Controlled Thiol-Ene Functionalization of Polyferrocenylsilane-block-Polyvinylsiloxane Copolymers

David J. Lunn, Charlotte E. Boott, Kelly E. Bass, Timothy A. Shuttleworth, Niall McCreanor, Sofia Papadouli, Ian Manners*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

23 Citations (Scopus)

Abstract

A general route for the controlled functionalization of polyferrocenylsilane-block-polyvinylsiloxane copolymers, which should be transferable to other silicone-based materials, is developed utilizing the photoinitiated thiol-ene reaction. Poly(ferrocenyldimethylsilane) 54-block-poly(methylvinylsiloxane)510 (PFDMS 54-b-PMVS510) is synthesized via sequential living anionic polymerization and quantitatively functionalized with a range of thiols, with the aim of tuning the solubility of the resulting materials for self-assembly studies or incorporating more complex functionality for subsequent applications. When functionalization is attempted using a deficit of thiol, the photoinitiator 2,2-dimethoxy-2-phenylacetophenone, used to accelerate the radical reaction, is found to cause significant cross-linking of the polysiloxane chain. Reproducible percentage thiol-ene functionalization of the polysiloxane block can be achieved by the use of PFDMS53-b-PMVS 58/PDMS444 (PDMS = polydimethylsiloxane), prepared by the copolymerization of cyclic siloxane monomers, [Me(CHi CH2)SiO] 3 and [Me2SiO]3, to tune the vinyl group incorporation pre-functionalization. Functional block copolymers: a general route for the controlled functionalization of polyferrocenylsilane-block- polyvinylsiloxane (PFDMS-b-PMVS) copolymers is achieved utilizing the photoinitiated thiol-ene reaction. This method is developed with the aim of tuning the solubility of the resulting materials for self-assembly studies or incorporating more complex functionality for subsequent applications. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Original languageEnglish
Pages (from-to)2813-2820
Number of pages8
JournalMacromolecular Chemistry and Physics
Volume214
Issue number24
DOIs
Publication statusPublished - 1 Dec 2013

Structured keywords

  • BCS and TECS CDTs

Keywords

  • anionic polymerization
  • block copolymers
  • functionalization of polymers
  • thiol-ene reaction
  • CROSS-LINKED MICELLES
  • DIBLOCK COPOLYMERS
  • TRIBLOCK COPOLYMER
  • CYLINDRICAL MICELLES
  • MULTICOMPARTMENT MICELLES
  • POLYMER VESICLES
  • POLYBUTADIENE-BLOCK-POLY(ETHYLENE OXIDE)
  • POLYETHYLENE CORES
  • CONTROLLED LENGTH
  • CRYSTALLINE-CORE

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