US 4,888,032 A · Salts of cationic-metal dry cave complexes

Abstract

Salts containing cations of the formula: ##STR1## (in which M is Co, Fe, Cr or Mn, X, Y, R.sub.1, The Government has rights in this invention pursuant to Contract Number CHE-75-14837 awarded by the National Science Foundation.

Claims208

Dependent claims

A salt of a cationic metal complex of the formula:

##STR17## wherein:
M is Co, Fe, Cu, or Mn;
n+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge, said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula:
--(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --
where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group, or a methylimino group, subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula ##STR18## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino bridge.

12 more elements

A salt comprising a cationic metal complex of the formula:

##STR23## wherein:
M is Co, Fe, Cu or Mn;
n+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b -- where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group or a methylimino group, subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula:
##STR24## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino bridge;
and
Z is an electron donor selected from the group consisting of the halide ions, cyanate, thiocyanate, azide, acetonitrile, water, an alkanol containing not more than about five carbon atoms, pyridine, 4-aminopyridine, imidazole and N-methylimidazole.

13 more elements

A method for removing molecular oxygen from a gaseous mixture which comprises:

exposing a salt of the formula:
##STR32## wherein:
M is Co, Fe, Cu or Mn;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge, said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula:
--(CH.sub.2).sub.1 --G--(CH.sub.2).sub.b --
where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1, 4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group, or a methylimino group, subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula ##STR33## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino group,
to said mixture thereby allowing said cationic metal complex to complex molecular oxygen and thus to absorb oxygen from said gaseous mixture.

14 more elements

A method for removing molecular oxygen from a gaseous mixture, which comprises:

exposing a salt of the formula:
##STR34## wherein:
M is Co, Fe, Cu or Mn;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene 2-(2-pyridyl)-trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group or a methylimino group, subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula:
##STR35## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino group;
and
Z is an electron donor selected from the group consisting of the halide ions, cyanate, thiocyanate, azide, acetonitrile, water, an alkanol containing not more than about five carbon atoms, pyridine, 4-aminopyridine, imidazole and N-methylimidazole,
to said mixture thereby allowing said cationic metal complex to complex molecular oxygen and thus to absorb oxygen from said gaseous mixture.

15 more elements

In a method for increasing the proportion of a molecular oxygen in a gaseous mixture, which comprises:

passing said gaseous mixture over one face of an immobilized liquid membrane containing an oxygen-complexing compound;
allowing molecular oxygen to diffuse selectively through said liquid membrane;
removing from adjacent the opposed face of said liquid membrane an oxygen-enriched gas containing a higher proportion of molecular oxygen than said gaseous mixture,
the improvement which comprises using as said liquid membrane a liquid membrane containing a solution of salt comprising a cationic metal complex of the formula:
##STR36## wherein M is Co, Fe, Cu or Mn;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene, or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group consisting not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge, said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula:
--(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --
where a and b are each independently 1,2, or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group, or a methylimino group subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula:
##STR37## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino bridge.

16 more elements

In a method for increasing the proportion of a molecular oxygen in a gaseous mixture, which comprises:

passing said gaseous mixture over one face of an immobilized liquid membrane containing an oxygen-complexing compound;
allowing molecular oxygen to diffuse selectively through said liquid membrane;
removing from adjacent the opposed face of said liquid membrane an oxygen-enriched gas containing a higher proportion of molecular oxygen than said gaseous mixture,
the improvement which comprises using as said liquid membrane a liquid membrane containing a solution of a salt comprising a cationic metal complex of the formula:
##STR38## wherein:
M is Co, Fe, Cu or Mn;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyul group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
R.sub.6 independently is hydrogen or a methyl group, or the two R.sub.6 groups together form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula:
##STR39## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino bridge;
and
Z is an electron donor selected from the group consisting of the halide ions, cyanate, thiocyanate, azide, acetonitrile, water, an alkanol containing not more than about five carbon atoms, pyridine, 4-aminopyridine, imidazole and N-methylimidazole.

16 more elements

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing an atmospheric air feed stream into contact with a solution containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex which is a salt of a cation having the structure ##STR40## wherein:
M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about 4 carbon atoms, a phenyl group or a benzyl group;
R is a polymethylene group containing from about 4 to about 12 carbon atoms, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted-1,4-phenylene group, a 9,9-fluorylene group, an imino group or a methylimino group, subject to the proviso that, when G is an imino group or a methylimino group, the sum of a and b is at least 4;
and X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl-substituted-trimethylene or 2-(N-methyl-2-2 pyridino)-trimethylene group,
said solution adsorbing oxygen from said atmospheric air feed stream;
(b) collecting nitrogen from the atmospheric air feed stream after the oxygen has been adsorbed;
(c) desorbing oxygen from said solution to a gaseous product stream;
and
(d) collecting oxygen from the product stream after the oxygen has been desorbed.

11 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous, oxygen-containing feed stream into contact with a solution containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex which is a salt of a cation having the formula ##STR41## wherein:
M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about 4 carbon atoms, a phenyl group or a benzyl group;
R is a polymethylene group containing from about 4 to about 12 carbon atoms, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted-1,4-phenylene group, a 9,9-fluorylene group, an imino group or a methylimino group, subject to the proviso that when G is an imino group or a methylimino group, the sum of a and b is at least 4;
and X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl-substituted-trimethylene or 2-(N-methyl-2-2-pyridino)-trimethylene group,
said solution adsorbing oxygen from said gaseous oxygen-containing feed stream;
(b) desorbing oxygen from said solution to a gaseous product stream;
and
(c) collecting oxygen from the product stream after the oxygen has been desorbed.

10 more elements

A solution useful for the separation of oxygen and nitrogen from atmospheric air comprising a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving said axial base and said oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex which is a salt of a cation having the structure

wherein:
##STR44## M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about 4 carbon atoms, a phenyl group or a benzyl group;
R is a polymethylene group containing from about 4 to about 12 carbon atoms, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted-1,4-phenylene group, a 9,9-fluorylene group, an imino group or a methylimino group, subject to the proviso that when G is an imino group or a methylimino group, the sum of a and b is at least 4;
and X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl-substituted-trimethylene or 2-(N-methyl-2-2 pyridino)-trimethylene group.

6 more elements

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing atmospheric air into contact with a membrane, said membrane separating said atmospheric air into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the oxygen partial pressure on the product-stream side of said membrane lower than the oxygen partial pressure on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR51## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous oxygen-containing stream into contact with a membrane, said membrane separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the oxygen partial pressure on the product-stream side of said membrane lower than the oxygen partial pressure on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR52## wherein m is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing atmospheric air into contact with a membrane, said membrane separating said atmospheric air into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the temperature on the product-stream side of said membrane higher than the temperature on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR53## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous oxygen-containing stream into contact with a membrane, said membrane separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the temperature on the product-stream side of said membrane higher than the temperature on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR54## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

A membrane useful for the separation of oxygen and nitrogen from atmospheric air comprising a membrane support, said membrane support containing a solvent or solvent mixture, axial base, and oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR56## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;

n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

6 more elements

Apparatus for the separation and purification of oxygen and nitrogen comprising:

(a) membrane means,
(b) means for bringing atmospheric air into contact with said membrane means, said membrane means separating said atmospheric air into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) means for maintaining the oxygen partial pressure on the product-stream side of said membrane means lower than the oxygen partial pressure on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane means comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR58## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

11 more elements

Apparatus for the separation and purification of oxygen comprising:

(a) a membrane means,
(b) means for bringing a gaseous oxygen-containing stream into contact with said membrane means, said membrane means separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) means for maintaining the oxygen partial pressure on the product-stream side of said membrane means lower than the oxygen partial pressure on the feed-stream side of said membrane means.
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane means comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR59## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group, and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

Apparatus for the separation and purification of oxygen and nitrogen comprising:

(a) membrane means,
(b) means for bringing atmospheric air into contact with said membrane means, said membrane means separating said atmospheric air into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) temperature maintenance means for maintaining the temperature on the product-stream side of said membrane means higher than the temperature on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane means comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR60## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

11 more elements

Apparatus for the separation and purification of oxygen comprising:

(a) membrane means,
(b) means for bringing a gaseous oxygen-containing stream into contact with said membrane means, said membrane means separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) temperature maintenance means for maintaining the temperature on the product-stream side of said membrane means higher than the temperature on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane means comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR61## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

11 more elements

Dependencies are inferred from the claim text.

Facts

Application

06/571,812Filed 18 Jan 1984 · continuation in part

Priority

23 Jan 1980

Granted

19 Dec 1989

Term ends

Not estimatedThe source records don’t support an estimate.

Classification9 codes

C01B 13/0244
Chemical processing only: by complexation
C01B 13/0285
Physical processing only: by absorption in liquids
C07F 1/005
Compounds containing elements of Groups 1 or 11 of the Periodic Table: without C-Metal linkages
C07F 13/005
Compounds containing elements of Groups 7 or 17 of the Periodic Table: compounds without a metal-carbon linkage

Abstract

Claims208

Dependent claims

A salt of a cationic metal complex of the formula:

##STR17## wherein:
M is Co, Fe, Cu, or Mn;
n+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge, said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula:
--(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --
where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group, or a methylimino group, subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula ##STR18## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino bridge.

12 more elements

A salt comprising a cationic metal complex of the formula:

##STR23## wherein:
M is Co, Fe, Cu or Mn;
n+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b -- where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group or a methylimino group, subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula:
##STR24## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino bridge;
and
Z is an electron donor selected from the group consisting of the halide ions, cyanate, thiocyanate, azide, acetonitrile, water, an alkanol containing not more than about five carbon atoms, pyridine, 4-aminopyridine, imidazole and N-methylimidazole.

13 more elements

A method for removing molecular oxygen from a gaseous mixture which comprises:

exposing a salt of the formula:
##STR32## wherein:
M is Co, Fe, Cu or Mn;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge, said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula:
--(CH.sub.2).sub.1 --G--(CH.sub.2).sub.b --
where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1, 4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group, or a methylimino group, subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula ##STR33## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino group,
to said mixture thereby allowing said cationic metal complex to complex molecular oxygen and thus to absorb oxygen from said gaseous mixture.

14 more elements

A method for removing molecular oxygen from a gaseous mixture, which comprises:

exposing a salt of the formula:
##STR34## wherein:
M is Co, Fe, Cu or Mn;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene 2-(2-pyridyl)-trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group or a methylimino group, subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula:
##STR35## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino group;
and
Z is an electron donor selected from the group consisting of the halide ions, cyanate, thiocyanate, azide, acetonitrile, water, an alkanol containing not more than about five carbon atoms, pyridine, 4-aminopyridine, imidazole and N-methylimidazole,
to said mixture thereby allowing said cationic metal complex to complex molecular oxygen and thus to absorb oxygen from said gaseous mixture.

15 more elements

In a method for increasing the proportion of a molecular oxygen in a gaseous mixture, which comprises:

passing said gaseous mixture over one face of an immobilized liquid membrane containing an oxygen-complexing compound;
allowing molecular oxygen to diffuse selectively through said liquid membrane;
removing from adjacent the opposed face of said liquid membrane an oxygen-enriched gas containing a higher proportion of molecular oxygen than said gaseous mixture,
the improvement which comprises using as said liquid membrane a liquid membrane containing a solution of salt comprising a cationic metal complex of the formula:
##STR36## wherein M is Co, Fe, Cu or Mn;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene, or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group consisting not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
each R.sub.6 independently is hydrogen or a methyl group;
or the two R.sub.6 groups together form a nitrogen-nitrogen bridge, said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula:
--(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --
where a and b are each independently 1,2, or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, an imino group, or a methylimino group subject to the proviso that when G is a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula:
##STR37## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino bridge.

16 more elements

In a method for increasing the proportion of a molecular oxygen in a gaseous mixture, which comprises:

passing said gaseous mixture over one face of an immobilized liquid membrane containing an oxygen-complexing compound;
allowing molecular oxygen to diffuse selectively through said liquid membrane;
removing from adjacent the opposed face of said liquid membrane an oxygen-enriched gas containing a higher proportion of molecular oxygen than said gaseous mixture,
the improvement which comprises using as said liquid membrane a liquid membrane containing a solution of a salt comprising a cationic metal complex of the formula:
##STR38## wherein:
M is Co, Fe, Cu or Mn;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or 2-(N-methyl-2-pyridino)-trimethylene group;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyul group substituted by a halogen atom or by one or two methoxy groups;
or the two R.sub.3 groups together form a carbon-carbon bridge, said carbon-carbon bridge comprising a polymethylene bridge containing from 7 to about 12 carbon atoms or an m- or p-xylylene group;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about four carbon atoms, a phenyl group or a benzyl group;
R.sub.6 independently is hydrogen or a methyl group, or the two R.sub.6 groups together form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridge comprising a polymethylene group containing from 4 to about 12 carbon atoms, a polymethylene group containing from 4 to about 12 carbon atoms and substituted by a methoxycarbonyl group, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, a imino group or a methylimino group, the sum of a and b is at least 4;
or the two NR.sub.4 R.sub.6 groups together form a bis-piperazino bridge of the formula:
##STR39## where D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene group substituted by one or more methyl groups, a 9,10-anthracene group or a 2,6-pyridylene group
subject to the proviso that when the two R.sub.3 groups do not form a carbon-carbon bridge, either the two R.sub.6 groups must form a nitrogen-nitrogen bridge or the two NR.sub.4 R.sub.6 groups must form a bis-piperazino bridge;
and
Z is an electron donor selected from the group consisting of the halide ions, cyanate, thiocyanate, azide, acetonitrile, water, an alkanol containing not more than about five carbon atoms, pyridine, 4-aminopyridine, imidazole and N-methylimidazole.

16 more elements

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing an atmospheric air feed stream into contact with a solution containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex which is a salt of a cation having the structure ##STR40## wherein:
M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about 4 carbon atoms, a phenyl group or a benzyl group;
R is a polymethylene group containing from about 4 to about 12 carbon atoms, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted-1,4-phenylene group, a 9,9-fluorylene group, an imino group or a methylimino group, subject to the proviso that, when G is an imino group or a methylimino group, the sum of a and b is at least 4;
and X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl-substituted-trimethylene or 2-(N-methyl-2-2 pyridino)-trimethylene group,
said solution adsorbing oxygen from said atmospheric air feed stream;
(b) collecting nitrogen from the atmospheric air feed stream after the oxygen has been adsorbed;
(c) desorbing oxygen from said solution to a gaseous product stream;
and
(d) collecting oxygen from the product stream after the oxygen has been desorbed.

11 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous, oxygen-containing feed stream into contact with a solution containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex which is a salt of a cation having the formula ##STR41## wherein:
M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about 4 carbon atoms, a phenyl group or a benzyl group;
R is a polymethylene group containing from about 4 to about 12 carbon atoms, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted-1,4-phenylene group, a 9,9-fluorylene group, an imino group or a methylimino group, subject to the proviso that when G is an imino group or a methylimino group, the sum of a and b is at least 4;
and X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl-substituted-trimethylene or 2-(N-methyl-2-2-pyridino)-trimethylene group,
said solution adsorbing oxygen from said gaseous oxygen-containing feed stream;
(b) desorbing oxygen from said solution to a gaseous product stream;
and
(c) collecting oxygen from the product stream after the oxygen has been desorbed.

10 more elements

wherein:
##STR44## M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3;
each R.sub.1 independently is hydrogen or a methyl group;
each R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, an alkyl group containing not more than about 17 carbon atoms, a benzyl group, a phenyl group, or a phenyl group substituted by a halogen atom or by one or two methoxy groups;
each R.sub.4 independently is hydrogen, an alkyl group containing not more than about 4 carbon atoms, a cyanoalkyl group containing not more than about 4 carbon atoms, a phenyl group or a benzyl group;
R is a polymethylene group containing from about 4 to about 12 carbon atoms, or a grouping of the formula --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted-1,4-phenylene group, a 9,9-fluorylene group, an imino group or a methylimino group, subject to the proviso that when G is an imino group or a methylimino group, the sum of a and b is at least 4;
and X and Y are each independently an o-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl-substituted-trimethylene or 2-(N-methyl-2-2 pyridino)-trimethylene group.

6 more elements

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing atmospheric air into contact with a membrane, said membrane separating said atmospheric air into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the oxygen partial pressure on the product-stream side of said membrane lower than the oxygen partial pressure on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR51## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous oxygen-containing stream into contact with a membrane, said membrane separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the oxygen partial pressure on the product-stream side of said membrane lower than the oxygen partial pressure on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR52## wherein m is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing atmospheric air into contact with a membrane, said membrane separating said atmospheric air into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the temperature on the product-stream side of said membrane higher than the temperature on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR53## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous oxygen-containing stream into contact with a membrane, said membrane separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the temperature on the product-stream side of said membrane higher than the temperature on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR54## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

6 more elements

Apparatus for the separation and purification of oxygen and nitrogen comprising:

(a) membrane means,
(b) means for bringing atmospheric air into contact with said membrane means, said membrane means separating said atmospheric air into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) means for maintaining the oxygen partial pressure on the product-stream side of said membrane means lower than the oxygen partial pressure on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane means comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR58## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

11 more elements

Apparatus for the separation and purification of oxygen comprising:

(a) a membrane means,
(b) means for bringing a gaseous oxygen-containing stream into contact with said membrane means, said membrane means separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) means for maintaining the oxygen partial pressure on the product-stream side of said membrane means lower than the oxygen partial pressure on the feed-stream side of said membrane means.
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane means comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR59## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group, and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

10 more elements

Apparatus for the separation and purification of oxygen and nitrogen comprising:

(a) membrane means,
(b) means for bringing atmospheric air into contact with said membrane means, said membrane means separating said atmospheric air into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) temperature maintenance means for maintaining the temperature on the product-stream side of said membrane means higher than the temperature on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane means comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR60## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

11 more elements

Apparatus for the separation and purification of oxygen comprising:

(a) membrane means,
(b) means for bringing a gaseous oxygen-containing stream into contact with said membrane means, said membrane means separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) temperature maintenance means for maintaining the temperature on the product-stream side of said membrane means higher than the temperature on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane means comprising a membrane support, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base, and oxygen carrier being in the liquid phase when present together, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having either of the structures ##STR61## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
n.sup.+ is a positive oxidation state of M, n being not greater than 3:
in Formula I, each R.sub.1 is hydrogen and each R.sub.2 is methyl, while in Formula III, each R.sub.1 and R.sub.2 independently is hydrogen or a methyl group;
each R.sub.3 independently is hydrogen, alkyl or aryl;
each R.sub.4 independently is hydrogen, or an alkyl or aryl group;
R is an alkylene or arylene group or a nitrogen-containing moiety;
R.sub.5 is an alkylene or arylene group;
each R.sub.6 independently is hydrogen or an alkyl group;
and
X and Y are each independently an alkylene or arylene group or a nitrogen-containing moiety.

11 more elements

Dependencies are inferred from the claim text.

Salts of cationic-metal dry cave complexes

Life of this patent

Abstract

Claims208

Salts of cationic-metal dry cave complexes

Life of this patent

Abstract

Claims208