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Last Updated: January 26, 2022

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Claims for Patent: 6,545,102

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Summary for Patent: 6,545,102
Title: Polymer-supported photosensitizers
Abstract:Improved polymer-immobilized photosensitizer are disclosed as well as methods of preparing and using them. The polymer-immobilized photosensitizers comprise a cross-linked polymer backbone, a plurality of cationic ammonium or phosphonium groups covalently bound to the polymer backbone and an immobilized photosensitizer. The average total number of carbon atoms in the ammonium or phosphonium group is at least four and preferably at least 12. The photosensitizer can be either covalently or ionically bound to the polymer. Polymer-supported photosensitizers of the invention are unexpectedly superior in catalyzing the photosensitized oxidation of compounds containing carbon-carbon double bonds.
Inventor(s): Akhavan-Tafti; Hashem (Howell, MI), Handley; Richard S. (Canton, MI), Sandison; Mark D. (Dearborn, MI), Larkin; Randall K. (West Bloomfield, MI)
Assignee: Lumigen, Inc. (Southfield, MI)
Application Number:09/965,692
Patent Claims:1. A polymer-immobilized photosensitizer comprising a cross-linked polymer backbone to which is bound a plurality of anionic photosensitizer groups and a plurality of cationic groups .sup.+ QR.sub.3 wherein Q is selected from phosphorus and nitrogen, each R is independently a straight, branched or cyclic alkyl group of 1 to about 20 carbons or an aralkyl group and the average total number of carbon atoms in the group QR.sub.3 is at least four.

2. The polymer-immobilized photosensitizer of claim 1 wherein the average total number of carbon atoms in the group QR.sub.3 is from 4 to about 40.

3. The polymer-immobilized photosensitizer of claim 1 wherein the average total number of carbon atoms in the group QR.sub.3 is from 12 to about 30.

4. The polymer-immobilized photosensitizer of claim 1 wherein all groups QR.sub.3 are identical.

5. The polymer-immobilized photosensitizer of claim 1 comprising at least two different groups QR.sub.3.

6. The polymer-immobilized photosensitizer of claim 4 wherein Q is a phosphorus atom.

7. The polymer-immobilized photosensitizer of claim 1 wherein the photosensitizer group is selected from Rose Bengal, Eosin Y, Alizarin Red S, Congo Red, Orange G, fluorescein dyes, rhodamine dyes, Erythrosin B, chlorophyllin trisodium salt, salts of hemin, hematoporphyrin, Methylene Blue, Crystal Violet and Malachite Green.

8. The polymer-immobilized photosensitizer of claim 1 wherein the photosensitizer group is Rose Bengal.

9. The polymer-immobilized photosensitizer of claim 1 wherein the photosensitizer groups are covalently linked to the polymer backbone through linker groups.

10. The polymer-immobilized photosensitizer of claim 1 wherein the photosensitizer groups are bound to the polymer by electrostatic attraction to the cationic groups.

11. The polymer-immobilized photosensitizer of claim 1 wherein Q is a phosphorus atom, the average total number of carbon atoms in the group QR.sub.3 is from 12 to about 30 and the photosensitizer group is Rose Bengal.

12. The polymer-immobilized photosensitizer of claim 1 having the formula: ##STR12##

wherein A, B and C together with the two carbons of the polymer chain represent ethylenically unsaturated monomer units which can include alkyl substituents on the chains, A is a monovalent group selected from hydrogen, halogen, alkyl, aryl, aralkyl, carboxyl ester --COOR, oxycarbonyl, --OC(.dbd.O)R, and carboxamide --C(.dbd.O)NR.sub.2, B and C are each either a bond or a divalent linker group selected from alkylene, arylene, aralkylene, carboxyl --COO--, oxycarbonyl, --OC(.dbd.O)--, and carboxamide --C(.dbd.O)NR--, wherein m, n and p represent the mole fraction of the respective monomer units wherein p is from about 0.01 to about 0.1, m is from 0 to about 0.95, n is from about 0.05 to about 0.95, wherein Q is selected from phosphorus and nitrogen, each R is independently a straight, branched or cyclic alkyl group of 1 to about 20 carbons or an aralkyl group and the average total number of carbon atoms in the group QR.sub.3 is at least 4 and Sens is an anionic photosensitizer group.

13. The polymer-immobilized photosensitizer of claim 12 having the formula: ##STR13##

wherein A is a phenyl group, B is a benzyl group, C is a p-phenylene group.

14. The polymer-immobilized photosensitizer of claim 13 wherein Q is a phosphorus atom, the average total number of carbon atoms in the group QR.sub.3 is from 12 to about 30 and the photosensitizer group is Rose Bengal.

15. The polymer-immobilized photosensitizer of claim 1 having the formula: ##STR14##

wherein A, B and C together with the two carbons of the polymer chain represent ethylenically unsaturated monomer units which can include alkyl substituents on the chains, A is a monovalent group selected from hydrogen, halogen, alkyl, aryl, aralkyl, carboxyl ester --COOR, oxycarbonyl, --OC(.dbd.O)R, and carboxamide --C(.dbd.O)NR.sub.2, B and C are each either a bond or a divalent linker group selected from alkylene, arylene, aralkylene, carboxyl --COO--, oxycarbonyl, --OC(.dbd.O)--, and carboxamide --C(.dbd.O)NR--, wherein l, m, n and p represent the mole fraction of the respective monomer units wherein p is from about 0.01 to about 0.1, m is from 0 to about 0.95, n is from about 0.05 to about 0.95, l is from about 0.05 to about 0.95, wherein Q is selected from phosphorus and nitrogen, each R is independently a straight, branched or cyclic alkyl group of 1 to about 20 carbons or an aralkyl group and the average total number of carbon atoms in the group QR.sub.3 is at least 4, wherein X is selected from halide and sulfonate ester and Sens is a photosensitizer group.

16. The polymer-immobilized photosensitizer of claim 15 having the formula: ##STR15##

wherein in the precursor polymer, A is a phenyl group, B is a benzyl group, C is a p-phenylene group, wherein p is from 0.01 to about 0.1, m is from 0.5 to 0.95, l and n are each from about 0.05 to about 0.5.

17. The polymer-immobilized photosensitizer of claim 16 wherein Q is a phosphorus atom, the average total number of carbon atoms in the group QR.sub.3 is from 12 to about 30 and the photosensitizer group is Rose Bengal.

18. A polymer-immobilized photosensitizer prepared by a) providing a precursor polymer having the formula ##STR16## wherein A, B and C together with the two carbons of the polymer chain represent ethylenically unsaturated monomer units which can include alkyl substituents on the chains, A is a monovalent group selected from hydrogen, halogen, alkyl, aryl, aralkyl, carboxyl ester --COOR, oxycarbonyl, --OC(.dbd.O)R, and carboxamide --C(.dbd.O)NR.sub.2, B and C are each either a bond or a divalent linker group selected from alkylene, arylene, aralkylene, carboxyl --COO--, oxycarbonyl, --OC(.dbd.O)--, and carboxamide --C(.dbd.O)NR--, X is a reactive leaving group capable of being displaced in a nucleophilic displacement reaction, m, n and p represent the mole fraction of the respective monomer units wherein p is from about 0.01 to about 0.1, m is from 0 to about 0.95, n is from about 0.05 to about 0.95; b) reacting the polymer with at least 1 amine or phosphine of the formula QR.sub.3, wherein Q is selected from phosphorus and nitrogen, each R is independently a straight, branched or cyclic alkyl group of 1 to about 20 carbons or an aralkyl group provided that the average total number of carbon atoms in the group QR.sub.3 is from 4 to about 40, to produce a cationic polymer in which some of the reactive groups are converted to quaternary ammonium or phosphonium groups .sup.+ QR.sub.3 X.sup.- ; and c) reacting the resulting polymer with an anionic photosensitizer to substantially exchange the anion X.sup.- for the sensitizer Sens.sup.- producing the polymer-immobilized photosensitizer.

19. The polymer-immobilized photosensitizer prepared by the process of claim 18 wherein the reactive groups are substantially converted to quaternary ammonium or phosphonium groups .sup.+ QR.sub.3 X.sup.-.

20. The polymer-immobilized photosensitizer prepared by the process of claim 18 wherein Sens.sup.- is selected from Rose Bengal, Eosin Y, Alizarin Red S, Congo Red, Orange G, fluorescein dyes, rhodamine dyes, Erythrosin B, chlorophyllin trisodium salt, salts of hemin and hematoporphyrin.

21. The polymer-immobilized photosensitizer prepared by the process of claim 18 wherein Sens.sup.- is Rose Bengal.

22. The polymer prepared by the process of claim 18 wherein the average total number of carbon atoms in the group QR.sub.3 is from about 12 to about 30.

23. The polymer prepared by the process of claim 18 wherein only one compound QR.sub.3 is used and each R is an alkyl group.

24. The polymer prepared by the process of claim 18 wherein more than one compound QR.sub.3 is used and each R is an alkyl group.

25. The polymer-immobilized photosensitizer prepared by the process of claim 18 wherein in the precursor polymer, A is a phenyl group, B is a benzyl group, C is a p-phenylene group and having the formula: ##STR17##

wherein the amount of cross-linking (p) is from about 0.1 to about 0.01, m is from about 0.75 to about 0.95, n is from about 0.05 to about 0.25 and the group X is a halogen atom.

26. The polymer-immobilized photosensitizer prepared by the process of claim 25 wherein Sens.sup.- is selected from Rose Bengal, Eosin Y, Alizarin Red S, Congo Red, Orange G, fluorescein dyes, rhodamine dyes, Erythrosin B, chlorophyllin trisodium salt, salts of hemin and hematoporphyrin.

27. The polymer-immobilized photosensitizer prepared by the process of claim 25 wherein Sens.sup.- is Rose Bengal.

28. The polymer prepared by the process of claim 25 wherein the average total number of carbon atoms in the group QR.sub.3 is from 4 to about 40.

29. The polymer prepared by the process of claim 25 wherein the average total number of carbon atoms in the group QR.sub.3 is from about 12 to about 30.

30. The polymer prepared by the process of claim 25 wherein only one compound QR.sub.3 is used and each R is an alkyl group.

31. The polymer prepared by the process of claim 25 wherein more than one compound QR.sub.3 is used and each R is an alkyl group.

32. The polymer prepared by the process of claim 25 wherein only one compound QR.sub.3 is used and each R is an alkyl group, the average total number of carbon atoms in the group QR.sub.3 is from 12 to about 30, and Sens.sup.- is Rose Bengal.

33. A polymer-immobilized photosensitizer prepared by a) providing a precursor polymer having the formula ##STR18## wherein A, B and C together with the two carbons of the polymer chain represent ethylenically unsaturated monomer units which can include alkyl substituents on the chains, A is a monovalent group selected from hydrogen, halogen, alkyl, aryl, aralkyl, carboxyl ester --COOR, oxycarbonyl, --OC(.dbd.O)R, and carboxamide --C(.dbd.O)NR.sub.2, B and C are each either a bond or a divalent linker group selected from alkylene, arylene, aralkylene, carboxyl --COO--, oxycarbonyl, --OC(.dbd.O)--, and carboxamide --C(.dbd.O)NR--, X is a reactive leaving group capable of being displaced in a nucleophilic displacement reaction, m, n and p represent the mole fraction of the respective monomer units wherein p is from about 0.01 to about 0.1, m is from 0 to about 0.95, n is from about 0.05 to about 0.95; b) reacting the precursor polymer with 1) a specified limiting amount of a photosensitizer in a solvent to effect covalent bonding of the photosensitizer to the polymer by displacement of some of the leaving groups and 2) at least 1 amine or phosphine of the formula QR.sub.3, wherein Q is selected from phosphorus and nitrogen, each R is independently a straight, branched or cyclic alkyl group of 1 to about 20 carbons or an aralkyl group provided that the average total number of carbon atoms in the group QR.sub.3 is at least four, to displace additional leaving groups with QR.sub.3 thereby forming quaternary ammonium or phosphonium groups .sup.+ QR.sub.3 X.sup.-.

34. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein in the precursor polymer, A is a phenyl group, B is a benzyl group, C is a p-phenylene group and having the formula: ##STR19##

wherein the amount of cross-linking (p) is from about 0.1 to about 0.01, m is from about 0.75 to about 0.95, n is from about 0.05 to about 0.25 and the group X is a halogen atom.

35. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein the limiting amount of photosensitizer molecules results in displacement of from about 0.01% to about 50% of the reactive groups X.

36. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein the limiting amount of photosensitizer molecules results in displacement of from about 0.1% to about 20% of the reactive groups X.

37. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein in the second step at least 50% of the available reactive groups are displaced with QR.sub.3.

38. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein in the second step the available reactive groups are substantially completely displaced with QR.sub.3.

39. The polymer prepared by the process of claim 33 wherein Sens.sup.- is selected from Rose Bengal, Eosin Y, Alizarin Red S, Congo Red, Orange G, fluorescein dyes, rhodamine dyes, Erythrosin B, chlorophyllin trisodium salt, salts of hemin, hematoporphyrin, Methylene Blue, Crystal Violet and Malachite Green.

40. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein Sens.sup.- is Rose Bengal.

41. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein the average total number of carbon atoms in the group QR.sub.3 is from 4 to about 40.

42. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein the average total number of carbon atoms in the group QR.sub.3 is from about 12 to about 30.

43. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein only one compound QR.sub.3 is used and each R is an alkyl group.

44. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein more than one compound QR.sub.3 is used and each R is an alkyl group.

45. The polymer-immobilized photosensitizer prepared by the process of claim 33 wherein the precursor polymer is first reacted with the limiting amount of the photosensitizer and then with the amines or phosphines QR.sub.3.

46. The polymer-immobilized photosensitizer prepared by the process of claim 34 wherein only one compound QR.sub.3 is used, each R is an alkyl group, the average total number of carbon atoms in the group QR.sub.3 is from 12 to about 30, Sens.sup.- is Rose Bengal, wherein the limiting amount of photosensitizer molecules results in displacement of from about 0.1% to about 20% of the reactive groups X, and wherein in the second step the available reactive groups are substantially completely displaced with QR.sub.3.

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