Synthesis of norbornene derivatives by Diels-Alder cycloaddition and subsequent copolymerization with maleic anhydride

Anthony J. Pasquale, Ann R. Fornof, Timothy Edward Long

Research output: Contribution to journalArticle

10 Citations (Scopus)

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 languageEnglish
Pages (from-to)621-627
Number of pages7
JournalMacromolecular Chemistry and Physics
Volume205
Issue number5
DOIs
Publication statusPublished - 2004 Mar 25
Externally publishedYes

Fingerprint

Maleic Anhydrides
Cycloaddition
cycloaddition
Maleic anhydride
copolymerization
anhydrides
Copolymerization
Derivatives
synthesis
Hydrolysis
Nitriles
hydrolysis
nitriles
Electrons
free radicals
Copolymers
copolymers
Cyclopentanes
Organophosphonates
Anhydrides

Keywords

  • Copolymerization
  • Diels-Alder polymers
  • Norbornene

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

Synthesis of norbornene derivatives by Diels-Alder cycloaddition and subsequent copolymerization with maleic anhydride. / Pasquale, Anthony J.; Fornof, Ann R.; Long, Timothy Edward.

In: Macromolecular Chemistry and Physics, Vol. 205, No. 5, 25.03.2004, p. 621-627.

Research output: Contribution to journalArticle

Pasquale, Anthony J. ; Fornof, Ann R. ; Long, Timothy Edward. / Synthesis of norbornene derivatives by Diels-Alder cycloaddition and subsequent copolymerization with maleic anhydride. In: Macromolecular Chemistry and Physics. 2004 ; Vol. 205, No. 5. pp. 621-627.
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