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Chain transfer to solvent in the radical polymerization of structurally diverse acrylamide monomers using straight-chain and branched alcohols as solvents
Magee, Christopher; Sugihara, Yusuke; Zetterlund, Per B.; Aldabbagh, Fawaz
Chain transfer to solvent in conventional radical polymerizations of N-tert-butylacrylamide (TBAM) and N-(2-morpholin-4-ylethyl) acrylamide (MEA) in a range of alcohol solvents is investigated. Mayo analysis of polymerization of TBAM in linear alcohols (C-3-C-9) resulted in an approximately linear increase in chain transfer to solvent constant (C-tr,(S)) with the number of methylene (CH2) units in the solvent. The branched alcohol 3-methyl-3-pentanol gave the smallest C-tr,C-S (using Mayo analysis), and thus allowed attainment of higher molecular weights (MWs) in the nitroxide-mediated polymerizations (NMP) of TBAM. Overall, the data show that MEA is more prone to chain transfer to solvent than TBAM (higher C-tr,C-S), and further analysis of the conventional radical polymerization of MEA in 3-methyl-3-pentanol indicate chain transfer to monomer may also be occurring. The first controlled/ living polymerizations of MEA are detailed with chain transfer having a greater impact on maximum achievable MWs in NMP in comparison to TBAM.
Keyword(s): supercritical carbon-dioxide; n-tert-butylacrylamide; molecular-weight; precipitation polymerization; raft polymerization; styrene; isopropylacrylamide; copolymerization; polydispersity; delivery
Publication Date:
Type: Journal article
Peer-Reviewed: Unknown
Institution: NUI Galway
Publisher(s): Royal Society of Chemistry (RSC)
First Indexed: 2019-03-23 06:27:37 Last Updated: 2019-03-23 06:27:37