TY - JOUR

T1 - Impact of the RAFT/MADIX agent on protonated diallylammonium monomer cyclopolymerization with efficient chain transfer to monomer

AU - Simonova, Yulia A.

AU - Topchiy, Maxim A.

AU - Filatova, Marina P.

AU - Yevlampieva, Natalia P.

AU - Slyusarenko, Mariya A.

AU - Bondarenko, Galina N.

AU - Asachenko, Andrey F.

AU - Nechaev, Mikhail S.

AU - Timofeeva, Larisa M.

N1 - Funding Information: Authors are very grateful to Prof. Alexandr S. Shashkov (IOC RAS) for their help in two-dimensional HSQC and 13C NMR study of polymers. This work was carried out within the State Program of TIPS RAS. The raw/processed data required to reproduce these findings cannot be shared at this time due to legal or ethical reasons as well time limitations. Publisher Copyright: © 2019 Elsevier Ltd Copyright: Copyright 2019 Elsevier B.V., All rights reserved.

PY - 2020/1/5

Y1 - 2020/1/5

N2 - We have studied applicability of reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) method to radical cyclopolymerization of protonated diallylammonium monomer, namely diallylammonium trifluoroacetate (DAATFA), occurring with efficient chain transfer to monomer reaction. The latter drives to a significant extent polymerization, noticeably setting molecular weight, MW, of polymers and their polydispersity (polydispersity index (PDI) = 2.8–3.0). For the first time, upon DAATFA polymerization in presence of RAFT ethylxanthogenacetic acid (xanthate) in aqueous solutions at 70 °C, the side chain transfer reaction was inhibited and control of the polydispersity was achieved, the PDI = 1.2–1.3. The structural characteristic of poly(diallylammonium trifluoroacetate) (PDAATFA) polymers was analyzed via 1H and 13C NMR and IFS FTIR (ATR) spectroscopy. It was proved that the structure of polymers obtained by RAFT polymerization fully corresponds to the polymers PDAATFA containing cationic pyrrolidinium links and trifluoroacetate-counterions. At the optimal xanthate concentrations, the main products are polymers with the end dithiocarbonate group, i.e. macro-RAFT PDAATFA. Static/dynamic light scattering, viscometry and ultracentrifugation were used for polymers characterization. Molecular weight was determined by two independent methods: static light scattering (Mw) and hydrodynamic parameters analysis (MDη). The PDI Mw/Mn was calculated on the basis of Fujita approach, using the determined distributions of sedimentation coefficients. The experimental number average molecular weights, Mn, grow with polymerization time, 6700 g mol−1 < Mn < 10500 g mol−1, but did not correspond to the theoretical one. The rate of polymerization mediated by xanthate was shown to increase approximately twice in comparison to free-radical process that distinguishes DAATFA RAFT polymerization from other processes mediated by RAFT agent.

AB - We have studied applicability of reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) method to radical cyclopolymerization of protonated diallylammonium monomer, namely diallylammonium trifluoroacetate (DAATFA), occurring with efficient chain transfer to monomer reaction. The latter drives to a significant extent polymerization, noticeably setting molecular weight, MW, of polymers and their polydispersity (polydispersity index (PDI) = 2.8–3.0). For the first time, upon DAATFA polymerization in presence of RAFT ethylxanthogenacetic acid (xanthate) in aqueous solutions at 70 °C, the side chain transfer reaction was inhibited and control of the polydispersity was achieved, the PDI = 1.2–1.3. The structural characteristic of poly(diallylammonium trifluoroacetate) (PDAATFA) polymers was analyzed via 1H and 13C NMR and IFS FTIR (ATR) spectroscopy. It was proved that the structure of polymers obtained by RAFT polymerization fully corresponds to the polymers PDAATFA containing cationic pyrrolidinium links and trifluoroacetate-counterions. At the optimal xanthate concentrations, the main products are polymers with the end dithiocarbonate group, i.e. macro-RAFT PDAATFA. Static/dynamic light scattering, viscometry and ultracentrifugation were used for polymers characterization. Molecular weight was determined by two independent methods: static light scattering (Mw) and hydrodynamic parameters analysis (MDη). The PDI Mw/Mn was calculated on the basis of Fujita approach, using the determined distributions of sedimentation coefficients. The experimental number average molecular weights, Mn, grow with polymerization time, 6700 g mol−1 < Mn < 10500 g mol−1, but did not correspond to the theoretical one. The rate of polymerization mediated by xanthate was shown to increase approximately twice in comparison to free-radical process that distinguishes DAATFA RAFT polymerization from other processes mediated by RAFT agent.

KW - Chain transfer to monomer

KW - Narrow polydispersity

KW - Protonated diallylamine

KW - Protonated polydiallylamine

KW - Radical cyclopolymerization

KW - RAFT/MADIX polymerization

KW - Xanthate

KW - POLYMERS

KW - MOLECULAR-WEIGHT

KW - REACTIVITY

KW - CONTROLLED RADICAL POLYMERIZATION

KW - RAFT POLYMERIZATION

KW - DIALLYLDIMETHYLAMMONIUM CHLORIDE

KW - WATER-SOLUBLE (CO)POLYMERS

UR - http://www.scopus.com/inward/record.url?scp=85075904014&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/78827d1b-1b07-3cfc-b492-1afb3559810e/

U2 - 10.1016/j.eurpolymj.2019.109363

DO - 10.1016/j.eurpolymj.2019.109363

M3 - Article

AN - SCOPUS:85075904014

VL - 122

JO - European Polymer Journal

JF - European Polymer Journal

SN - 0014-3057

M1 - 109363

ER -