Journal
MACROMOLECULES
Volume 44, Issue 1, Pages 166-174Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma101893u
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- Karlsruhe Institute of Technology (KIT)
- German Research Council (DFG)
- Ministry of Science and Arts of the state of Baden-Wurttemberg
- Alexander von Humboldt Foundation
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We report the photoinduced conjugation of polymers synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization with a number of low molecular weight (functional) olefins. Upon irradiation of a solution of an aliphatic alkene and the benzyl dithioacetic acid ester (CPDA) or dodecyl trithiocarbonate (DoPAT) functional poly(alkyl acrylate) at the absorption wavelength of the thiocarbonyl group (315 nm), incorporation of the alkene at the polymer chain-end occurred. The most efficient systems identified with regard to the rate of reaction and yield were poly(butyl acrylate)/CPDA/ethyl vinyl ether (78% monoinsertion product after 1 h) and poly(butyl acrylate)/CPDA/1-pentene (73% insertion product after 7 h) at ambient temperature. An in-depth analysis of the reaction mechanism by H-1 NMR and online size-exclusion chromatography-electrospray ionization tandem mass spectrometry (SEC/ESI-MSn) revealed that a possible [2 + 2] photoaddition mechanism of conjugation does not take place. Instead, fast beta-cleavage of the photoexcited RAFT-end group with subsequent radical addition of an alkene was observed for all employed systems. The presented reaction thus provides a means of spatial and temporal control for the conjugation of alkenes to thiocarbonyl thio-capped macromolecules via the use of UV radiation.
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