Ab initio calculation of the rate coefficient for short-chain branching in free-radical polymerizations

J. S S Toh; D. M. Huang; P. A. Lovell; R. G. Gilbert

doi:10.1016/S0032-3861(00)00519-X

Ab initio calculation of the rate coefficient for short-chain branching in free-radical polymerizations

J. S S Toh, D. M. Huang, P. A. Lovell, R. G. Gilbert

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

Abstract

Short-chain branching in polyethylene, which involves a six-centre transition state, is studied by ab initio quantum mechanics up to the QCISD(T) level. The calculation gives a (low-pressure) activation energy of 73 kJ mol-1 and a frequency factor of 4.8 × 1012 s-1. The frequency factor for this six-centre transition state is expected to be of acceptable accuracy and also applicable to homologous systems, such as short-chain branching to polymer in acrylates. These results overestimate the amount of ethylene short-chain branching observed in experiment, but the discrepancy is within the uncertainties of both experiment and calculation. © 2000 Elsevier Science Ltd. All rights reserved.

Original language	English
Pages (from-to)	1915-1920
Number of pages	5
Journal	Polymer
Volume	42
Issue number	5
DOIs	https://doi.org/10.1016/S0032-3861(00)00519-X
Publication status	Published - 2001

Keywords

Ab inito calculations
Free-radical polymerization
Short-chain branching

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10.1016/S0032-3861(00)00519-X

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@article{5b59b9826be14babba4535ab4fa41ce3,

title = "Ab initio calculation of the rate coefficient for short-chain branching in free-radical polymerizations",

abstract = "Short-chain branching in polyethylene, which involves a six-centre transition state, is studied by ab initio quantum mechanics up to the QCISD(T) level. The calculation gives a (low-pressure) activation energy of 73 kJ mol-1 and a frequency factor of 4.8 × 1012 s-1. The frequency factor for this six-centre transition state is expected to be of acceptable accuracy and also applicable to homologous systems, such as short-chain branching to polymer in acrylates. These results overestimate the amount of ethylene short-chain branching observed in experiment, but the discrepancy is within the uncertainties of both experiment and calculation. {\textcopyright} 2000 Elsevier Science Ltd. All rights reserved.",

keywords = "Ab inito calculations, Free-radical polymerization, Short-chain branching",

author = "Toh, {J. S S} and Huang, {D. M.} and Lovell, {P. A.} and Gilbert, {R. G.}",

year = "2001",

doi = "10.1016/S0032-3861(00)00519-X",

language = "English",

volume = "42",

pages = "1915--1920",

journal = "Polymer",

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TY - JOUR

T1 - Ab initio calculation of the rate coefficient for short-chain branching in free-radical polymerizations

AU - Toh, J. S S

AU - Huang, D. M.

AU - Lovell, P. A.

AU - Gilbert, R. G.

PY - 2001

Y1 - 2001

N2 - Short-chain branching in polyethylene, which involves a six-centre transition state, is studied by ab initio quantum mechanics up to the QCISD(T) level. The calculation gives a (low-pressure) activation energy of 73 kJ mol-1 and a frequency factor of 4.8 × 1012 s-1. The frequency factor for this six-centre transition state is expected to be of acceptable accuracy and also applicable to homologous systems, such as short-chain branching to polymer in acrylates. These results overestimate the amount of ethylene short-chain branching observed in experiment, but the discrepancy is within the uncertainties of both experiment and calculation. © 2000 Elsevier Science Ltd. All rights reserved.

AB - Short-chain branching in polyethylene, which involves a six-centre transition state, is studied by ab initio quantum mechanics up to the QCISD(T) level. The calculation gives a (low-pressure) activation energy of 73 kJ mol-1 and a frequency factor of 4.8 × 1012 s-1. The frequency factor for this six-centre transition state is expected to be of acceptable accuracy and also applicable to homologous systems, such as short-chain branching to polymer in acrylates. These results overestimate the amount of ethylene short-chain branching observed in experiment, but the discrepancy is within the uncertainties of both experiment and calculation. © 2000 Elsevier Science Ltd. All rights reserved.

KW - Ab inito calculations

KW - Free-radical polymerization

KW - Short-chain branching

U2 - 10.1016/S0032-3861(00)00519-X

DO - 10.1016/S0032-3861(00)00519-X

M3 - Article

VL - 42

SP - 1915

EP - 1920

JO - Polymer

JF - Polymer

IS - 5

ER -

Ab initio calculation of the rate coefficient for short-chain branching in free-radical polymerizations

Abstract

Keywords

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