NMR and mass spectral analysis of step-growth polymers from azide alkyne cycloaddition and regioselectivity afforded by copper(I) and ruthenium(II) catalysts
| Autor: | R. Hunter Cooke, Mark R. Brei, Robson F. Storey, Christina T. Gray, Daniel J. Hanson |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Polymers and Plastics 010405 organic chemistry Alkyne chemistry.chemical_element Regioselectivity Ether General Chemistry 010402 general chemistry 01 natural sciences Cycloaddition 0104 chemical sciences Ruthenium Step-growth polymerization chemistry.chemical_compound Monomer chemistry Polymer chemistry Materials Chemistry Ceramics and Composites Organic chemistry Azide |
| Zdroj: | Journal of Macromolecular Science, Part A. 53:413-423 |
| ISSN: | 1520-5738 1060-1325 |
| DOI: | 10.1080/10601325.2016.1176442 |
| Popis: | Azide alkyne cycloaddition was applied to step growth polymerization of the diazido monomer, di(3-azido-2-hydroxypropyl) ether of bisphenol-A (DAHP-BPA) with either tetraethyleneglycol dipropargyl ether (TEGDPE) or tetraethyleneglycol dipropiolate (TEGDP). Polymerizations were conducted without catalyst and in the presence of Cu(I) or Ru(II) complex. The resulting oligomers and polymers were characterized using 1H- and 13C-NMR spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), with an emphasis on the relative abundance of 1,4- vs. 1,5-disubstituted regioisomeric 1,2,3-triazoles. Uncatalyzed reaction of DAHP-BPA/TEGDPE at 70°C yielded a 55/45 mixture of 1,4/1,5-disubstituted triazoles; reaction was slow and residual alkyne end groups were observed, suggesting attritional loss of azide. Catalyzed with Cu(PPh3)3Br, the same system yielded 93/7, 1,4/1,5-disubstituted triazoles, and few residual end groups were detected, consistent with higher ... |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
| Nepřihlášeným uživatelům se plný text nezobrazuje | K zobrazení výsledku je třeba se přihlásit. |