphatic, or a halo-substituted C 5-20 cycloaliphatic hydrocarbon; W is the residue of a monofunctional aliphatic alcohol, aromatic alcohol, thiol, or amine.
Claim 7
Dependent Claim
46 words
The method of claim 5 wherein R 1 is a divalent C 1-6 hydrocarbon; R 2 is a divalent C 5-20 cycloaliphatic, a C 6-20 aromatic radical, a halo-substituted C 5-20 cycloaliphatic, or a C 6-20 halo-substituted aromatic hydrocarbon; W is a C 1-20 hydrocarbyloxy radical.
Claim 8
Dependent Claim
52 words
The method of claim 6 wherein R 1 is a divalent C 1-6 alkylidiene; R 2 is ##STR10## wherein R 3 separately in each occurrence chlorine. fluorine, phenyl, or halogenated alkyl; a is 0 to 4; and W is a C 1-20 alkoxy, C 6-20 aryloxy, or C 7-20 alkyl-substituted aryloxy radical.
Claim 9
Dependent Claim
21 words
The method of claim 7 wherein R 1 is propylidine; R 2 is ##STR11## and W is p-tert butylphenyloxy or methoxy.
Claim 10
Dependent Claim
22 words
The method of claim 8 wherein the polyestercarbonate is derived from bisphenol A, and a mixture of terephthaloyl chloride, and isophthaloyl chloride.
Claim 11
Independent Claim
114 words
A method of separating oxygen from a mixture of gases comprising nitrogen and oxygen wherein the method comprises a. contacting the gas mixture with on asymmetric or composite membrane comprising a thin, descriminating layer of polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, under conditions such that the oxygen selectively permeates through the membrane to the other side of the membrane; and b. removing the permeated oxygen from the other side of the membrane; wherein the membrane exhibits separation factor for oxygen and nitrogen is 6.5 or greater at about 24° C. and a reduced flux of 8.53×10 -8 cm/cm 2 -sec cmHg or greater oxygen.
Claim 12
Independent Claim
114 words
A method of separating oxygen from a mixture of gases comprising nitrogen and oxygen wherein the method comprises a. contacting the gas mixture with on asymmetric or composite membrane comprising a thin, descriminating layer of polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, under conditions such that the oxygen selectively permeates through the membrane to the other side of the membrane; and b. removing the permeated oxygen from the other side of the membrane; wherein the membrane exhibits separation factor for oxygen and nitrogen is 6.5 or greater at about 24° C. and a reduced flux of 8.53×10 -8 cm/cm 2 -sec cmHg or greater oxygen.
Claim 13
Dependent Claim
50 words
The method of claim 10 wherein a pressure differential is maintained across the membrane between the side of the membrane in contact with the gas mixture and the other side of the membrane, the higher pressure is maintained on the side of the membrane in contact with the gas mixture.
Claim 14
Dependent Claim
120 words
The method of claim 11 wherein the polyestercarbonate corresponds to the formula ##STR12## wherein R 1 is separately in each instances direct bond, ##STR13## a C 1-6 divalent hydrocarbon, a C 1-6 divalent fluorocarbon, or an inertly substituted C 1-6 divalent hydrocarbon radical; R 2 is separately in each instance a C 1-20 divalent hydrocarbon, or a C 1-20 divalent hydrocarbon substituted with one or more halo moieties; W is the residue of a monofunctional compound which is reactive with a chloroformate functionality; x is 0 or 1; y is 0 or 1; n is 50 or greater; with the proviso that the ratio of units wherein x=1 to units where y=1 is between about 99:1 to about 1:99, inclusive.
Claim 15
Dependent Claim
33 words
The method of claim 12 which has a separation factor for oxygen and nitrogen of 7.0 or greater and a reduced flux of 5.69×10 -6 cc/cm 2 -sec cmHg or greater for oxygen.
Claim 16
Dependent Claim
83 words
The method of claim 13 wherein R 1 is separately in each occurrence a direct bond, a C 1-6 divalent hydrocarbon, a C 1-6 divalent fluorocarbon, or an inertly substituted divalent C 1-6 hydrocarbon; R 2 is separately in each occurrence a divalent C 1-20 aliphatic, C 5-20 cycloaliphatic, C 6-20 aromatic, a halo-substituted C 6-20 aromatic, a halo-substituted C 1-20 aliphatic, or a halo-substituted C 5-20 cycloaliphatic hydrocarbon; W is the residue of a monofunctional aliphatic alcohol, aromatic alcohol, thiol, or amine.
Claim 17
Dependent Claim
46 words
The method of claim 14 wherein R 1 is a divalent C 1-6 hydrocarbon; R 2 is a divalent C 5-20 cycloaliphatic, a C 6-20 aromatic radical, a halo-substituted C 5-20 cycloaliphatic, or a C 6-20 halo-substituted aromatic hydrocarbon; W is a C 1-20 hydrocarbyloxy radical.
Claim 18
Dependent Claim
53 words
The method of claim 15 wherein R 1 is a divalent C 1-6 alkylidiene; R 2 is ##STR14## wherein R 3 is separately in each occurrence chlorine, fluorine, phenyl, or halogenated alkyl; a is 0 to 4; and W is a C 1-20 alkoxy, C 6-20 aryloxy, or C 7-20 alkyl-substituted aryloxy radical.
Claim 19
Dependent Claim
21 words
The method of claim 16 wherein R 1 is propylidene; R 2 is ##STR15## and W is p-tert butylphenyloxy or methoxy.
Claim 20
Dependent Claim
22 words
The method of claim 17 wherein the polyestercarbonate is derived from bisphenol A, and a mixture of terephthaloyl chloride, and isophthaloyl chloride.
Claim 21
Dependent Claim
58 words
A membrane comprising a dense skin of a polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, wherein the membrane has a separation factor for oxygen and nitrogen of 6.5 or greater at about 24° C. and a reduced flux of 1.25×10 -8 cc/cm 2 -sec cmHg or greater for oxygen.
Claim 22
Dependent Claim
58 words
A membrane comprising a dense skin of a polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, wherein the membrane has a separation factor for oxygen and nitrogen of 6.5 or greater at about 24° C. and a reduced flux of 1.25×10 -8 cc/cm 2 -sec cmHg or greater for oxygen.
Claim 23
Dependent Claim
125 words
The membrane of claim 19 wherein the polyestercarbonate corresponds to the formula ##STR16## wherein A is ##STR17## R 1 is separately in each instance a single direct bond, ##STR18## a C 1-6 divalent hydrocarbon, a C 1-6 divalent fluorocarbon, or an inertly substituted C 1-6 divalent hydrocarbon radical; R 2 is separately in each instance a C 1-20 divalent hydrocarbon or a C 1-20 divalent hydrocarbon, substituted with one or more halo moieties; W is the residue of a monofunctional compound which is reactive with a chloroformate functionality; x is 0 or 1; y is 0 or 1; n is 50 or greater; with the proviso that the ratio of units wherein x=1 to units wherein y=1 is between about 99:1 to about 1:99, inclusive.
Claim 24
Dependent Claim
33 words
A membrane of claim 20 which has a separation factor for oxygen and nitrogen of 7.0 or greater and the reduced flux of 7.56×10 -8 cc/cm 2 -sec cmHg or greater for oxygen.
Claim 25
Dependent Claim
83 words
The membrane of claim 21 wherein R 1 is separately in each occurrence a direct bond, a C 1-6 divalent hydrocarbon, a C 1-6 divalent fluorocarbon, or an inertly substituted divalent C 1-6 hydrocarbon; R 2 is separately in each occurrence a divalent C 1-20 aliphatic, C 5-20 cycloaliphatic, C 6-20 aromatic, a halo-substituted C 6-20 aromatic, a halo-substituted C 1-20 aliphatic, or a halo-substituted C 5-20 cycloaliphatic hydrocarbon; W is the residue of a monofunctional aliphatic alcohol, aromatic alcohol, thiol, or amine.
Claim 26
Dependent Claim
45 words
The membrane of claim 22 wherein R 1 is a divalent C 1-6 hydrocarbon; R 2 is a divalent C 5-20 cycloaliphatic, C 6-20 aromatic radical, a halo-substituted C 5-20 cycloaliphatic, or a C 6-20 halo-substituted aromatic hydrocarbon; W is a C 1-20 hydrocarbyloxy radical.
Claim 27
Dependent Claim
53 words
The membrane of claim 23 wherein R 1 is a divalent C 1-6 alkylidiene; R 2 is ##STR19## wherein R 3 is separately in each occurrence chlorine, fluorine, phenyl, or halogenated alkyl; a is 0 to 4: and W is a C 1-20 alkoxy, C 6-20 aryloxy, or C 7-20 alkyl-substituted aryloxy radical.
Claim 28
Dependent Claim
21 words
A membrane of claim 24 wherein R 1 is propylidene; R 2 is ##STR20## and W is para-tertiary phenyloxy or methoxy.
Claim 29
Dependent Claim
22 words
A membrane of claim 25 wherein the polyestercarbonate is derived from bisphenol A, and a mixture of terephthaloyl chloride, and isophthaloyl chloride.
Claim 30
Dependent Claim
61 words
An asymmetric or composite membrane comprising a thin discriminating layer of a polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, wherein the membrane has a separation factor for oxygen and nitrogen of 6.5 or greater at about 24° C. and a reduced flux of 8.53×10 -8 cc/cm 2 -cmHg or greater for oxygen.
Claim 31
Dependent Claim
61 words
An asymmetric or composite membrane comprising a thin discriminating layer of a polyestercarbonate, wherein the diphenolic residue in the backbone of the polyestercarbonate is a tetrabromo diphenolic residue, wherein the membrane has a separation factor for oxygen and nitrogen of 6.5 or greater at about 24° C. and a reduced flux of 8.53×10 -8 cc/cm 2 -cmHg or greater for oxygen.
Claim 32
Dependent Claim
126 words
The membrane of claim 27 wherein the polyestercarbonate corresponds to the formula ##STR21## wherein A is ##STR22## R 1 is separately in each instance a single direct bond, ##STR23## a C 1-6 divalent hydrocarbon, a C 1-6 divalent fluorocarbon, or an inertly substituted C 1-6 divalent hydrocarbon radical; R 2 is separately in each instance a C 1-20 divalent hydrocarbon or a C 1-20 divalent hydrocarbon, substituted with one or more halo moieties; W is the residue of a monofunctional compound which is reactive with a chloroformate functionality: x is 0 or 1; y is 0 or 1; n is 50 or greater: with the proviso that the ratio of units wherein x=1 to units wherein y =1 is between about 99:1 to about 1:99, inclusive.
Claim 33
Dependent Claim
33 words
A membrane of claim 28 which has a separation factor for oxygen and nitrogen of 7.0 or greater and a reduced flux of 5.69×10 -6 cc/cm 2 -sec cmHg or greater for oxygen.
Claim 34
Dependent Claim
83 words
The membrane of claim 29 wherein R 1 is separately in each occurrence a direct bond, a C 1-6 divalent hydrocarbon, a C 1-6 divalent fluorocarbon, or an inertly substituted divalent C 1-6 hydrocarbon; R 2 is separately in each occurrence a divalent C 1-20 aliphatic, C 5-20 cycloaliphatic, C 6-20 aromatic, a halo-substituted C 6-20 aromatic, a halo-substituted C 1-20 aliphatic, or a halo-substituted C 5-20 cycloaliphatic hydrocarbon; W is the residue of a monofunctional aliphatic alcohol, aromatic alcohol, thiol, or amine.
Claim 35
Dependent Claim
45 words
The membrane of claim 30 wherein R 1 is a divalent C 1-6 hydrocarbon: R 2 is a divalent C 5-20 cycloaliphatic, C 6-20 aromatic radical, a halo-substituted C 5-20 cycloaliphatic, or a C 6-20 halo-substituted aromatic hydrocarbon; W is a C 1-20 hydrocarbyloxy radical.
Claim 36
Dependent Claim
53 words
The membrane of claim 31 wherein R 1 is a divalent C 1-6 alkylidiene; R 2 is ##STR24## wherein R 3 is separately in each occurrence chlorine, fluorine, phenyl, or halogenated alkyl; a is 0 to 4; and W is a C 1-20 alkoxy, C 6-20 aryloxy, or C 7-20 alkyl-substituted aryloxy radical.
Claim 37
Dependent Claim
22 words
The membrane of claim 32 wherein R 1 is propylidene: R 2 is ##STR25## and W is paratertiary butyl phenyloxy or methoxy.
Claim 38
Dependent Claim
23 words
The membrane of claim 33 wherein the polyestercarbonate is derived from bisphenol A, and a mixture of terephthaloyl chloride, and isophthaloyl chloride. pg,50
Claim 39
Dependent Claim
16 words
The membrane of claim 28 with a flux of 1.77×10 -5 cc/cm 2 -sec for oxygen.
Claim 40
Dependent Claim
18 words
The membrane of claim 35 with a flux of 1.15×10 -3 cc/cm 2 -sec or greater for oxygen.
References Cited (Backward Citations)
US3028364A
Cited
US3030331A
Cited
US3169121A
Cited
US3207814A
Cited
US3256675A
Cited
US3334154A
Cited
US3729447A
Cited
US3720721A
Cited
US3945926A
Cited
US3776887A
Cited
US3794617A
Cited
US4086310A
Cited
JPS49123997A
Cited
US3873504A
Cited
US4156069A
Cited
US4169868A
Cited
US4066623A
Cited
JPS5366880A
Cited
US4297455A
Cited
US4195157A
Cited
US4390682A
Cited
US4194038A
Cited
US4255556A
Cited
JPS56107351A
Cited
JPS56131657A
Cited
JPS56133332A
Cited
US4310652A
Cited
US4322521A
Cited
US4346209A
Cited
JPS588511A
Cited
US4429083A
Cited
JPS5922724A
Cited
US4526956A
Cited
JPS59120206A
Cited
DE3400238A1
Cited
JPS60228531A
Cited
EP0242147A2
Cited
US4717393A
Cited
USRE35351E
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1992-06-19 | 1992-12-19 | 1993-06-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-06-19 | 1996-12-19 | 1997-06-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-06-19 | 2000-12-19 | 2001-06-20 | $7700.00 | Window Closed / Lapsed |