Aminopyridyl siloxanes
| Title: | Aminopyridyl siloxanes |
|---|---|
| Patent Number: | 5,194,555 |
| Publication Date: | March 16, 1993 |
| Appl. No: | 07/664,871 |
| Application Filed: | March 05, 1991 |
| Abstract: | Silanes and Siloxanes incorporating the 4-dialkylaminopyridine functionality are described. Preferred silanes are catalytically active and also serve as precursors to the siloxanes. Preferred polysiloxanes incorporating DAAP functionality exhibit excellent physical and dynamic-mechanical properties while maintaining a substantial percentage of the DAAP catalytic behavior. |
| Inventors: | Zeldin, Martel (Indianapolis, IN); Fife, Wilmer K. (Indianapolis, IN); Rubinsztajn, Slawomir (Carmel, IN) |
| Assignees: | Indiana University Foundation (IN) |
| Claim: | What is claimed is |
| Claim: | 1. A nucleophilic and basic composition comprising a siloxane polymer incorporating 4-dialkylaminopyridine functionality. |
| Claim: | 2. The composition of claim 1 which is effective as a catalyst for an acylation, ester rearrangement, polymerization, oxidation or reduction reaction. |
| Claim: | 3. The composition of claim 1 which comprises a siloxane having 4-dialkylaminopyridine groups pendant from or incorporated into its polymer backbone. |
| Claim: | 4. The composition of claim 3 wherein the siloxane is thermally stable at temperatures of at least about 375.degree. C. |
| Claim: | 5. The composition of claim 3 wherein the siloxane catalyzes a transacylation of 1-methylcyclohexanol and acetic anhydride at a rate of at least about 75% that of 4-dimethylaminopyridine. |
| Claim: | 6. The composition of claim 3 wherein the siloxane has a molecular weight of about 1.times.10.sup.3 to about 1.times.10.sup.6. |
| Claim: | 7. The composition of claim 6 wherein the siloxane is a homopolymer. |
| Claim: | 8. The composition of claim 7 wherein said siloxane has a molecular weight from about 3000 to about 10,000. |
| Claim: | 9. The composition of claim 6 wherein the siloxane is a co-polymer. |
| Claim: | 10. The composition of claim 9 wherein the siloxane has a molecular weight of at least about 100,000. |
| Claim: | 11. The composition of claim 6 wherein the siloxane is a linear polymer. |
| Claim: | 12. The composition of claim 6 wherein the siloxane is a cross-linked polymer. |
| Claim: | 13. The composition of claim 6 wherein the siloxane has 4-dialkylaminopyridine groups pendant from its polymer backbone. |
| Claim: | 14. The composition of claim 6 wherein the siloxane has 4-dialkylaminopyridine groups included in its polymer backbone. |
| Claim: | 15. The composition of claim 6 wherein the siloxane has repeating units derived from a silane including a 4-dialkylaminopyridine group having at least one alkoxysilyl group connected to its 4-dialkylamino moiety. |
| Claim: | 16. The composition of claim 13 wherein the siloxane has repeating units derived from a silane including a single 4-dialkylaminopyridine group having a single alkoxysilyl group connected to its 4-dialkylamino moiety. |
| Claim: | 17. The composition of claim 13 wherein the siloxane has repeating units derived from N-(3-Diethoxy(methyl)silyl)propyl)-N-methyl-4-aminopyridine. |
| Claim: | 18. The composition of claim 13 wherein the siloxane has repeating units derived from N-(3-(Triethoxysilyl)propyl)-N-methyl-4-aminopyridine. |
| Claim: | 19. The composition of claim 14 wherein the siloxane has repeating units derived from a silane which includes a single 4-dialkylaminopyridine group having two alkoxysilyl groups attached to its 4-dialkylamino moiety. |
| Claim: | 20. The composition of claim 14 wherein the siloxane has repeating units derived from N,N[Bis(3-(dimethyl(ethoxy)silyl)propyl)]-4-aminopyridine. |
| Claim: | 21. The composition of claim 14 wherein the siloxane has repeating units derived from N,N[Bis(3-diethoxy(methyl)silyl)propyl)]-4-aminopyridine. |
| Claim: | 22. The composition of claim 14 wherein the siloxane has repeating units derived from N,N[Bis(3-triethoxysilyl)propyl)]-4-aminopyridine. |
| Claim: | 23. A polymer comprising a chemically active, heat stable siloxane having repeating monomeric units having the formula: ##STR6## where Me=methyl. |
| Claim: | 24. The polymer of claim 23 having repeating monomeric units having the formula: ##STR7## where Me=methyl. |
| Claim: | 25. The polymer of claim 24 which also comprises repeating units of the formula: ##STR8## |
| Claim: | 26. The polymer of claim 24 which is crosslinked with MeSi(OEt).sub.3 or Si(OEt).sub.4, where Et=ethyl. |
| Claim: | 27. The polymer of claim 25 which is crosslinked with MeSi(OEt).sub.3 or Si(OEt).sub.4, where Et=ethyl. |
| Claim: | 28. A process for preparing a nucleophilic and basic silane composition, comprising the step of hydrosilating 4-(N-methylallylamino)pyridine or 4-(N-diallylamino)pyridine with an alkoxyhydrosilane. |
| Claim: | 29. The process of claim 28 wherein said hydrosilating step occurs upon heating said reactants in the presence of a suitable hydrosilation catalyst. |
| Claim: | 30. The process of claim 29 wherein said alkoxyhydrosilane has the formula: ##STR9## wherein n=0, 1 or 2 and R=methyl, ethyl, propyl, or iso-propyl, and Me=methyl. |
| Claim: | 31. The process of claim 30 wherein said hydrosilation catalyst comprises chloroplatinic acid, PdCl.sub.2, RhCl(PPh.sub.3).sub.3 or Co(CO).sub.8. |
| Claim: | 32. The process of claim 31 wherein said alkoxyhydrosilane is diethoxy(methyl)silane or dimethyl(ethoxy)silane. |
| Claim: | 33. The process of claim 32 wherein said heating step includes heating at a temperature of about 130.degree. C. for about 10 hours. |
| Claim: | 34. A process for preparing a chemically active, heat stable polymeric catalyst composition, comprising the step of hydrolysis polymerization of a silane monomer including a 4-dialkylaminopyridine function having at least one alkoxysilyl group attached to its 4-dialkylamino moiety in the presence of a suitable base catalyst. |
| Claim: | 35. The process of claim 34 wherein the silane is selected from the group consisting of |
| Claim: | N-(3-(diethoxy(methyl)silyl)propyl)-N-methyl-4-aminopyridine |
| Claim: | N-(3-(triethoxysilyl)propyl)-N-methyl-4-aminopyridine |
| Claim: | N,N[bis(3-(dimethyl(ethoxy)silyl)propyl)]-4-aminopyridine |
| Claim: | N,N[bis(3-(diethoxy(methyl)silyl)propyl)]-4-aminopyridine, and |
| Claim: | N,N[bis(3-(triethoxysilyl)propyl)]-4-aminopyridine. |
| Claim: | 36. The process of claim 35 wherein said base catalyst includes a negatively-charged oxygen species. |
| Claim: | 37. The process of claim 36 wherein said base catalyst is Me.sub.4 NOH or KOH. |
| Claim: | 38. The polymer of claim 23 having repeating monomeric units having the formula: ##STR10## where Me=methyl. |
| Claim: | 39. The polymer of claim 38 which also comprises repeating units of the formula: ##STR11## where Me=methyl. |
| Claim: | 40. The polymer of claim 38 which is crosslinked with MeSi(OEt).sub.3 or Si(OEt).sub.4, where Et=ethyl. |
| Claim: | 41. The polymer of claim 39 which is crosslinked with MeSi(OEt).sub.3 or Si(OEt).sub.4, where Et=ethyl. |
| Current U.S. Class: | 528/21; 528/27; 528/28; 528/31; 528/34; 528/35; 528/38; 546/14 |
| Current International Class: | C08C 7704; C08C 7706; C08C 7712 |
| Primary Examiner: | Ivy, C. Warren |
| Assistant Examiner: | Covington, Raymond |
| Attorney, Agent or Firm: | Woodard, Emhardt, Naughton, Moriarty & McNett |
| Accession Number: | edspgr.05194555 |
| Database: | USPTO Patent Grants |
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| Header | DbId: edspgr DbLabel: USPTO Patent Grants An: edspgr.05194555 RelevancyScore: 699 AccessLevel: 3 PubType: Patent PubTypeId: patent PreciseRelevancyScore: 699.285827636719 |
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| Items | – Name: Title Label: Title Group: Ti Data: Aminopyridyl siloxanes – Name: DocumentID Label: Patent Number Group: Patent Data: 5,194,555 – Name: DateEntry Label: Publication Date Group: Patent Data: March 16, 1993 – Name: DocumentID Label: Appl. No Group: Patent Data: 07/664,871 – Name: DateFiled Label: Application Filed Group: Patent Data: March 05, 1991 – Name: Abstract Label: Abstract Group: Ab Data: Silanes and Siloxanes incorporating the 4-dialkylaminopyridine functionality are described. Preferred silanes are catalytically active and also serve as precursors to the siloxanes. Preferred polysiloxanes incorporating DAAP functionality exhibit excellent physical and dynamic-mechanical properties while maintaining a substantial percentage of the DAAP catalytic behavior. – Name: Author Label: Inventors Group: Patent Data: <searchLink fieldCode="ZA" term="%22Zeldin%2C+Martel%22">Zeldin, Martel</searchLink> (Indianapolis, IN); <searchLink fieldCode="ZA" term="%22Fife%2C+Wilmer+K%2E%22">Fife, Wilmer K.</searchLink> (Indianapolis, IN); <searchLink fieldCode="ZA" term="%22Rubinsztajn%2C+Slawomir%22">Rubinsztajn, Slawomir</searchLink> (Carmel, IN) – Name: OtherAuthors Label: Assignees Group: Patent Data: <searchLink fieldCode="ZS" term="%22Indiana+University+Foundation%22">Indiana University Foundation</searchLink> (IN) – Name: Comment Label: Claim Group: Patent Data: What is claimed is – Name: Comment Label: Claim Group: Patent Data: 1. A nucleophilic and basic composition comprising a siloxane polymer incorporating 4-dialkylaminopyridine functionality. – Name: Comment Label: Claim Group: Patent Data: 2. The composition of claim 1 which is effective as a catalyst for an acylation, ester rearrangement, polymerization, oxidation or reduction reaction. – Name: Comment Label: Claim Group: Patent Data: 3. The composition of claim 1 which comprises a siloxane having 4-dialkylaminopyridine groups pendant from or incorporated into its polymer backbone. – Name: Comment Label: Claim Group: Patent Data: 4. The composition of claim 3 wherein the siloxane is thermally stable at temperatures of at least about 375.degree. C. – Name: Comment Label: Claim Group: Patent Data: 5. The composition of claim 3 wherein the siloxane catalyzes a transacylation of 1-methylcyclohexanol and acetic anhydride at a rate of at least about 75% that of 4-dimethylaminopyridine. – Name: Comment Label: Claim Group: Patent Data: 6. The composition of claim 3 wherein the siloxane has a molecular weight of about 1.times.10.sup.3 to about 1.times.10.sup.6. – Name: Comment Label: Claim Group: Patent Data: 7. The composition of claim 6 wherein the siloxane is a homopolymer. – Name: Comment Label: Claim Group: Patent Data: 8. The composition of claim 7 wherein said siloxane has a molecular weight from about 3000 to about 10,000. – Name: Comment Label: Claim Group: Patent Data: 9. The composition of claim 6 wherein the siloxane is a co-polymer. – Name: Comment Label: Claim Group: Patent Data: 10. The composition of claim 9 wherein the siloxane has a molecular weight of at least about 100,000. – Name: Comment Label: Claim Group: Patent Data: 11. The composition of claim 6 wherein the siloxane is a linear polymer. – Name: Comment Label: Claim Group: Patent Data: 12. The composition of claim 6 wherein the siloxane is a cross-linked polymer. – Name: Comment Label: Claim Group: Patent Data: 13. The composition of claim 6 wherein the siloxane has 4-dialkylaminopyridine groups pendant from its polymer backbone. – Name: Comment Label: Claim Group: Patent Data: 14. The composition of claim 6 wherein the siloxane has 4-dialkylaminopyridine groups included in its polymer backbone. – Name: Comment Label: Claim Group: Patent Data: 15. The composition of claim 6 wherein the siloxane has repeating units derived from a silane including a 4-dialkylaminopyridine group having at least one alkoxysilyl group connected to its 4-dialkylamino moiety. – Name: Comment Label: Claim Group: Patent Data: 16. The composition of claim 13 wherein the siloxane has repeating units derived from a silane including a single 4-dialkylaminopyridine group having a single alkoxysilyl group connected to its 4-dialkylamino moiety. – Name: Comment Label: Claim Group: Patent Data: 17. The composition of claim 13 wherein the siloxane has repeating units derived from N-(3-Diethoxy(methyl)silyl)propyl)-N-methyl-4-aminopyridine. – Name: Comment Label: Claim Group: Patent Data: 18. The composition of claim 13 wherein the siloxane has repeating units derived from N-(3-(Triethoxysilyl)propyl)-N-methyl-4-aminopyridine. – Name: Comment Label: Claim Group: Patent Data: 19. The composition of claim 14 wherein the siloxane has repeating units derived from a silane which includes a single 4-dialkylaminopyridine group having two alkoxysilyl groups attached to its 4-dialkylamino moiety. – Name: Comment Label: Claim Group: Patent Data: 20. The composition of claim 14 wherein the siloxane has repeating units derived from N,N[Bis(3-(dimethyl(ethoxy)silyl)propyl)]-4-aminopyridine. – Name: Comment Label: Claim Group: Patent Data: 21. The composition of claim 14 wherein the siloxane has repeating units derived from N,N[Bis(3-diethoxy(methyl)silyl)propyl)]-4-aminopyridine. – Name: Comment Label: Claim Group: Patent Data: 22. The composition of claim 14 wherein the siloxane has repeating units derived from N,N[Bis(3-triethoxysilyl)propyl)]-4-aminopyridine. – Name: Comment Label: Claim Group: Patent Data: 23. A polymer comprising a chemically active, heat stable siloxane having repeating monomeric units having the formula: ##STR6## where Me=methyl. – Name: Comment Label: Claim Group: Patent Data: 24. The polymer of claim 23 having repeating monomeric units having the formula: ##STR7## where Me=methyl. – Name: Comment Label: Claim Group: Patent Data: 25. The polymer of claim 24 which also comprises repeating units of the formula: ##STR8## – Name: Comment Label: Claim Group: Patent Data: 26. The polymer of claim 24 which is crosslinked with MeSi(OEt).sub.3 or Si(OEt).sub.4, where Et=ethyl. – Name: Comment Label: Claim Group: Patent Data: 27. The polymer of claim 25 which is crosslinked with MeSi(OEt).sub.3 or Si(OEt).sub.4, where Et=ethyl. – Name: Comment Label: Claim Group: Patent Data: 28. A process for preparing a nucleophilic and basic silane composition, comprising the step of hydrosilating 4-(N-methylallylamino)pyridine or 4-(N-diallylamino)pyridine with an alkoxyhydrosilane. – Name: Comment Label: Claim Group: Patent Data: 29. The process of claim 28 wherein said hydrosilating step occurs upon heating said reactants in the presence of a suitable hydrosilation catalyst. – Name: Comment Label: Claim Group: Patent Data: 30. The process of claim 29 wherein said alkoxyhydrosilane has the formula: ##STR9## wherein n=0, 1 or 2 and R=methyl, ethyl, propyl, or iso-propyl, and Me=methyl. – Name: Comment Label: Claim Group: Patent Data: 31. The process of claim 30 wherein said hydrosilation catalyst comprises chloroplatinic acid, PdCl.sub.2, RhCl(PPh.sub.3).sub.3 or Co(CO).sub.8. – Name: Comment Label: Claim Group: Patent Data: 32. The process of claim 31 wherein said alkoxyhydrosilane is diethoxy(methyl)silane or dimethyl(ethoxy)silane. – Name: Comment Label: Claim Group: Patent Data: 33. The process of claim 32 wherein said heating step includes heating at a temperature of about 130.degree. C. for about 10 hours. – Name: Comment Label: Claim Group: Patent Data: 34. A process for preparing a chemically active, heat stable polymeric catalyst composition, comprising the step of hydrolysis polymerization of a silane monomer including a 4-dialkylaminopyridine function having at least one alkoxysilyl group attached to its 4-dialkylamino moiety in the presence of a suitable base catalyst. – Name: Comment Label: Claim Group: Patent Data: 35. The process of claim 34 wherein the silane is selected from the group consisting of – Name: Comment Label: Claim Group: Patent Data: N-(3-(diethoxy(methyl)silyl)propyl)-N-methyl-4-aminopyridine – Name: Comment Label: Claim Group: Patent Data: N-(3-(triethoxysilyl)propyl)-N-methyl-4-aminopyridine – Name: Comment Label: Claim Group: Patent Data: N,N[bis(3-(dimethyl(ethoxy)silyl)propyl)]-4-aminopyridine – Name: Comment Label: Claim Group: Patent Data: N,N[bis(3-(diethoxy(methyl)silyl)propyl)]-4-aminopyridine, and – Name: Comment Label: Claim Group: Patent Data: N,N[bis(3-(triethoxysilyl)propyl)]-4-aminopyridine. – Name: Comment Label: Claim Group: Patent Data: 36. The process of claim 35 wherein said base catalyst includes a negatively-charged oxygen species. – Name: Comment Label: Claim Group: Patent Data: 37. The process of claim 36 wherein said base catalyst is Me.sub.4 NOH or KOH. – Name: Comment Label: Claim Group: Patent Data: 38. The polymer of claim 23 having repeating monomeric units having the formula: ##STR10## where Me=methyl. – Name: Comment Label: Claim Group: Patent Data: 39. The polymer of claim 38 which also comprises repeating units of the formula: ##STR11## where Me=methyl. – Name: Comment Label: Claim Group: Patent Data: 40. The polymer of claim 38 which is crosslinked with MeSi(OEt).sub.3 or Si(OEt).sub.4, where Et=ethyl. – Name: Comment Label: Claim Group: Patent Data: 41. The polymer of claim 39 which is crosslinked with MeSi(OEt).sub.3 or Si(OEt).sub.4, where Et=ethyl. – Name: CodeClass Label: Current U.S. Class Group: Patent Data: 528/21; 528/27; 528/28; 528/31; 528/34; 528/35; 528/38; 546/14 – Name: CodeClass Label: Current International Class Group: Patent Data: C08C 7704; C08C 7706; C08C 7712 – Name: AuthorEditor Label: Primary Examiner Group: Patent Data: <searchLink fieldCode="ZE" term="%22Ivy%2C+C%2E+Warren%22">Ivy, C. Warren</searchLink> – Name: AuthorEditor Label: Assistant Examiner Group: Patent Data: <searchLink fieldCode="ZE" term="%22Covington%2C+Raymond%22">Covington, Raymond</searchLink> – Name: AuthorCorporate Label: Attorney, Agent or Firm Group: Patent Data: <searchLink fieldCode="ZG" term="%22Woodard%2C+Emhardt%2C+Naughton%2C+Moriarty+%26+McNett%22">Woodard, Emhardt, Naughton, Moriarty & McNett</searchLink> – Name: AN Label: Accession Number Group: ID Data: edspgr.05194555 |
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| RecordInfo | BibRecord: BibEntity: Languages: – Text: English Titles: – TitleFull: Aminopyridyl siloxanes Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Zeldin, Martel – PersonEntity: Name: NameFull: Fife, Wilmer K. – PersonEntity: Name: NameFull: Rubinsztajn, Slawomir IsPartOfRelationships: – BibEntity: Dates: – D: 16 M: 03 Text: March 16, 1993 Type: published Y: 1993 |
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