A facile route to well-defined imidazolium-based poly(ionic liquid)s of enhanced conductivity via RAFT. Issue 35 (14th August 2017)

• Record Type: Journal Article
• Authors: Maksym, Paulina; Tarnacka, Magdalena; Dzienia, Andrzej; Erfurt, Karol; Chrobok, Anna; Zięba, Andrzej; Wolnica, Kamila; Kaminski, Kamil; Paluch, Marian
• Is Part Of: Polymer chemistry. Volume 8:Issue 35(2017)
• Page Start: 5433
• Page End: 5443
• Publication Date: 2017-08-14
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/c7py01046j
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : Examining the relationship between the glass transition temperature, conductivity and molecular weight of tailored imidazolium-based PILs synthesized via RAFT. Abstract : The synthesis of well-defined imidazolium-based poly(ionic liquid)s (PILs) by reversible addition–fragmentation chain transfer (RAFT) polymerization is demonstrated. Two specially designed monomeric ionic liquids (MILs), such as 1-methyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide [MVIM][NTf2 ] and 1-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide [EVIM][NTf2 ] were polymerized with the 2, 2′-azobisisobutyronitrile (AIBN) initiator in the presence of a trithiocarbonate RAFT agent. Depending on the varied ratios of the monomer to CTA ([monomer]/[CTA] = 100/1; 400/1; 1000/1) we obtained P[MVIM][NTf2 ] and P[EVIM][NTf2 ] homopolymers with the number-average molecular weights ( M n ) in a broad range M n = 2.5–340.0 kDa and M n = 2.1–450.0 kDa, respectively. The controlled character of the polymerization of each ionic monomer was confirmed by the pseudo-first order kinetic, a linear increase in the M n with conversion and relatively narrow dispersity indices ( Đ = 1.09–1.37 for P[MVIM][NTf2 ] and Đ = 1.10–1.41 for P[EVIM][NTf2 ]). Additionally, the obtained macromolecules are characterized by the enhanced/or comparable conductivity in comparison with those reported in the literature [Wojnarowska et al., Macromolecules, 2014, 47, 4056–4065 and Fan et al., Macromolecules, 2016, 49, 4557–4570], indicating that we are able to produce polymers of high molecular weights characterized by relatively high conductivity ( σ dc ∼ 10 −9 at T g ). Finally, we found quite unexpected evolution of T g vs. M n of the produced polymers in the limit of low molecular weight, which seems to correspond to those observed in the case of van der Waals polymers such as polystyrene or polyisobutylene.