Detailed analysis of termination kinetics in radical polymerization

Buback, Michael; Russell, Gregory T.

doi:10.1002/pi.6501

Cited by 5 publications

(6 citation statements)

References 76 publications

(230 reference statements)

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“…His personality explains the great breadth and reach of the papers that we have in this series 6–15 . I’d like to mention some of these briefly, as all are excellent and so very well speak for themselves.…”

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confidence: 93%

“…His personality explains the great breadth and reach of the papers that we have in this series. [6][7][8][9][10][11][12][13][14][15] I'd like to mention some of these briefly, as all are excellent and so very well speak for themselves. The paper by Graeme Moad reflects with gentle humour on how he, Dick and Aubrey Jenkins, a prior Chair of SPT, struggled with the development of a clear terminology for specific types of controlled chain polymerizations, and more particularly with the term reversible-deactivation radical polymerization (RDRP).…”

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confidence: 96%

“…The paper by Graeme Moad reflects with gentle humour on how he, Dick and Aubrey Jenkins, a prior Chair of SPT, struggled with the development of a clear terminology for specific types of controlled chain polymerizations, and more particularly with the term reversible‐deactivation radical polymerization (RDRP) 6 . In two papers right up Dick's street, are Michael Buback and Greg Russell's work which really is a complete and comprehensive review of the characterisation and understanding around chain‐termination in radical polymerizations, 7 and Natalie Stingelin and Blair Brettmann's fantastic paper with their colleagues on degrees of polymer crystallinity versus polymer crystalline quality 8 . We also should spend a moment to reflect on Prof. Melissa Chin Han Chan, who so very sadly, and so young, passed away last year.…”

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confidence: 99%

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Special issue: visionary polymer research for a better world. The professor R.G. ‘Dick’ Jones commemorative issue

Hiorns

2023

Polymer International

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This special issue has been published to celebrate the life of Professor R.G. 'Dick' Jones, who passed away on the 23rd of December 2021. This series, by its extraordinary breadth and depth, reflects the reach of Dick Jones into many scientists' lives, in ways many of us are not even aware of.Dick was born in Nottingham (UK) and then grew up in New Zealand. At the age of 23 he returned on a long, propeller-buzzed flight to study his PhD at Leeds, entitled, 'Photosensitisation, Retardation and Inhibition of Polymerisations of Acrylonitrile by Fe(III) and Cu(II) Salts'. His supervisor was Lord Dainton and Dick revelled in some of his phrases, such as 'the fountain of science'. While the rest of his career was in the UK, with many visits to far-flung places around the world, of which later, he kept New Zealand close to his heart, managing regular visits over the years. His career was cemented with his appointment in 1970 to the then new University of Kent, which had been chartered only five years earlier. His winning a Professorship in 1998, and his subsequent appointment to the Head of the School Physical Sciences spoke greatly of his rigor and his exceptional management skills. These were much in demand, sadly due to restructuring which he had to carry out to save that department during a difficult period for chemistry in the UK.Looking back to that time, there were few groups in chemistry in Canterbury who had strong financing and real international clout, given its relatively short history, but his was one of them. He was extremely successful in finding Japanese NEDO funding, and this underpinned a highly creative and productive scientific period. His numerous publications were wide-ranging and touched on subjects such as developing electron-beam polymer-resists for microlithography, 1 understanding the appearance of an extraordinary blue colour during the Wurtz reaction, 2 the multimodal molecular weight distribution of polysilane syntheses, 3 and the first examples of conjugated amphiphilic multi-block copolymers. 4 What was astonishing in this period was the way in which he managed to work several subjects in parallel, each with complete thoroughness, and this speaks of someone who applied themselves with great seriousness, even though his general demeanour would never hint at this. He was always looking for humour, and often the research group would end up at a BBQ at his place, to enjoy good wine and the beautiful garden maintained by David Cheung his partner, his life, and rock for forty years. Dick (right) and his partner, David Cheung, with Kapiti at Canterbury (UK) in 2014 (photo: Roger Hiorns).

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Special issue: visionary polymer research for a better world. The professor R.G. ‘Dick’ Jones commemorative issue

Hiorns

2023

Polymer International

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“…Numerous studies on the kinetics of free radical polymerization reactions have converged on a consensus, indicating that the overall kinetic coefficients for the various stages of these reactions can be determined by considering two pivotal factors: the kinetic coefficient associated with the chemical step and the kinetic coefficient corresponding to the diffusive step. These coefficients are denoted in Equations ( 17) and ( 18) for the termination and propagation stages, respectively [16,[24][25][26]. The chemical step occurs when participating species are in close proximity and capable of reacting, while the diffusive step concerns the journey and challenges that participating species face in order to meet and initiate their respective reactions.…”

Section: Discussionmentioning

confidence: 99%

“…In the field of free radical polymerization, exploring the relationship between polymeric radicals and the termination coefficient is an intriguing subject. The length of radicals can trigger diffusive effects, leading to distinctive behaviors in the evolution of termination coefficients [16].…”

Section: Introductionmentioning

confidence: 99%

Exploring Some Kinetic Aspects of the Free Radical Polymerization of PDMS-MA

Victoria-Valenzuela,

Morales-Cepeda

2024

Processes

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This study conducts a theoretical exploration of the free radical polymerization of polydimethylsiloxane homopolymers with a methyl methacrylate end group (PDMS-MA). To achieve this, a methodology is developed to model and simulate experimental data previously reported by one of the authors. The model incorporates a typical chain reaction mechanism, encompassing initiation, propagation, chain transfer, and termination stages. The resulting ordinary differential equations from this mechanistic approach are numerically integrated over time. Employing a semi-heuristic procedure, the study derives estimated values for the diffusive steps of termination (ktd) and propagation (kpd). Methodological accuracy is assessed through a comparison of the mathematical model results and experimental data. This evaluation includes the estimation of conversion and the average molecular weight (both number (Mn) and weight (Mw)) at three distinct monomer concentrations, considering a 4.78% mol initiator-to-monomer ratio. The theoretical results obtained from this study contribute to a better understanding of the evolution of diffusion coefficients. These coefficients play a crucial role in influencing the behavior of the studied reactions, particularly in relation to the absence of the autoacceleration effect in these reactions.

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