Ferrocenyl-functionalized long chain branched polydienes

Frederik Wurm, Francisco Javier López-Villanueva, Holger Frey*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

12 Citations (Scopus)
1 Downloads (Pure)

Abstract

A convenient two-step approach for the synthesis of ferrocenyl-functional- ized long chain branched polydienes, based on both butadiene and isoprene, respectively, is presented. Classical living anionic polymerization was used to synthesize different ABn type poly(diene) macromonomers with moderate molecular weights between 1700 and 3200 g/mol and narrow polydispersity. Quantitative end-capping with chlorodimethylsilane resulted in the desired ABn macromonomer structures. In the ensuing Pt-catalyzed hydrosilylation polyaddition, branched, functionalized poly- dienes were obtained by a concurrent ABn + AR type of copolymerization with mono- and difunctional ferrocenyl silanes (fcSiMe2Horfc2SiMeH). Molecular weights of the branched polymers were in the range of 10,000 to 44,000 g/mol (SEC/MALLS). Because of the large number of functional end groups, high loading with ferrocene units up to 63 wt % of ferrocene was achieved. Detailed studies showed full conversion of the functional silanes and incorporation into the branched polymer. Further studies using DSC, TGA, and cyclovoltammetry (CV) measurements have been performed. Electrochemical studies demonstrated different electrochemical properties for fcSiMe2- and fc2SiMe-units. The CVs of polymers modified with diferrocenylsilane units exhibit the pattern of communicating ferrocenyl sites with two distinct, separate oxidation waves. The polymers were also deposited on an electrode surface and the electrodes investigated via CV, showing formation of electroactive films with promising results for the use of the materials in biosensors.

Original languageEnglish
Pages (from-to)2518-2529
Number of pages12
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume47
Issue number10
DOIs
Publication statusPublished - 15 May 2009
Externally publishedYes

Keywords

  • Anionic polymerization
  • Branched
  • Electroactive polymers
  • Electrochemistry
  • Ferrocene
  • Hyperbranched polymers
  • Polybutadiene

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