Kinetics of Amine-Bis(phenolate) Iron-Mediated ATRP Up to High Pressure

Hendrik Schroeder; Michael Buback; Michael P. Shaver

doi:10.1021/acs.macromol.5b01390

Kinetics of Amine-Bis(phenolate) Iron-Mediated ATRP Up to High Pressure

Hendrik Schroeder, Michael Buback, Michael P. Shaver

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

Abstract

Atom-transfer radical polymerization (ATRP) of styrene catalyzed by chloro-substituted amine-bis(phenolate)iron complexes was investigated via online vis/NIR spectroscopy up to 6000 bar. Pressure significantly increases the rate of ATRP by enhancing both the equilibrium constant, K-ATRP, and the propagation rate coefficient, k(p). The observed negative reaction volume, Delta V-r(K-ATRP), is due to a stronger contraction of the ligand sphere for the Lewis-acidic Fe-III complex compared to the Fe-II complex. Despite the enormous rate enhancement of ATRP, narrow molar mass distributions may be obtained even at very high pressure and thus very high rates.

Original language	English
Pages (from-to)	6114-6120
Number of pages	7
Journal	Macromolecules
Volume	48
Issue number	17
DOIs	https://doi.org/10.1021/acs.macromol.5b01390
Publication status	Published - 8 Sept 2015

Keywords

TRANSFER RADICAL POLYMERIZATION
ACTIVATION-DEACTIVATION EQUILIBRIUM
PROPAGATION RATE COEFFICIENT
METAL SPIN-STATE
ATOM-TRANSFER
METHYL-METHACRYLATE
TERMINATION KINETICS
RATE CONSTANTS
IRON(III) COMPLEXES
RAFT-POLYMERIZATION

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10.1021/acs.macromol.5b01390

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title = "Kinetics of Amine-Bis(phenolate) Iron-Mediated ATRP Up to High Pressure",

abstract = "Atom-transfer radical polymerization (ATRP) of styrene catalyzed by chloro-substituted amine-bis(phenolate)iron complexes was investigated via online vis/NIR spectroscopy up to 6000 bar. Pressure significantly increases the rate of ATRP by enhancing both the equilibrium constant, K-ATRP, and the propagation rate coefficient, k(p). The observed negative reaction volume, Delta V-r(K-ATRP), is due to a stronger contraction of the ligand sphere for the Lewis-acidic Fe-III complex compared to the Fe-II complex. Despite the enormous rate enhancement of ATRP, narrow molar mass distributions may be obtained even at very high pressure and thus very high rates.",

keywords = "TRANSFER RADICAL POLYMERIZATION, ACTIVATION-DEACTIVATION EQUILIBRIUM, PROPAGATION RATE COEFFICIENT, METAL SPIN-STATE, ATOM-TRANSFER, METHYL-METHACRYLATE, TERMINATION KINETICS, RATE CONSTANTS, IRON(III) COMPLEXES, RAFT-POLYMERIZATION",

author = "Hendrik Schroeder and Michael Buback and Shaver, {Michael P.}",

year = "2015",

month = sep,

day = "8",

doi = "10.1021/acs.macromol.5b01390",

language = "English",

volume = "48",

pages = "6114--6120",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "17",

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TY - JOUR

T1 - Kinetics of Amine-Bis(phenolate) Iron-Mediated ATRP Up to High Pressure

AU - Schroeder, Hendrik

AU - Buback, Michael

AU - Shaver, Michael P.

PY - 2015/9/8

Y1 - 2015/9/8

N2 - Atom-transfer radical polymerization (ATRP) of styrene catalyzed by chloro-substituted amine-bis(phenolate)iron complexes was investigated via online vis/NIR spectroscopy up to 6000 bar. Pressure significantly increases the rate of ATRP by enhancing both the equilibrium constant, K-ATRP, and the propagation rate coefficient, k(p). The observed negative reaction volume, Delta V-r(K-ATRP), is due to a stronger contraction of the ligand sphere for the Lewis-acidic Fe-III complex compared to the Fe-II complex. Despite the enormous rate enhancement of ATRP, narrow molar mass distributions may be obtained even at very high pressure and thus very high rates.

AB - Atom-transfer radical polymerization (ATRP) of styrene catalyzed by chloro-substituted amine-bis(phenolate)iron complexes was investigated via online vis/NIR spectroscopy up to 6000 bar. Pressure significantly increases the rate of ATRP by enhancing both the equilibrium constant, K-ATRP, and the propagation rate coefficient, k(p). The observed negative reaction volume, Delta V-r(K-ATRP), is due to a stronger contraction of the ligand sphere for the Lewis-acidic Fe-III complex compared to the Fe-II complex. Despite the enormous rate enhancement of ATRP, narrow molar mass distributions may be obtained even at very high pressure and thus very high rates.

KW - TRANSFER RADICAL POLYMERIZATION

KW - ACTIVATION-DEACTIVATION EQUILIBRIUM

KW - PROPAGATION RATE COEFFICIENT

KW - METAL SPIN-STATE

KW - ATOM-TRANSFER

KW - METHYL-METHACRYLATE

KW - TERMINATION KINETICS

KW - RATE CONSTANTS

KW - IRON(III) COMPLEXES

KW - RAFT-POLYMERIZATION

U2 - 10.1021/acs.macromol.5b01390

DO - 10.1021/acs.macromol.5b01390

M3 - Article

SN - 0024-9297

VL - 48

SP - 6114

EP - 6120

JO - Macromolecules

JF - Macromolecules

IS - 17

ER -

Kinetics of Amine-Bis(phenolate) Iron-Mediated ATRP Up to High Pressure

Abstract

Keywords

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