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Controlled Thiol‐Ene Functionalization of Polyferrocenylsilane‐ block ‐Polyvinylsiloxane Copolymers
Author(s) -
Lunn David J.,
Boott Charlotte E.,
Bass Kelly E.,
Shuttleworth Timothy A.,
McCreanor Niall G.,
Papadouli Sofia,
Manners Ian
Publication year - 2013
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201300520
Subject(s) - copolymer , surface modification , polymer chemistry , siloxane , polydimethylsiloxane , photoinitiator , materials science , silicone , monomer , ene reaction , thiol , telechelic polymer , chemistry , polymer , end group , organic chemistry , nanotechnology
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 ‐PMVS 510 ) 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 PFDMS 53 ‐ b ‐PMVS 58 /PDMS 444 (PDMS = polydimethylsiloxane), prepared by the copolymerization of cyclic siloxane monomers, [Me(CHCH 2 )SiO] 3 and [Me 2 SiO] 3 , to tune the vinyl group incorporation pre‐functionalization.