Method for supporting metalloporphyrins on polybenzimidazole porous articles

Claim 2

A process for the production of a microporous polybenzimidazole article onto which a metalloporphyrin complex has been bound comprising: (a) preparing a microporous polybenzimidazole shaped article; (b) reacting the microporous polybenzimidazole article with a strong base to produce a polybenzimidazole anion on the surface of the article; and (c) mixing the anionized polybenzimidazole article with a metalloporphyrin salt solution to form a microporous polybenzimidazole article supporting a metalloporphyrin complex.

Claim 3

A process for the production of a polybenzimidazole article onto which a metalloporphyrin complex has been bound comprising: (a) preparing a microporous polybenzimidazole particulate wherein the polybenzimidazole polymer is characterized by recurring monomeric units of: ##STR5## wherein R is a tetravalent aromatic nucleus, with the nitrogen atoms forming the benzimidazole rings paired adjacent carbon atoms of said aromatic nucleus, and R' is selected from the group consisting of (1) an aromatic ring, (2) an alkylene group having from four to eight carbon atoms, and (3) a heterocyclic ring selected from the group consisting of (a) pyridine, (b) pyrazine, (c) furan, (d) quinoline, (e) thiophene and (f) pyran; (b) reacting the microporous polybenzimidazole particulate with a solution of a strong base with a pka of at least about 9 to produce a polybenzimidazole anion on the surface of the polybenzimidazole particulate; and (c) mixing the anionized, microporous polybenzimidazole particulate with a metalloporphyrin salt solution, wherein the metal of the metalloporphyrin is selected from the group consisting of chromium, manganese, iron, cobalt, rhodium and nickel, to form a microporous polybenzimidazole particulate supporting a metalloporphyrin complex.

Claim 4

A process for the production of a polybenzimidazole article onto which a metalloporphyrin complex has been bound comprising: (a) preparing a microporous polybenzimidazole particulate wherein the polybenzimidazole polymer is characterized by recurring monomeric units of: ##STR5## wherein R is a tetravalent aromatic nucleus, with the nitrogen atoms forming the benzimidazole rings paired adjacent carbon atoms of said aromatic nucleus, and R' is selected from the group consisting of (1) an aromatic ring, (2) an alkylene group having from four to eight carbon atoms, and (3) a heterocyclic ring selected from the group consisting of (a) pyridine, (b) pyrazine, (c) furan, (d) quinoline, (e) thiophene and (f) pyran; (b) reacting the microporous polybenzimidazole particulate with a solution of a strong base with a pka of at least about 9 to produce a polybenzimidazole anion on the surface of the polybenzimidazole particulate; and (c) mixing the anionized, microporous polybenzimidazole particulate with a metalloporphyrin salt solution, wherein the metal of the metalloporphyrin is selected from the group consisting of chromium, manganese, iron, cobalt, rhodium and nickel, to form a microporous polybenzimidazole particulate supporting a metalloporphyrin complex.

Claim 5

A process for the production of a polybenzimidazole article onto which a metalloporphyrin complex has been bound comprising: (a) preparing a microporous polybenzimidazole particulate wherein the polybenzimidazole polymer is poly-2,2-(m-phenylene)-5,5-bibenzimidzole; (b) reacting the microporous polybenzimidazole particulate with sodium methoxide with a pka of at least about 9 to produce a polybenzimidazole anion on the surface of the polybenzimidazole particulate; and (c) mixing the anionized microporous polybenzimidazole particulate with an iron metalloporphyrin salt to form a microporous, polybenzimidazole particulate supporting an iron metalloporphyrin complex.

Claim 6

A process for the production of a polybenzimidazole article onto which a metalloporphyrin complex has been bound comprising: (a) preparing a microporous polybenzimidazole particulate wherein the polybenzimidazole polymer is poly-2,2-(m-phenylene)-5,5-bibenzimidzole; (b) reacting the microporous polybenzimidazole particulate with sodium methoxide with a pka of at least about 9 to produce a polybenzimidazole anion on the surface of the polybenzimidazole particulate; and (c) mixing the anionized microporous polybenzimidazole particulate with an iron metalloporphyrin salt to form a microporous, polybenzimidazole particulate supporting an iron metalloporphyrin complex.

Claim 7

The process as in any of claims 2 or 3 wherein the particulates have a porosity of at least about 10 percent.

Claim 8

The process as in any of claims 2 or 3 wherein the particulates have a specific area of at least about 10m 2 /g and an average pore diameter of from about 50 to about 500 Angstroms.

Claim 9

The process as in any of claims 1 or 2 wherein the strong base is selected from the group consisting of alkali metal hydroxides, hydrides, C 1 -C 6 alkoxides and other bases having a pka of at least about 9.

Claim 10

The process of claim 6 wherein the strong base is sodium methoxide.

Claim 11

The process as in any of claims 1 or 2 wherein the ratio of the equivalents of strong base anion to polybenzimidazole imidazole group equivalent is from about 1 to to 1 to about 8 to 1.

Claim 12

The process as in any of claims 1 or 2 wherein the ratio of the equivalents of the strong base anion to the polybenzimidazole imidazole group equivalent is from about 5 to 1 to about 8 to 1.

Claim 13

The process as in any of claim 2 or 3 wherein the microporous polybenzimidazole polymer particulate/strong base solution is reacted under an inert atmosphere for a period of about 1 to about 10 hours.

Claim 14

The product produced in accordance with the process of claim 1.

Claim 15

The product produced in accordance with the process of claim 2.

Claim 16

The product produced in accordance with the process of claim 3.

Claim 17

A catalyst comprised of a metalloporphyrin bound through its metal cation to a polybenzimidazole article.

Claim 18

A catalyst comprised of a metalloporphyrin bound through its metal cation to a polybenzimidazole article.

Claim 19

The product of claim 14 wherein the polybenzimidazole article is a particulate.

Claim 20

The product of claim 14 wherein the polybenzimidazole article is a film.

Claim 21

The product of claim 14 wherein the metal of the metalloporphyrin salt is selected from the group consisting of metals belonging to groups VIA, VIIA, VIII, VIIIA, IB, and IIIB of the fourth to the sixth periods of the periodic table.

Claim 22

The product of claim 14 wherein the metal of the metalloporphyrin is selected from the group consisting of chromium, manganese, iron, cobalt, rhodium and nickel.

Claim 23

The product of claim 14, wherein the metal of the metalloporphyrin is iron.

Claim 24

A process for the production of a microporous polybenzimidazole article onto which a metalloporphyrin complex has been bound comprising: (a) preparing a microporous polybenzimidazole shaped article; and (b) mixing the polybenzimidazole shaped article with a metalloporphyrin salt solution to form a microporous polybenzimidazole article supporting a metalloporphyrin complex.

Claim 25

A process for the production of a microporous polybenzimidazole article onto which a metalloporphyrin complex has been bound comprising: (a) preparing a microporous polybenzimidazole shaped article; and (b) mixing the polybenzimidazole shaped article with a metalloporphyrin salt solution to form a microporous polybenzimidazole article supporting a metalloporphyrin complex.

Claim 26

The process as in any of claims 1, 2, 3 or 20 wherein the polybenzimidazole article is a particulate.

Claim 27

The process as in any of claims 1 or 20 wherein the polybenzimidazole article is a film.

Claim 28

The process as in any of claims 1 or 20 wherein the polybenzimidazole article is a fiber.

Claim 29

The process as in any of claims 1, 2, 3 or 20 wherein the metal of the metalloporphyrin salt is selected from the group consisting of metals belonging to groups VIA, VIIA, VIII, VIIIB, IB, and IIIB of the fourth to the sixth periods of the periodic table.

Claim 30

The process of claim 24 wherein the metal of the metalloporphyrin is selected from the group consisting of chromium, manganese, iron, cobalt, rhodium and nickel.

Claim 31

The process as in any of claims 1, 2 or 20 wherein the metal of the metalloporphyrin is iron.

Claim 32

The process as in any of claims 1 or 20 wherein the polybenzimidazole polymer consists essentially of recurring units of the formula: ##STR6## wherein R is a tetravalent aromatic nucleus, with the nitrogen atoms forming the benzimidazole rings paired adjacent carbon atoms of said aromatic nucleus, and R' is selected from the group consisting of (1) an aromatic ring, (2) an alkylene group having from four to eight carbon atoms, and (3) a heterocyclic ring selected from the group consisting of (a) pyridine, (b) pyrazine, (c) furan, (d) quinoline, (e) thiophene and (f) pyran.

Claim 33

The process as in any of claims 1 or 20 wherein the polybenzimidazole polymer consists essentially of recurring units of the formula: ##STR7## wherein Z is an aromatic nucleus having the nitrogen atoms forming the benzimidazole rings paired upon adjacent carbon atoms of said aromatic nucleus.

Claim 34

The process as in any of claims 1 or 20 wherein the polybenzimidazole polymer is poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole.

Claim 35

The process as in any of claims 1, 2, 3 or 20 wherein the solvent for the metalloporphyrin is selected from the group consisting of chloroform, dichloromethane, methanol, toluene, benzene, hexane and ethanol.

Claim 36

The process of claim 30 wherein the solvent for the metalloporphyrin salt is dichloromethane.

Claim 37

The process of claim 20 wherein the anion of the metalloporphyrin salt is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate and perchlorate.

Claim 38

The process of claim 20 wherein the anion of the metalloporphyrin salt is tetrafluoroborate.

Claim 39

The process of claim 20 wherein the metalloporphyrin salt is octaethylporphyrin manganese tetrafluoroborate.

Claim 40

The process of claim 20 wherein the polybenzimidazole articles and the metalloporphyrin solution are mixed for 48 to 240 hours.

Claim 41

The process as in any of claims 1, 2, 3 or 20 wherein about 0.01 to about 1 percent of the imidazole nitrogen sites on the polybenzimidazole article are bound to the metalloporphyrin.

Claim 42

The product produced in accordance with the process of claim 20.