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EnglishAtom transfer radical polymerization (ATRP) is often used for grafting from fluorinated polymers. Nevertheless, the possibility to initiate an ATRP from a C-F functionality and the activity of the catalysts in the presence of fluoride anions are essentially unexplored. Therefore, we investigated the thermodynamics and kinetics of C-F bond activation by ATRP catalysts and compared it with other halide systems. The ATRP equilibrium constant was estimated to be small for the reaction between [CuITPMA]+ and benzyl fluoride (TPMA = tris(2-pyridylmethyl)- amine). However, [CuITPMA] + could react with the more active initiator diethyl fluoromalonate (DEFM). With DEFM as initiator and CuIBr/TPMA as catalyst, ATRP of methyl acrylate and styrene displayed initiation efficiencies of 73% and 95%, respectively. ATRP deactivation by [F-CuIITPMA] + was slow and followed by even slower activation of newly formed C-F bonds, leading to limited conversion. Comparison with other halides indicates that Br- and Cl-based ATRP systems are more efficient that I- and F-based systems.
Lanzalaco, S., Fantin, M., Scialdone, O., Galia, A., Isse, A., Gennaro, A., et al. (2016). Atom transfer radical polymerization with different halides (F, Cl, Br, and I): Is the process "living" in the presence of fluorinated initiators?. MACROMOLECULES, 50(2), 192-202 [10.1021/acs.macromol.6b02286].
| Data di pubblicazione: | 2016 | |
| Titolo: | Atom transfer radical polymerization with different halides (F, Cl, Br, and I): Is the process "living" in the presence of fluorinated initiators? | |
| Autori: | ||
| Citazione: | Lanzalaco, S., Fantin, M., Scialdone, O., Galia, A., Isse, A., Gennaro, A., et al. (2016). Atom transfer radical polymerization with different halides (F, Cl, Br, and I): Is the process "living" in the presence of fluorinated initiators?. MACROMOLECULES, 50(2), 192-202 [10.1021/acs.macromol.6b02286]. | |
| Rivista: | ||
| Digital Object Identifier (DOI): | http://dx.doi.org/10.1021/acs.macromol.6b02286 | |
| Abstract: | Atom transfer radical polymerization (ATRP) is often used for grafting from fluorinated polymers. Nevertheless, the possibility to initiate an ATRP from a C-F functionality and the activity of the catalysts in the presence of fluoride anions are essentially unexplored. Therefore, we investigated the thermodynamics and kinetics of C-F bond activation by ATRP catalysts and compared it with other halide systems. The ATRP equilibrium constant was estimated to be small for the reaction between [CuITPMA]+ and benzyl fluoride (TPMA = tris(2-pyridylmethyl)- amine). However, [CuITPMA] + could react with the more active initiator diethyl fluoromalonate (DEFM). With DEFM as initiator and CuIBr/TPMA as catalyst, ATRP of methyl acrylate and styrene displayed initiation efficiencies of 73% and 95%, respectively. ATRP deactivation by [F-CuIITPMA] + was slow and followed by even slower activation of newly formed C-F bonds, leading to limited conversion. Comparison with other halides indicates that Br- and Cl-based ATRP systems are more efficient that I- and F-based systems. | |
| Settore Scientifico Disciplinare: | Settore ING-IND/27 - Chimica Industriale E Tecnologica | |
| Appare nelle tipologie: | 1.01 Articolo in rivista |
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http://hdl.handle.net/10447/230782
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