Abstract
Several norboraene (Nb) derivatives were synthesized by facile Diels-Alder cycloaddition reactions of cyclopentadiene with α-olefins containing electron-with-drawing groups such as nitrile (CN), phosphonate, and ester. The Diels-Alder adducts were subsequently copolymerized with maleic anhydride (MAH) using free radical polymerization conditions previously determined for MAH/Nb copolymerizations. Further functionality was introduced into the copolymers through acid-catalyzed hydrolysis of poly(Nb-alt-MAH) and poly(NbCN-alt-MAH) copolymers. FTIR confirmed hydrolysis of the anhydrides to carboxylic acid-functionalities and indicated no appreciable hydrolysis of the nitrile functionality. Observed copolymerization rates (kobs) were measured using in situ FTIR. A dramatic decrease in the rate of copolymerization was observed for the Nb derivatives that contained a strong electron-withdrawing functionality. This observation suggested a significant electronic influence on the free radical copolymerization rate with maleic anhydride due to the electron-withdrawing nature of the Nb substituents.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 621-627 |
| Number of pages | 7 |
| Journal | Macromolecular Chemistry and Physics |
| Volume | 205 |
| Issue number | 5 |
| DOIs | |
| State | Published - Mar 25 2004 |
| Externally published | Yes |
Keywords
- Copolymerization
- Diels-Alder polymers
- Norbornene
ASJC Scopus subject areas
- Condensed Matter Physics
- Physical and Theoretical Chemistry
- Organic Chemistry
- Polymers and Plastics
- Materials Chemistry