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US4728346A
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Permeation modified asymmetric gas separation membranes having graded density skins
Assignee: Permea Inc
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Filing: 1986-08-15
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Granted: 1988-03-01
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Expires: 2006-08-15
Abstract
Abstract Asymmetric gas separation membranes having graded density skins and macrovoid-free morphology comprised of glassy, hydrophobic polymers which when contacted on the graded density skin surface with an effective amount of permeation modifier and a coating in occluding contact, exhibit permeation selectivities greater than the intrinsic permeation selectivities for at least one gas of a gaseous mixture than a bulk sample of the polymers. The permeation modified membranes have increased free volume as evidenced by the membrane first heat T g which is greater than the T g of the bulk sample of the glassy, hydrophobic polymers; however the permeation modified membranes having an effective amount of permeation modifier added in non-uniform mode are achieved without significant loss in the physical properties of the membrane, including T g .
Inventors
- 👤 Milton K. Murphy
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 11:05
CPC Classifications
B; B01; B01D; B01D67/00; B01D67/0081; B01D67/0088; B01D69/00; B01D69/12
Claims Analysis
Total Claims: 41
Claim 1
Independent Claim
191 words
A multicomponent gas separation membrane exhibiting significantly enhanced gas separation selectivity and increased permeability comprising: a preformed asymmetric gas separation membrane having a graded density skin and macrovoid-free morphology comprised of glassy, hydrophobic polymers, the membrane having increased free volume as evidenced by the membrane first heat T g which is greater than the T g of a bulk sample of the glassy hydrophobic polymers, the polymers of the membrane having a separation factor for one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture which when contacted on one or both sides with an effective amount of a permeation modifier and when combined with a coating in occluding contact with the graded density skin provides a multicomponent gas separation membrane which exhibits a separation factor greater than the determined intrinsic separation factor of the bulk sample of the polymers of the asymmetric separation membrane, greater than the determined separation factor of the preformed asymmetric separation membranes, and greater than the determined intrinsic separation factor of the material of the coating with respect to at least one pair of gases in the mixture.
Claim 2
Dependent Claim
191 words
A multicomponent gas separation membrane exhibiting significantly enhanced gas separation selectivity and increased permeability comprising: a preformed asymmetric gas separation membrane having a graded density skin and macrovoid-free morphology comprised of glassy, hydrophobic polymers, the membrane having increased free volume as evidenced by the membrane first heat T g which is greater than the T g of a bulk sample of the glassy hydrophobic polymers, the polymers of the membrane having a separation factor for one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture which when contacted on one or both sides with an effective amount of a permeation modifier and when combined with a coating in occluding contact with the graded density skin provides a multicomponent gas separation membrane which exhibits a separation factor greater than the determined intrinsic separation factor of the bulk sample of the polymers of the asymmetric separation membrane, greater than the determined separation factor of the preformed asymmetric separation membranes, and greater than the determined intrinsic separation factor of the material of the coating with respect to at least one pair of gases in the mixture.
Claim 3
Dependent Claim
41 words
The multicomponent gas separation membrane of claim 1 wherein the effective amount of permeation modifier added to the preformed asymmetric separation membrane provides a multicomponent gas separation membrane having no appreciable loss in physical properties as exemplified by T g measurement.
Claim 4
Dependent Claim
34 words
The multicomponent gas separation membrane of claim 1 wherein the effective amount of permeation modifier added to the preformed asymmetric separation membrane comprises from about 0.01 to about 1% by weight of the membrane.
Claim 5
Dependent Claim
39 words
The multicomponent gas separation membrane of claim 3 wherein the effective amount of permeation modifier is distributed in the graded density skin of the preformed asymmetric separation membrane in a non-uniform distribution across the preformed asymmetric separation membrane wall.
Claim 6
Dependent Claim
22 words
The multicomponent gas separation membrane according to claim 1 wherein the permeation modifier is physically or chemically combined with the coating material.
Claim 7
Dependent Claim
20 words
The multicomponent gas separation membrane of claim 1 wherein the permeation modifier is comprised of one or more component materials.
Claim 8
Dependent Claim
24 words
The multicomponent gas separation membrane according to claim 1 wherein the permeation modifier is comprised of an aromatic, rigid, polar material exhibiting antiplasticizing behavior.
Claim 9
Dependent Claim
18 words
The multicomponent gas separation membrane of claim 1 wherein the permeation modifier is comprised of an antiplasticizer composition.
Claim 10
Dependent Claim
125 words
The multicomponent gas separation membrane of claim 1 wherein the permeation modified asymmetric membrane for gas separation is modified by an effective amount of a permeation modifier of the formula: ##STR4## in which n is one to three, R and R 1 independently are hydroxy, chloro, bromo, amino, alkylamino, dialkylamino, nitro, alkoxy, hydroxyalkyl, hydroalkoxy, carboalkoxy, carboxyalkoxy, or glycidylocy, and R 2 and R 3 independently are hydrogen or alkyl, or; ##STR5## in which R, R 1 , R 2 and R 3 are the same as in the formula (a), X is oxygen, sulfur, dithio, carbonyl, alkylene or cycloalkylene, and n 1 and n 2 are zero to three with the proviso that the sum of n 1 and n 2 is at least two.
Claim 11
Dependent Claim
48 words
The multicomponent gas separation membrane of claim 1 wherein the permeation modified asymmetric membrane for gas separation is modified by an effective amount of a permeation modifier of the formula: ##STR6## where R, R 1 , R 2 and R 3 are independently hydrogen, alkyl, alkenyl or aryl.
Claim 12
Dependent Claim
110 words
A permeation modified asymmetric gas separation membrane having a graded density skin and macrovoid-free morphology comprised of glassy, hydrophobic polymers, the membrane having increased free volume as evidenced by the membrane first heat T g which is greater than the T g of a bulk sample of the glassy, hydrophobic polymers, the membrane having been contacted on the graded density skin with an effective amount of a permeation modifier and when combined with a coating in contact with the graded density skin exhibits a separation factor greater than the intrinsic separation factor of a dense membrane of the bulk sample of the polymers for one gas of a gaseous mixture.
Claim 13
Dependent Claim
110 words
A permeation modified asymmetric gas separation membrane having a graded density skin and macrovoid-free morphology comprised of glassy, hydrophobic polymers, the membrane having increased free volume as evidenced by the membrane first heat T g which is greater than the T g of a bulk sample of the glassy, hydrophobic polymers, the membrane having been contacted on the graded density skin with an effective amount of a permeation modifier and when combined with a coating in contact with the graded density skin exhibits a separation factor greater than the intrinsic separation factor of a dense membrane of the bulk sample of the polymers for one gas of a gaseous mixture.
Claim 14
Dependent Claim
41 words
The multicomponent gas separation membrane of claim 11 wherein the effective amount of permeation modifier added to the preformed asymmetric separation membrane provides a multicomponent gas separation membrane having no appreciable loss in physical properties as exemplified by T g measurement.
Claim 15
Dependent Claim
34 words
The multicomponent gas separation membrane of claim 11 wherein the effective amount of permeation modifier added to the preformed asymmetric separation membrane comprises from about 0.01 to about 1% by weight of the membrane.
Claim 16
Dependent Claim
39 words
The multicomponent gas separation membrane of claim 11 wherein the effective amount of permeation modifier is distributed in the graded density skin of the preformed asymmetric separation membrane in a non-uniform distribution across the preformed asymmetric separation membrane wall.
Claim 17
Dependent Claim
22 words
The multicomponent gas separation membrane according to claim 11 wherein the permeation modifier is physically or chemically combined with the coating material.
Claim 18
Dependent Claim
20 words
The multicomponent gas separation membrane of claim 11 wherein the permeation modifier is comprised of one or more component materials.
Claim 19
Dependent Claim
24 words
The multicomponent gas separation membrane according to claim 11 wherein the permeation modifier is comprised of an aromatic, rigid, polar material exhibiting antiplasticizing behavior.
Claim 20
Dependent Claim
125 words
The multicomponent gas separation membrane of claim 11 wherein the permeation modified asymmetric membrane for gas separation is modified by an effective amount of a permeation modifier of the formula: ##STR7## in which n is one to three, R and R 1 independently are hydroxy, chloro, bromo, amino, alkylamino, dialkylamino, nitro, alkoxy, hydroxyalkyl, hydroalkoxy, carboalkoxy, carboxyalkoxy, or glycidylocy, and R 2 and R 3 independently are hydrogen or alkyl, or; ##STR8## in which R, R 1 , R 2 and R 3 are the same as in the formula (a), X is oxygen, sulfur, dithio, carbonyl, alkylene or cycloalkylene, and n 1 and n 2 are zero to three with the proviso that the sum of n 1 and n 2 is at least two.
Claim 21
Dependent Claim
48 words
The multicomponent gas separation membrane of claim 11 wherein the permeation modified asymmetric membrane for gas separation is modified by an effective amount of a permeation modifier of the formula: ##STR9## where R, R 1 , R 2 and R 3 are independently hydrogen, alkyl, alkenyl or aryl.
Claim 22
Dependent Claim
181 words
A permeation modified asymmetric gas separation membrane comprised of a coating in occluding contact with a graded density skin of an asymmetric membrane which has macrovoid-free morphology and is comprised of glassy, hydrophobic polymers, the graded density skin being characterized as having an active layer and a transition layer which communicates with the active layer and a porous substrate of the membrane, wherein all three provide increased free volume to the membrane as evidenced by the membrane first heat T g which is greater than the T g of a bulk sample of the glassy, hydrophobic polymers, the membrane having been contacted on the graded density skin with an effective amount of a permeation modifier, the permeation modified membrane exhibits a separation factor greater than the determined intrinsic separation factor of a dense membrane of the bulk sample of the polymers for one gas of a gaseous mixture and an increase in permeability for the one gas of the gaseous mixture when compared to unmodified asymmetric membranes of the same polymers having uniform skins and coated with the same coating materials.
Claim 23
Dependent Claim
181 words
A permeation modified asymmetric gas separation membrane comprised of a coating in occluding contact with a graded density skin of an asymmetric membrane which has macrovoid-free morphology and is comprised of glassy, hydrophobic polymers, the graded density skin being characterized as having an active layer and a transition layer which communicates with the active layer and a porous substrate of the membrane, wherein all three provide increased free volume to the membrane as evidenced by the membrane first heat T g which is greater than the T g of a bulk sample of the glassy, hydrophobic polymers, the membrane having been contacted on the graded density skin with an effective amount of a permeation modifier, the permeation modified membrane exhibits a separation factor greater than the determined intrinsic separation factor of a dense membrane of the bulk sample of the polymers for one gas of a gaseous mixture and an increase in permeability for the one gas of the gaseous mixture when compared to unmodified asymmetric membranes of the same polymers having uniform skins and coated with the same coating materials.
Claim 24
Dependent Claim
41 words
The multicomponent gas separation membrane of claim 20 wherein the effective amount of permeation modifier added to the preformed asymmetric separation membrane provides a multicomponent gas separation membrane having no appreciable loss in physical properties as exemplified by T g measurement.
Claim 25
Dependent Claim
34 words
The multicomponent gas separation membrane of claim 20 wherein the effective amount of permeation modifier added to the preformed asymmetric separation membrane comprises from about 0.01 to about 1% by weight of the membrane.
Claim 26
Dependent Claim
39 words
The multicomponent gas separation membrane of claim 20 wherein the effective amount of permeation modifier is distributed in the graded density skin of the preformed asymmetric separation membrane in a non-uniform distribution across the preformed asymmetric separation membrane wall.
Claim 27
Dependent Claim
22 words
The multicomponent gas separation membrane according to claim 20 wherein the permeation modifier is physically or chemically combined with the coating material.
Claim 28
Dependent Claim
20 words
The multicomponent gas separation membrane of claim 20 wherein the permeation modifier is comprised of one or more component materials.
Claim 29
Dependent Claim
24 words
The multicomponent gas separation membrane according to claim 20 wherein the permeation modifier is comprised of an aromatic, rigid, polar material exhibiting antiplasticizing behavior.
Claim 30
Dependent Claim
125 words
The multicomponent gas separation membrane of claim 20 wherein the permeation modified asymmetric membrane for gas separation is modified by an effective amount of a permeation modifier of the formula: ##STR10## in which n is one to three, and R and R 1 independently are hydroxy, chloro, bromo, amino, alkylamino, dialkylamino, nitro, hydroxyalkyl, hydroalkoxy, carboalkoxy, carboxyalkoxy, or glycidylocy, and R 2 and R 3 independently are hydrogen or alkyl, or; ##STR11## in which R, R 1 , R 2 and R 3 are the same as in the formula (a), X is oxygen, sulfur, dithio, carbonyl, alkylene or cycloalkylene, and n 1 and n 2 are zero to three with the proviso that the sum of n 1 and n 2 is at least two.
Claim 31
Dependent Claim
48 words
The multicomponent gas separation membrane of claim 20 wherein the permeation modified asymmetric membrane for gas separation is modified by an effective amount of a permeation modifier of the formula: ##STR12## where R, R 1 , R 2 and R 3 are independently hydrogen, alkyl, alkenyl or aryl.
Claim 32
Dependent Claim
169 words
A process for producing a multicomponent gas separation membrane exhibiting significantly enhanced separation selectivity and increased permeabilities comprising the steps: (a) producing an asymmetric gas separation membrane having a graded density skin and macrovoid-free morphology which is comprised of glassy, hydrophobic polymers, the membranes having increased free volume as evidenced by the membrane first heat T g which is greater than the T g of the bulk sample of the glassy, hydrophobic polymers, the polymers having a separation factor for one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture; (b) contacting the asymmetric separation membrane on the graded density skin with an effective amount of a permeation modifier; and (c) coating the permeation modified, preformed, asymmetric separation membrane with a coating which forms onto the membrane in occluding contact, the material of the coating exhibiting a determined intrinsic separation factor which is less than the determined intrinsic separation factor of the bulk sample of the polymers of the asymmetric membrane.
Claim 33
Dependent Claim
169 words
A process for producing a multicomponent gas separation membrane exhibiting significantly enhanced separation selectivity and increased permeabilities comprising the steps: (a) producing an asymmetric gas separation membrane having a graded density skin and macrovoid-free morphology which is comprised of glassy, hydrophobic polymers, the membranes having increased free volume as evidenced by the membrane first heat T g which is greater than the T g of the bulk sample of the glassy, hydrophobic polymers, the polymers having a separation factor for one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture; (b) contacting the asymmetric separation membrane on the graded density skin with an effective amount of a permeation modifier; and (c) coating the permeation modified, preformed, asymmetric separation membrane with a coating which forms onto the membrane in occluding contact, the material of the coating exhibiting a determined intrinsic separation factor which is less than the determined intrinsic separation factor of the bulk sample of the polymers of the asymmetric membrane.
Claim 34
Dependent Claim
42 words
The process according to claim 29 wherein the effective amount of permeation modifier added to the preformed membrane provides a permeation modified, asymmetric gas separation membrane having no appreciable changes in physical properties as, for example, a loss in T g .
Claim 35
Dependent Claim
30 words
The process according to claim 29 wherein the effective amount of permeation modifier added to the membrane comprises from about 0.01 to about 1.0 percent by weight of the membrane.
Claim 36
Dependent Claim
43 words
The process according to claim 29 wherein the effective amount of permeation modifier is distributed onto the graded density skin surface of the preformed membrane resulting in a non-uniform distribution across the wall of the preformed graded density skin asymmetric gas separation membrane.
Claim 37
Dependent Claim
18 words
The process according to claim 29 wherein the permeation modifier is comprised of one or more component materials.
Claim 38
Dependent Claim
16 words
The process according to claim 29 wherein the permeation modifier is comprised of an antiplasticizer composition.
Claim 39
Dependent Claim
21 words
The process according to claim 29 wherein the permeation modifier is comprised of an aromatic, rigid, polar material exhibiting antiplasticizing behavior.
Claim 40
Dependent Claim
129 words
The process according to claim 29 wherein the permeation modified membrane is a preformed graded density skin, asymmetric gas separation membrane modified by an effective amount of a permeation modifier having the formula: ##STR13## in which n is one to three, and R and R 1 independently are hydroxy, chloro, bromo, amino, alkylamino, dialkylamino, nitro, alkoxy, hydroaxyalkyl, hydroalkoxy, carboalkoxy, carboxyalkoxy, or glycidylocy, and R 2 and R 3 independently are hydrogen or alkyl, or; ##STR14## in which R, R 1 , R 2 and R 3 are the same as in the formula (a), X is oxygen, sulfur, dithio, carbonyl, alkylene or cycloalkylene, and n 1 and n 2 are zero to three with the proviso that the sum of n 1 and n 2 is at least two.
Claim 41
Dependent Claim
53 words
The process according to claim 29 wherein the permeation modified membrane is comprised of a preformed graded density skin, asymmetric gas separation membrane modified by an effective amount of a permeation modifier having the formula: ##STR15## where R, R 1 , R 2 and R 3 are independently hydrogen, alkyl, alkenyl or aryl.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1991-03-01 | 1991-08-31 | 1992-03-01 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1995-03-01 | 1995-08-31 | 1996-03-01 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1999-03-01 | 1999-08-31 | 2000-03-01 | $7700.00 | Window Closed / Lapsed |