Controlled Thiol‐Ene Functionalization of Polyferrocenylsilane‐block‐Polyvinylsiloxane Copolymers. Issue 24 (17th October 2013)

• Record Type: Journal Article
• Authors: Lunn, David J.; Boott, Charlotte E.; Bass, Kelly E.; Shuttleworth, Timothy A.; McCreanor, Niall G.; Papadouli, Sofia; Manners, Ian
• Is Part Of: Macromolecular chemistry and physics. Volume 214:Issue 24(2013:Dec.)
• Page Start: 2813
• Page End: 2820
• Publication Date: 2013-10-17
• Subjects: Polymers -- Periodicals; Polymerization -- Periodicals; Synthetic products -- Periodicals; Macromolecules -- Periodicals; 547.7
• DOI: 10.1002/macp.201300520
• Languages: English
• ISSNs: 1022-1352

Abstract

<abstract abstract-type="main" xml:lang="en"> <title> <x xml:space="preserve">Abstract</x> </title> <p>A general route for the controlled functionalization of polyferrocenylsilane‐<italic>block</italic>‐polyvinylsiloxane copolymers, which should be transferable to other silicone‐based materials, is developed utilizing the photoinitiated thiol‐ene reaction. Poly(ferrocenyldimethylsilane)<sub>54</sub>‐<italic>block</italic>‐poly(methylvinylsiloxane)<sub>510</sub> (PFDMS<sub>54</sub>‐<italic>b</italic>‐PMVS<sub>510</sub>) 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<sub>53</sub>‐<italic>b</italic>‐PMVS<sub>58</sub>/PDMS<sub>444</sub> (PDMS = polydimethylsiloxane), prepared by the copolymerization of cyclic siloxane monomers, [Me(CHCH<sub>2</sub>)SiO]<sub>3</sub> and [Me<sub>2</sub>SiO]<sub>3</sub>, to tune the vinyl group incorporation pre‐functionalization. <boxed-text content-type="graphic" position="anchor" orientation="portrait"><graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg3zs18q30" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></boxed-text></p> </abstract>