Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 1. Nitroxide-Mediated Polymerization

Yoshikawa, Chiaki; Goto, and Atsushi; Fukuda, Takeshi

doi:10.1021/ma012203t

Cited by 33 publications

(47 citation statements)

References 50 publications

(87 reference statements)

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“…1 ), where DEPN is N-tertbutyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide. 23 In the presence and absence of BPO, this system was confirmed to follow the stationary-state kinetics (eq 6) and the power-law kinetics (eq 11), respectively. The thermal initiation rate of S is negligibly small at this temperature.…”

Section: Gpc Polydispersity Methodsmentioning

confidence: 81%

“…Because, experimentally, stationary systems are much more easily achieved than power-law systems, the application of the polydispersity method is more recommended for the former systems. In fact, the polydispersity method has been so far applied to power-law systems to experimentally test the theory, 23,25 rather than to determine the rate constant.…”

Section: Reliability Of the Gpc Methodsmentioning

confidence: 99%

“…One is to add a sufficient amount of a suitable radical initiator to the power-law or power-law-type system, 22,23,[25][26][27][28] as already discussed. The other is to add a sufficiently large amount of the capping agent, X ⅐ , before polymerization, so that the X ⅐ concentration and hence the P ⅐ concentration (cf.…”

Section: Reliability Of the Gpc Methodsmentioning

confidence: 99%

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Fundamental kinetic aspects of living radical polymerization and the use of gel permeation chromatography to shed light on them

Fukuda

2004

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:The control achievable by living radical polymerization (LRP) is based on a kinetic balance of the activation-deactivation reversible reactions, which are specific to LRP, with conventional elementary reactions such as initiation, propagation, and termination. This work describes, as plainly as possible, how chains grow and how their polydispersity evolves as they experience activation-deactivation cycles and how these processes can be quantitatively analyzed by gel permeation chromatography. A comprehensive probability theory on the polydispersity indices of LRP polymers is presented.

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Section: Gpc Polydispersity Methodsmentioning

confidence: 81%

Section: Reliability Of the Gpc Methodsmentioning

confidence: 99%

Section: Reliability Of the Gpc Methodsmentioning

confidence: 99%

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Fundamental kinetic aspects of living radical polymerization and the use of gel permeation chromatography to shed light on them

Fukuda

2004

J. Polym. Sci. A Polym. Chem.

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“…[24] Later Fukuda et al [3][4][5] derived a more general implicit equation for the evolution of the concentrations of P and N radicals. They started from Equation (5) assuming a constant rate of initiation R i and solved it together with Equation (6) by assuming:…”

Section: M 2pmentioning

confidence: 99%

“…Following Fischer, [6] Fukuda et al [3][4][5] approximated the quasi-equilibrium condition by the relaxed version Equation (2) and obtained a general solution of the kinetic equations under this approximation, arriving at Fischer's regimes as limiting cases of such solution.…”

mentioning

confidence: 99%

On the Nitroxide Quasi‐Equilibrium in the Alkoxyamine‐Mediated Radical Polymerization of Styrene

Saldívar‐Guerra

Bonilla

Becerril

et al. 2006

Macro Theory & Simulations

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Summary: The range of validity of two popular versions of the nitroxide quasi‐equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, kc[P][N] = kd[PN], where P, N and PN are living, nitroxide radicals and dormant species respectively, with kinetic constants kc and kd, is found valid only for small values of the equilibrium constant K (10−11–10−12 mol · L−1) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, kc[P][N] = kd[PN]0 was found to be remarkably good up to values of K around 10−8 mol · L−1. This upper bound is numerically found to be 2–3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico‐chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested.Validity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant.imageValidity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant.

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Nitroxide‐Mediated Polymerization

Vivaldo‐Lima

Jaramillo‐Soto

Penlidis

2016

Encyclopedia of Polymer Science and Technology

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Nitroxide‐mediated polymerization (NMP) has been studied abundantly in the past three decades. There are several very good and recent reviews on the topic available in the literature. Although in this article we provide an overview on the research efforts focused on the polymer chemistry of NMP, our emphasis is placed on research aspects of NMP from a polymer reaction engineering perspective. Namely, we emphasize the use of engineering tools (such as mathematical modeling) on the design, analysis, and control of NMP processes (process engineering) and the well‐defined microstructures obtained by NMP (product engineering). These aspects are not sufficiently discussed or even included in previous reviews on NMP. Despite of all the intensive research programs carried out in academia and industrial research centers over 30 years, there are still several issues that limit the commercial exploitation of NMP. These issues, which include slow polymerization rates, reduced amount of monomers amenable for polymerization by NMP, low molecular weights, and insufficient commercial availability of NMP controllers, are also discussed.

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Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 1. Nitroxide-Mediated Polymerization

Cited by 33 publications

References 50 publications

Fundamental kinetic aspects of living radical polymerization and the use of gel permeation chromatography to shed light on them

Fundamental kinetic aspects of living radical polymerization and the use of gel permeation chromatography to shed light on them

On the Nitroxide Quasi‐Equilibrium in the Alkoxyamine‐Mediated Radical Polymerization of Styrene

Nitroxide‐Mediated Polymerization

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