Reducing the degree of branching in polyacrylates via midchain radical patching : a quantitative melt-state NMR study

Marianne Gaborieau; Sandy P. S. Koo; Patrice Castignolles; Thomas Junkers; Christopher Barner-Kowollik

doi:10.1021/ma100991c

Reducing the degree of branching in polyacrylates via midchain radical patching : a quantitative melt-state NMR study

Marianne Gaborieau, Sandy P. S. Koo, Patrice Castignolles, Thomas Junkers, Christopher Barner-Kowollik

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

Abstract

Degrees of branching were measured with Cmelt-stateNMRin poly(n-butyl acrylates) synthesized in both the presence and absence of 1-octanethiol at various temperatures, and their precision calculated based on the signal-to-noise ratio of the quaternary carbon at the branching point. A significant decrease of branching was observed in the presence of a thiol during the polymerization process, experimentally confirming the “patching” effect of midchain tertiary radicals by the thiol. Thus, the addition of a chain transfer agent not only controls the chain length of the polyacrylate, but also the complexity of its microstructure is significantly reduced. In addition, the current work illustrates the potential of melt-state NMR for the quantitative determination of the degrees of branching with precision for example, for kinetics studies.

Original language	English
Pages (from-to)	5492-5495
Number of pages	4
Journal	Macromolecules
Volume	43
Issue number	13
DOIs	https://doi.org/10.1021/ma100991c
Publication status	Published - 2010

Keywords

nuclear magnetic resonance
polymerization

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10.1021/ma100991c

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title = "Reducing the degree of branching in polyacrylates via midchain radical patching : a quantitative melt-state NMR study",

abstract = "Degrees of branching were measured with Cmelt-stateNMRin poly(n-butyl acrylates) synthesized in both the presence and absence of 1-octanethiol at various temperatures, and their precision calculated based on the signal-to-noise ratio of the quaternary carbon at the branching point. A significant decrease of branching was observed in the presence of a thiol during the polymerization process, experimentally confirming the “patching” effect of midchain tertiary radicals by the thiol. Thus, the addition of a chain transfer agent not only controls the chain length of the polyacrylate, but also the complexity of its microstructure is significantly reduced. In addition, the current work illustrates the potential of melt-state NMR for the quantitative determination of the degrees of branching with precision for example, for kinetics studies.",

keywords = "nuclear magnetic resonance, polymerization",

author = "Marianne Gaborieau and Koo, {Sandy P. S.} and Patrice Castignolles and Thomas Junkers and Christopher Barner-Kowollik",

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T1 - Reducing the degree of branching in polyacrylates via midchain radical patching : a quantitative melt-state NMR study

AU - Gaborieau, Marianne

AU - Koo, Sandy P. S.

AU - Castignolles, Patrice

AU - Junkers, Thomas

AU - Barner-Kowollik, Christopher

PY - 2010

Y1 - 2010

N2 - Degrees of branching were measured with Cmelt-stateNMRin poly(n-butyl acrylates) synthesized in both the presence and absence of 1-octanethiol at various temperatures, and their precision calculated based on the signal-to-noise ratio of the quaternary carbon at the branching point. A significant decrease of branching was observed in the presence of a thiol during the polymerization process, experimentally confirming the “patching” effect of midchain tertiary radicals by the thiol. Thus, the addition of a chain transfer agent not only controls the chain length of the polyacrylate, but also the complexity of its microstructure is significantly reduced. In addition, the current work illustrates the potential of melt-state NMR for the quantitative determination of the degrees of branching with precision for example, for kinetics studies.

AB - Degrees of branching were measured with Cmelt-stateNMRin poly(n-butyl acrylates) synthesized in both the presence and absence of 1-octanethiol at various temperatures, and their precision calculated based on the signal-to-noise ratio of the quaternary carbon at the branching point. A significant decrease of branching was observed in the presence of a thiol during the polymerization process, experimentally confirming the “patching” effect of midchain tertiary radicals by the thiol. Thus, the addition of a chain transfer agent not only controls the chain length of the polyacrylate, but also the complexity of its microstructure is significantly reduced. In addition, the current work illustrates the potential of melt-state NMR for the quantitative determination of the degrees of branching with precision for example, for kinetics studies.

KW - nuclear magnetic resonance

KW - polymerization

UR - http://handle.uws.edu.au:8081/1959.7/552061

U2 - 10.1021/ma100991c

DO - 10.1021/ma100991c

M3 - Article

SN - 0024-9297

VL - 43

SP - 5492

EP - 5495

JO - Macromolecules

JF - Macromolecules

IS - 13

ER -

Reducing the degree of branching in polyacrylates via midchain radical patching : a quantitative melt-state NMR study

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