Estimation of free radical polymerization rate coefficients using computational chemistry

Siziwe Bebe; Xinrui Yu; Robin A. Hutchinson; Linda J. Broadbelt

doi:10.1002/masy.200651117

Estimation of free radical polymerization rate coefficients using computational chemistry

Siziwe Bebe, Xinrui Yu, Robin A. Hutchinson^*, Linda J. Broadbelt

^*Corresponding author for this work

Chemical and Biological Engineering

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

10 Scopus citations

Abstract

This study explores the application of computational chemistry to estimate free radical polymerization rate coefficients. The Evans-Polanyi relationship is combined with computed heats of polymerization to estimate copolymerization reactivity ratios for many vinyl monomer pairs, focusing on acrylates, methacrylates and styrene, with accuracy assessed by comparison to experimental values. The effect of different optimization approaches on the values of thermodynamic properties is explored, and it is concluded that a combination of conventional optimization and relaxed potential energy scans was most effective at identifying global minima. The difference between thermodynamic properties calculated using the harmonic oscillator treatment and a hindered rotor model is evaluated for methyl methacrylate polymerization.

Original language	English (US)
Pages (from-to)	179-189
Number of pages	11
Journal	Macromolecular Symposia
Volume	243
DOIs	https://doi.org/10.1002/masy.200651117
State	Published - 2006

Keywords

Conformation optimization
Hindered rotor model
Kinetics (polym.)
Quantum chemistry
Radical polymerization
Reactivity ratios

ASJC Scopus subject areas

Condensed Matter Physics
Organic Chemistry
Polymers and Plastics
Materials Chemistry

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title = "Estimation of free radical polymerization rate coefficients using computational chemistry",

abstract = "This study explores the application of computational chemistry to estimate free radical polymerization rate coefficients. The Evans-Polanyi relationship is combined with computed heats of polymerization to estimate copolymerization reactivity ratios for many vinyl monomer pairs, focusing on acrylates, methacrylates and styrene, with accuracy assessed by comparison to experimental values. The effect of different optimization approaches on the values of thermodynamic properties is explored, and it is concluded that a combination of conventional optimization and relaxed potential energy scans was most effective at identifying global minima. The difference between thermodynamic properties calculated using the harmonic oscillator treatment and a hindered rotor model is evaluated for methyl methacrylate polymerization.",

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year = "2006",

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volume = "243",

pages = "179--189",

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T1 - Estimation of free radical polymerization rate coefficients using computational chemistry

AU - Bebe, Siziwe

AU - Yu, Xinrui

AU - Hutchinson, Robin A.

AU - Broadbelt, Linda J.

PY - 2006

Y1 - 2006

N2 - This study explores the application of computational chemistry to estimate free radical polymerization rate coefficients. The Evans-Polanyi relationship is combined with computed heats of polymerization to estimate copolymerization reactivity ratios for many vinyl monomer pairs, focusing on acrylates, methacrylates and styrene, with accuracy assessed by comparison to experimental values. The effect of different optimization approaches on the values of thermodynamic properties is explored, and it is concluded that a combination of conventional optimization and relaxed potential energy scans was most effective at identifying global minima. The difference between thermodynamic properties calculated using the harmonic oscillator treatment and a hindered rotor model is evaluated for methyl methacrylate polymerization.

AB - This study explores the application of computational chemistry to estimate free radical polymerization rate coefficients. The Evans-Polanyi relationship is combined with computed heats of polymerization to estimate copolymerization reactivity ratios for many vinyl monomer pairs, focusing on acrylates, methacrylates and styrene, with accuracy assessed by comparison to experimental values. The effect of different optimization approaches on the values of thermodynamic properties is explored, and it is concluded that a combination of conventional optimization and relaxed potential energy scans was most effective at identifying global minima. The difference between thermodynamic properties calculated using the harmonic oscillator treatment and a hindered rotor model is evaluated for methyl methacrylate polymerization.

KW - Conformation optimization

KW - Hindered rotor model

KW - Kinetics (polym.)

KW - Quantum chemistry

KW - Radical polymerization

KW - Reactivity ratios

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DO - 10.1002/masy.200651117

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EP - 189

JO - Macromolecular Symposia

JF - Macromolecular Symposia

SN - 1022-1360

ER -

Estimation of free radical polymerization rate coefficients using computational chemistry

Abstract

Keywords

ASJC Scopus subject areas

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