A Synthetic and Multispectroscopic Speciation Analysis of Controlled Radical Polymerization Mediated by Amine-Bis(phenolate)iron Complexes

Hendrik Schroeder; Benjamin R.M. Lake; Serhiy Demeshko; Michael P. Shaver; Michael Buback

doi:10.1021/acs.macromol.5b01175

A Synthetic and Multispectroscopic Speciation Analysis of Controlled Radical Polymerization Mediated by Amine-Bis(phenolate)iron Complexes

Hendrik Schroeder, Benjamin R.M. Lake, Serhiy Demeshko, Michael P. Shaver^*, Michael Buback

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

The mechanism of reversible-deactivation radical polymerization (RDRP) mediated by chloro-substituted amine-bis(phenolate)iron complexes was studied via a combination of Mössbauer, EPR, NMR, and online Vis/NIR spectroscopy. It was found that styrene polymerization operates via an atom-transfer radical polymerization (ATRP) mechanism when alkyl halide is present, whereas an interplay between ATRP and organometallic-mediated radical polymerization (OMRP) equilibria occurs during MMA polymerization. The preparation of the amine-bis(phenolate)iron(II) complex, [O₂NN′]Fe^II, allowed polymerizations to be performed under an OMRP-only regime free of alkyl halide that yields dispersities as low as 1.29 for MMA polymerization.

Original language	English
Pages (from-to)	4329-4338
Number of pages	10
Journal	Macromolecules
Volume	48
Issue number	13
DOIs	https://doi.org/10.1021/acs.macromol.5b01175
Publication status	Published - 14 Jul 2015

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title = "A Synthetic and Multispectroscopic Speciation Analysis of Controlled Radical Polymerization Mediated by Amine-Bis(phenolate)iron Complexes",

abstract = "The mechanism of reversible-deactivation radical polymerization (RDRP) mediated by chloro-substituted amine-bis(phenolate)iron complexes was studied via a combination of M{\"o}ssbauer, EPR, NMR, and online Vis/NIR spectroscopy. It was found that styrene polymerization operates via an atom-transfer radical polymerization (ATRP) mechanism when alkyl halide is present, whereas an interplay between ATRP and organometallic-mediated radical polymerization (OMRP) equilibria occurs during MMA polymerization. The preparation of the amine-bis(phenolate)iron(II) complex, [O2NN′]FeII, allowed polymerizations to be performed under an OMRP-only regime free of alkyl halide that yields dispersities as low as 1.29 for MMA polymerization.",

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AU - Lake, Benjamin R.M.

AU - Demeshko, Serhiy

AU - Shaver, Michael P.

AU - Buback, Michael

PY - 2015/7/14

Y1 - 2015/7/14

N2 - The mechanism of reversible-deactivation radical polymerization (RDRP) mediated by chloro-substituted amine-bis(phenolate)iron complexes was studied via a combination of Mössbauer, EPR, NMR, and online Vis/NIR spectroscopy. It was found that styrene polymerization operates via an atom-transfer radical polymerization (ATRP) mechanism when alkyl halide is present, whereas an interplay between ATRP and organometallic-mediated radical polymerization (OMRP) equilibria occurs during MMA polymerization. The preparation of the amine-bis(phenolate)iron(II) complex, [O2NN′]FeII, allowed polymerizations to be performed under an OMRP-only regime free of alkyl halide that yields dispersities as low as 1.29 for MMA polymerization.

AB - The mechanism of reversible-deactivation radical polymerization (RDRP) mediated by chloro-substituted amine-bis(phenolate)iron complexes was studied via a combination of Mössbauer, EPR, NMR, and online Vis/NIR spectroscopy. It was found that styrene polymerization operates via an atom-transfer radical polymerization (ATRP) mechanism when alkyl halide is present, whereas an interplay between ATRP and organometallic-mediated radical polymerization (OMRP) equilibria occurs during MMA polymerization. The preparation of the amine-bis(phenolate)iron(II) complex, [O2NN′]FeII, allowed polymerizations to be performed under an OMRP-only regime free of alkyl halide that yields dispersities as low as 1.29 for MMA polymerization.

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DO - 10.1021/acs.macromol.5b01175

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A Synthetic and Multispectroscopic Speciation Analysis of Controlled Radical Polymerization Mediated by Amine-Bis(phenolate)iron Complexes

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