US4818254A — Semi-permeable membranes consisting predominantly…

Claim 1

Independent Claim 139 words

A semi-permeable gas separation membrane comprising a thin discriminating layer consisting predominantly of a carbonate polymer derived from a bisphenol corresponding to formula I ##STR8## where R at each occurrence is independently H, Cl, Br, or C 1 -C 4 alkyl and R 1 is ##STR9## --S--, --SO 2 --, --O--, or a C 1 -C 6 divalent hydrocarbon a C 1 -C 6 divalent fluorocarbon radical or inertly substituted hydrocarbon radical, with the proviso that at least 25 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 24° C. of at least 6.1 and a reduced flux of 3.35×10 -9 cc/cm 2 -sec-cm Hg or greater for oxygen.

Claim 2

Dependent Claim 139 words

A semi-permeable gas separation membrane comprising a thin discriminating layer consisting predominantly of a carbonate polymer derived from a bisphenol corresponding to formula I ##STR8## where R at each occurrence is independently H, Cl, Br, or C 1 -C 4 alkyl and R 1 is ##STR9## --S--, --SO 2 --, --O--, or a C 1 -C 6 divalent hydrocarbon a C 1 -C 6 divalent fluorocarbon radical or inertly substituted hydrocarbon radical, with the proviso that at least 25 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 24° C. of at least 6.1 and a reduced flux of 3.35×10 -9 cc/cm 2 -sec-cm Hg or greater for oxygen.

Claim 3

Dependent Claim 36 words

The membrane of claim 1 wherein at least 35 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups with which are exclusively Br or Cl.

Claim 4

Dependent Claim 35 words

The membrane of claim 2 wherein at least 50 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl.

Claim 5

Dependent Claim 16 words

The membrane of claim 3 wherein R 1 is a C 1 -6 divalent hydrocarbon radical.

Claim 6

Dependent Claim 32 words

The membrane of claim 4 wherein the remainder of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively C 1-4 alkyl.

Claim 7

Dependent Claim 64 words

The membrane of claim 3 wherein the thin discriminating layer consists predominantly of a carbonate polymer derived from between about 50 and 100 percent of a bisphenol of Formula III ##STR10## and 0 and 50 percent of a bisphenol of Formula IV ##STR11## where R 1 is a C 1-6 divalent hydrocarbon; R 2 is C 1-4 alkyl; and X is chlorine or bromine.

Claim 8

Dependent Claim 10 words

The membrane of claim 6 wherein R 2 is methyl.

Claim 9

Dependent Claim 30 words

The membrane of claim 3 wherein 100 weight percent of the moieties derived from Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl.

Claim 10

Dependent Claim 30 words

The membrane of claim 8 wherein at least 50 weight percent of the moieties derived from Formula I present in the discriminating layer bear R groups which are exclusively Br.

Claim 11

Dependent Claim 64 words

The membrane of claim 2 wherein at least 35 weight percent of the moieties derived from Formula I present in the descriminating layer bear R groups which are exclusively Br, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 20° C. of at least 6.4 and a reduced flux of 1.12×10 -8 cc/cm 2 -sec-cm Hg or greater for oxygen.

Claim 12

Dependent Claim 25 words

The membrane of claim 10 wherein at least 50 weight percent of the moieties derived from Formula I bear R groups which are exclusively Br.

Claim 13

Dependent Claim 25 words

The membrane of claim 11 wherein the remainder of the R groups are C 1-4 alkyl, and R 1 is a C 1-6 divalent hydrocarbon.

Claim 14

Dependent Claim 23 words

The membrane of claim 12 wherein the remainder of the R groups are methyl and R 1 is a C 1-6 alkylidine moiety.

Claim 15

Dependent Claim 23 words

The membrane of claim 11 wherein 100 weight percent of the moieties derived from Formula I bear R groups which are exclusively bromine.

Claim 16

Dependent Claim 14 words

The membrane of claim 14 wherein R 1 is a C 1-6 divalent hydrocarbon.

Claim 17

Dependent Claim 28 words

The membrane of claim 15 wherein the bisphenol is tetrabromobisphenol A and the said gas separation membrane has a separation factor of at least 7.0 at 20° C.

Claim 18

Dependent Claim 37 words

A process for separating oxygen from nitrogen which comprises contacting a gaseous stream containing oxygen and nitrogen with the membrane of claim 1 under conditions such that oxygen selectively permeates through the membrane, in comparison to nitrogen.

Claim 19

Dependent Claim 47 words

The process of claim 17 wherein the membrane is sealingly engaged to a vessel which defines a space communicating with only one side of the membrane, such that the permeable oxygen contacting the other side of the membrane can permeate through the membrane to the non-communicating space.

Claim 20

Dependent Claim 55 words

The process of claim 18 which comprises a. contacting the gas stream, with the membrane under conditions such that oxygen selectively permeates through the membrane to the other side of the membrane; b. removing the permeated oxygen from the vicinity of the membrane; and c. removing the unpermeated nitrogen from the vicinity of the membrane.

Claim 21

Dependent Claim 19 words

The process of claim 19 wherein the membrane has a separation factor of 6.7 or greater at 20° C.

Claim 22

Dependent Claim 25 words

The process of claim 19 wherein the remainder of the R groups are hydrogen or methyl and R 1 is a C 1-6 divalent hydrocarbon.

Claim 23

Dependent Claim 23 words

The process of claim 21 wherein 100 weight percent of the moieties derived from Formula I bear R groups which are exclusively bromine.

Claim 24

Dependent Claim 14 words

The process of claim 22 wherein R 1 is a C 1-6 alkylidene moiety.

Claim 25

Dependent Claim 12 words

The process of claim 23 wherein the bisphenol is tetrabromo bisphenol A.

Claim 26

Dependent Claim 140 words

A semi-permeable asymmetric gas separation membrane comprising a thin discriminating layer consisting predominantly of a carbonate polymer derived from a bisphenol corresponding to Formula I ##STR12## where R at each occurrence is independently H, Cl, Br, or C 1 -C 4 alkyl and R 1 is ##STR13## --S--, --SO 2 --, --O--, or a C 1 -C 6 divalent hydrocarbon a C 1 -C 6 divalent fluorocarbon radical or inertly substituted hydrocarbon radical, with the proviso that at least 25 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 24° C. of at least 6.1 and a reduced flux of 8.53×10 -8 cc/cm 2 -sec-cm Hg or greater for oxygen.

Claim 27

Dependent Claim 140 words

A semi-permeable asymmetric gas separation membrane comprising a thin discriminating layer consisting predominantly of a carbonate polymer derived from a bisphenol corresponding to Formula I ##STR12## where R at each occurrence is independently H, Cl, Br, or C 1 -C 4 alkyl and R 1 is ##STR13## --S--, --SO 2 --, --O--, or a C 1 -C 6 divalent hydrocarbon a C 1 -C 6 divalent fluorocarbon radical or inertly substituted hydrocarbon radical, with the proviso that at least 25 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 24° C. of at least 6.1 and a reduced flux of 8.53×10 -8 cc/cm 2 -sec-cm Hg or greater for oxygen.

Claim 28

Dependent Claim 36 words

The membrane of claim 25 wherein at least 35 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups with which are exclusively Br or Cl.

Claim 29

Dependent Claim 35 words

The membrane of claim 26 wherein at least 50 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl.

Claim 30

Dependent Claim 15 words

The membrane of claim 27 wherein R 1 is a C 1-6 divalent hydrocarbon radical.

Claim 31

Dependent Claim 32 words

The membrane of claim 28 wherein the remainder of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively C 1-4 alkyl.

Claim 32

Dependent Claim 30 words

The membrane of claim 27 wherein 100 weight percent of the moieties derived from Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl.

Claim 33

Dependent Claim 30 words

The membrane of claim 30 wherein at least 50 weight percent of the moieties derived from Formula I present in the discriminating layer bear R groups which are exclusively Br.

Claim 34

Dependent Claim 64 words

The membrane of claim 26 wherein at least 35 weight percent of the moieties derived from Formula I present in the descriminating layer bear R groups which are exclusively Br, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 20° C. of at least 6.4 and a reduced flux of 5.69×10 -6 cc/cm 2 -sec-cm Hg or greater for oxygen.

Claim 35

Dependent Claim 25 words

The membrane of claim 32 wherein at least 50 weight percent of the moieties derived from Formula I bear R groups which are exclusively Br.

Claim 36

Dependent Claim 25 words

The membrane of claim 33 wherein the remainder of the R groups are C 1-4 alkyl, and R 1 is a C 1-6 divalent hydrocarbon.

Claim 37

Dependent Claim 23 words

The membrane of claim 34 wherein the remainder of the R groups are methyl and R 1 is a C 1-6 alkylidine moiety.

Claim 38

Dependent Claim 23 words

The membrane of claim 35 wherein 100 weight percent of the moieties derived from Formula I bear R groups which are exclusively bromine.

Claim 39

Dependent Claim 14 words

The membrane of claim 36 wherein R 1 is a C 1-6 divalent hydrocarbon.

Claim 40

Dependent Claim 28 words

The membrane of claim 37 wherein the bisphenol is tetrabromobisphenol A and the said gas separation membrane has a separation factor of at least 7.0 at 20° C.

Claim 41

Dependent Claim 37 words

A process for separating oxygen from nitrogen which comprises contacting a gaseous stream containing oxygen and nitrogen with the membrane of claim 25 under conditions such that oxygen selectively permeate through the membrane, in comparison to nitrogen.

Claim 42

Dependent Claim 47 words

The process of claim 39 wherein the membrane is sealingly engaged to a vessel which defines a space communicating with only one side of the membrane, such that the permeable oxygen contacting the other side of the membrane can permeate through the membrane to the non-communicating space.

Claim 43

Dependent Claim 135 words

An asymmetric gas separation membrane comprising a thin, discriminating layer consisting predominantly of a carbonate polymer derived from a bisphenol corresponding to Formula I ##STR14## wherein R at each occurrence is independently H, C, Br, or C 1 -C 4 alkyl and R 1 is ##STR15## --S--, --SO 2 --, --O--, or a C 1 -C 6 divalent hydrocarbon a C 1 -C 6 divalent fluorocarbon radical or inertly substituted hydrocarbon radical, with the proviso that at least 25 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 25° C. of at least 6.1 and a flux of 1.77×10 -5 cc/cm 2 -sec for oxygen.

Claim 44

Dependent Claim 135 words

An asymmetric gas separation membrane comprising a thin, discriminating layer consisting predominantly of a carbonate polymer derived from a bisphenol corresponding to Formula I ##STR14## wherein R at each occurrence is independently H, C, Br, or C 1 -C 4 alkyl and R 1 is ##STR15## --S--, --SO 2 --, --O--, or a C 1 -C 6 divalent hydrocarbon a C 1 -C 6 divalent fluorocarbon radical or inertly substituted hydrocarbon radical, with the proviso that at least 25 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 25° C. of at least 6.1 and a flux of 1.77×10 -5 cc/cm 2 -sec for oxygen.

Claim 45

Dependent Claim 35 words

The membrane of claim 41 wherein at least 50 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl.

Claim 46

Dependent Claim 15 words

The membrane of claim 42 wherein R 1 is a C 1-6 divalent hydrocarbon radical.

Claim 47

Dependent Claim 30 words

The membrane of claim 42 wherein 100 weight percent of the moieties derived from Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl.

Claim 48

Dependent Claim 62 words

The membrane of claim 41 wherein at least 35 weight percent of the moieties derived from Formula I present in the descriminating layer bear R groups which are exclusively Br, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 20° C. of at least 6.5 and a flux of 1.15×10 -3 cc/cm 2 -sec or greater for oxygen.

Claim 49

Dependent Claim 25 words

The membrane of claim 45 wherein at least 50 weight percent of the moieties derived from Formula I bear R groups which are exclusively Br.

Claim 50

Dependent Claim 23 words

The membrane of claim 46 wherein 100 weight percent of the moieties derived from Formula I bear R groups which are exclusively bromine.

Claim 51

Dependent Claim 14 words

The membrane of claim 47 wherein R 1 is a C 1-6 divalent hydrocarbon.

Claim 52

Dependent Claim 39 words

The membrane of claim 48 wherein the bisphenol is tetrabromobisphenol A and the said gas separation membrane has a separation factor of at least 7.0 at 20° C. with a flux of 3.52×10 -3 cc/cm 2 -sec or greater.

Claim 53

Dependent Claim 37 words

A process for separating oxygen from nitrogen which comprises contacting a gaseous stream containing oxygen and nitrogen with the membrane of claim 41 under conditions such that oxygen selectively permeates through the membrane, in comparison to nitrogen.

Claim 54

Dependent Claim 47 words

The process of claim 50 wherein the membrane is sealingly engaged to a vessel which defines a space communicating with only one side of the membrane, such that the permeable oxygen contacting the other side of the membrane can permeate through the membrane to the non-communicating space.

Claim 55

Dependent Claim 141 words

A composite gas separation membrane comprising a porous support and a thin, discriminating layer consisting predominantly of a carbonate polymer derived from a bisphenol corresponding to Formula I ##STR16## wherein R at each occurrence is independently H, Cl, Br, or C 1 -C 4 alkyl and R 1 is ##STR17## --S--, --SO 2 --, --O--, or a C 1 -C 6 divalent hydrocarbon or a C 1 -C 6 divalent fluorocarbon radical or inertly substituted hydrocarbon radical, with the proviso that at least 25 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 24° C. of at least 6.1 and a flux of 1.77×10 - 5 cc/cm 2 -sec for oxygen.

Claim 56

Dependent Claim 141 words

A composite gas separation membrane comprising a porous support and a thin, discriminating layer consisting predominantly of a carbonate polymer derived from a bisphenol corresponding to Formula I ##STR16## wherein R at each occurrence is independently H, Cl, Br, or C 1 -C 4 alkyl and R 1 is ##STR17## --S--, --SO 2 --, --O--, or a C 1 -C 6 divalent hydrocarbon or a C 1 -C 6 divalent fluorocarbon radical or inertly substituted hydrocarbon radical, with the proviso that at least 25 weight percent of the moieties derived from the bisphenol of Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 24° C. of at least 6.1 and a flux of 1.77×10 - 5 cc/cm 2 -sec for oxygen.

Claim 57

Dependent Claim 30 words

The membrane of claim 52 wherein 100 weight percent of the moieties derived from Formula I present in the discriminating layer bear R groups which are exclusively Br or Cl.

Claim 58

Dependent Claim 63 words

The membrane of claim 53 wherein at least 50 weight percent of the moieties derived from Formula I present in the discriminating layer bear R groups which are exclusively Br, said gas separation membrane exhibiting a separation factor for oxygen and nitrogen at 20° C. of at least 6.4 and a flux of 1.15×10 -3 cc/cm 2 -sec barrers or greater for oxygen.

Claim 59

Dependent Claim 23 words

The membrane of claim 54 wherein 100 weight percent of the moieties derived from Formula I bear R groups which are exclusively bromine.

Claim 60

Dependent Claim 14 words

The membrane of claim 55 wherein R 1 is a C 1-6 divalent hydrocarbon.

Claim 61

Dependent Claim 40 words

The membrane of claim 56 wherein the bisphenol is tetrabromobisphenol A and the said gas separation membrane has a separation factor of at least 7.0 at 20° C. with a flux of 3.52×10 -3 cc/cm 2 -sec barrers or greater.

Claim 62

Dependent Claim 37 words

A process for separating oxygen from nitrogen which comprises contacting a gaseous stream containing oxygen and nitrogen with the membrane of claim 52 under conditions such that oxygen selectively permeates through the membrane, in comparison to nitrogen.

Claim 63

Dependent Claim 47 words

The process of claim 58 wherein the membrane is sealingly engaged to a vessel which defines a space communicating with only one side of the membrane, such that the permeable oxygen contacting the other side of the membrane can permeate through the membrane to the non-communicating space.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1992-04-03	1992-10-03	1993-04-04	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1996-04-03	1996-10-03	1997-04-04	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2000-04-03	2000-10-03	2001-04-04	$7700.00	Window Closed / Lapsed

Semi-permeable membranes consisting predominantly of polycarbonates derived from tetrahalobisphenols

Abstract

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