Bibliographic Details
| 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 |
