| Autor: |
Emert, J. I., Dankworth, D. C., Gutierrez, A., Martella, D. J., Rucker, S. P., Stokes, J. P., Thaler, W., Worku, A., Padias, A. B., Hall, H. K., Jr. |
| Zdroj: |
Macromolecules; April 2001, Vol. 34 Issue: 9 p2766-2775, 10p |
| Abstrakt: |
Copolymers of ethylene and 1-butene were synthesized using a single-site zirconium-based coordination catalyst. The polymers terminated exclusively in 1-butene ends, predominantly ethylvinylidene. They were carbonylated under Koch−Haaf conditions using boron trifluoride, carbon monoxide, and phenols to give polymeric hydrocarbons containing a single carboaryloxy group. Both 1,3- and 1,5-rearrangements were observed in this synthesis. The amination reaction with polyethylene amines followed second-order kinetics, but with a steadily decreasing bimolecular rate constant. The physical properties along with the block composition of the resulting polyhydrocarbon polyamine make this a potential candidate for motor oil dispersant. To interpret the polymer results, appropriate model compounds consisting of appropriately branched carboxylic acids, aryl esters, and amides were synthesized. The 13C NMR and IR spectra, both of the quaternary carbons and the carbonyls, supported the structure assignment for the polymers. Finally, the kinetics of the reactions of the model esters with model monoamines N,N-dimethyltrimethylenediamine and N-2-(ethylamino)piperidine quantitatively reproduced the amidation kinetics observed for the polymeric ester. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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