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Light‐Triggered Radical Silane‐Ene Chemistry Using a Monosubstituted Bis(trimethylsilyl)silane
Author(s) -
Steindl Johannes,
Svirkova Anastasiya,
MarchettiDeschmann Martina,
Moszner Norbert,
Gorsche Christian
Publication year - 2017
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.201600563
Subject(s) - silane , acrylate , photopolymer , trimethylsilyl , chemistry , polymer chemistry , ene reaction , reactivity (psychology) , photochemistry , organic chemistry , polymerization , polymer , copolymer , medicine , alternative medicine , pathology
Chain transfer agents (e.g., thiols) enrich radical photopolymerization for use in advanced applications such as stereolithography, optical materials, and biomedicine. Resulting thiol‐ene‐based photopolymers exhibit numerous benefits such as tunable thermomechanical properties, and give access to spatially resolved functional materials. Silane‐ene chemistry could serve as alternative to this popular thiol‐ene approach. A monosubstituted bis(trimethylsilyl)silane (MSiH) is synthesized by a simple one pot procedure. Photoinitiated radical silane‐ene chemistry has been performed with multiple enes and the conversions are assessed by 1 H NMR spectroscopy. Compared to the most reactive silane from literature, tris(trimethylsilyl)silane (TTMSSiH), the radical reactivity of MSiH is reduced in all tested formulations, but the possibility for further functionalization and accessibility of multifunctional MSiH‐derivatives is upheld. A silane‐acrylate formulation is found to be most promising. In comparison to a thiol‐acrylate system, a more uniform conversion of the chain transfer agent and acrylate is shown for the silane‐acrylate formulation with MSiH. The promising results for the silane‐acrylate system are confirmed by further tests (i.e., NMR spectroscopy, GPC, and MALDI MS), giving additional information on molecular weight regulation and radical mechanism. First MSiH‐based photopolymer networks have been fabricated and analyzed via DMTA, thus paving the way for future silane‐acrylate networks.