Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization

Nicholas S. Hill; Benjamin B. Noble; Michelle L. Coote

doi:10.1021/bk-2018-1284.ch002

Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization

Nicholas S. Hill, Benjamin B. Noble, Michelle L. Coote

Research output: Chapter in Book/Report/Conference proceeding › Conference contribution › peer-review

Abstract

Theoretical calculations have been performed to model the effects of a model Lewis acid, boron trichloride (BCl₃) on the radical copolymerization of methyl methacrylate (MMA) and styrene (Sty). These calculations suggest that the high degree of alternation observed in the copolymer sequence distribution cannot be attributed to either ternary monomer complexes nor radical-monomer complexes. These complexes were not found to be sufficiently stable, particularly in the presence of competing solvation by toluene. However, this alternation can be satisfactorily explained via an enhanced cross-propagation mechanism, which originates from the matched donor/acceptor electronic character of the MMA(BCl₃)/Sty system.

Original language	English
Title of host publication	Reversible Deactivation Radical Polymerization
Subtitle of host publication	Mechanisms and Synthetic Methodologies
Editors	Nicolay V. Tsarevsky, Haifeng Gao, Krzysztof Matyjaszewski, Brent S. Sumerlin
Publisher	American Chemical Society
Pages	41-61
Number of pages	21
ISBN (Print)	9780841233188
DOIs	https://doi.org/10.1021/bk-2018-1284.ch002
Publication status	Published - 2018

Publication series

Name	ACS Symposium Series
Volume	1284
ISSN (Print)	0097-6156
ISSN (Electronic)	1947-5918

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10.1021/bk-2018-1284.ch002

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Hill, N. S., Noble, B. B., & Coote, M. L. (2018). Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization. In N. V. Tsarevsky, H. Gao, K. Matyjaszewski, & B. S. Sumerlin (Eds.), Reversible Deactivation Radical Polymerization: Mechanisms and Synthetic Methodologies (pp. 41-61). (ACS Symposium Series; Vol. 1284). American Chemical Society. https://doi.org/10.1021/bk-2018-1284.ch002

Hill, Nicholas S. ; Noble, Benjamin B. ; Coote, Michelle L. / Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization. Reversible Deactivation Radical Polymerization: Mechanisms and Synthetic Methodologies. editor / Nicolay V. Tsarevsky ; Haifeng Gao ; Krzysztof Matyjaszewski ; Brent S. Sumerlin. American Chemical Society, 2018. pp. 41-61 (ACS Symposium Series).

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title = "Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization",

abstract = "Theoretical calculations have been performed to model the effects of a model Lewis acid, boron trichloride (BCl3) on the radical copolymerization of methyl methacrylate (MMA) and styrene (Sty). These calculations suggest that the high degree of alternation observed in the copolymer sequence distribution cannot be attributed to either ternary monomer complexes nor radical-monomer complexes. These complexes were not found to be sufficiently stable, particularly in the presence of competing solvation by toluene. However, this alternation can be satisfactorily explained via an enhanced cross-propagation mechanism, which originates from the matched donor/acceptor electronic character of the MMA(BCl3)/Sty system.",

author = "Hill, {Nicholas S.} and Noble, {Benjamin B.} and Coote, {Michelle L.}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

doi = "10.1021/bk-2018-1284.ch002",

language = "English",

isbn = "9780841233188",

series = "ACS Symposium Series",

publisher = "American Chemical Society",

pages = "41--61",

editor = "Tsarevsky, {Nicolay V.} and Haifeng Gao and Krzysztof Matyjaszewski and Sumerlin, {Brent S.}",

booktitle = "Reversible Deactivation Radical Polymerization",

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Hill, NS, Noble, BB & Coote, ML 2018, Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization. in NV Tsarevsky, H Gao, K Matyjaszewski & BS Sumerlin (eds), Reversible Deactivation Radical Polymerization: Mechanisms and Synthetic Methodologies. ACS Symposium Series, vol. 1284, American Chemical Society, pp. 41-61. https://doi.org/10.1021/bk-2018-1284.ch002

Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization. / Hill, Nicholas S.; Noble, Benjamin B.; Coote, Michelle L.
Reversible Deactivation Radical Polymerization: Mechanisms and Synthetic Methodologies. ed. / Nicolay V. Tsarevsky; Haifeng Gao; Krzysztof Matyjaszewski; Brent S. Sumerlin. American Chemical Society, 2018. p. 41-61 (ACS Symposium Series; Vol. 1284).

Research output: Chapter in Book/Report/Conference proceeding › Conference contribution › peer-review

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N2 - Theoretical calculations have been performed to model the effects of a model Lewis acid, boron trichloride (BCl3) on the radical copolymerization of methyl methacrylate (MMA) and styrene (Sty). These calculations suggest that the high degree of alternation observed in the copolymer sequence distribution cannot be attributed to either ternary monomer complexes nor radical-monomer complexes. These complexes were not found to be sufficiently stable, particularly in the presence of competing solvation by toluene. However, this alternation can be satisfactorily explained via an enhanced cross-propagation mechanism, which originates from the matched donor/acceptor electronic character of the MMA(BCl3)/Sty system.

AB - Theoretical calculations have been performed to model the effects of a model Lewis acid, boron trichloride (BCl3) on the radical copolymerization of methyl methacrylate (MMA) and styrene (Sty). These calculations suggest that the high degree of alternation observed in the copolymer sequence distribution cannot be attributed to either ternary monomer complexes nor radical-monomer complexes. These complexes were not found to be sufficiently stable, particularly in the presence of competing solvation by toluene. However, this alternation can be satisfactorily explained via an enhanced cross-propagation mechanism, which originates from the matched donor/acceptor electronic character of the MMA(BCl3)/Sty system.

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BT - Reversible Deactivation Radical Polymerization

A2 - Tsarevsky, Nicolay V.

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Hill NS, Noble BB, Coote ML. Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization. In Tsarevsky NV, Gao H, Matyjaszewski K, Sumerlin BS, editors, Reversible Deactivation Radical Polymerization: Mechanisms and Synthetic Methodologies. American Chemical Society. 2018. p. 41-61. (ACS Symposium Series). doi: 10.1021/bk-2018-1284.ch002

Mechanistic insights into lewis acid mediated sequence- and stereo-control in radical copolymerization

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