Polymerisation reactions initiated by high electric fields. Kinetic applications in the field of free cationic polymerisations

Brendlé, M.; Ilvoas, Anne-Marie

doi:10.1002/pi.4980080103

Cited by 7 publications

(1 citation statement)

References 20 publications

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“…Before Roth and Mayr's article, it was asserted that reliable rate constants of attack on an alkenic monomer by an unpaired carbenium ion, solvated mainly by the monomer, were in the range of k

_{p}^{+}

∼ 10 3 –10 6 L mol −1 s −1 , depending on the reaction conditions 2. Tables 1–5 list rate constants published for various carbocationic polymerizations 1–34. High values ( k p > 10 7 L mol −1 s −1 ) were reported before Roth and Mayr's work for polymerizations initiated by high energy, with researchers arguing that the high values were due to the lack of counteranions.…”

Section: Introductionmentioning

confidence: 96%

Kinetics and mechanisms in carbocationic polymerization: The quest for true rate constants

Puskás

Chan

McAuley

et al. 2005

J. Polym. Sci. A Polym. Chem.

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This article is a critical analysis of kinetic dataavailable on carbocationic polymerizations. A survey of published propagation rate constant (kp) data revealed several orders of magnitude differences. In this article, an explanation of this apparent discrepancy is offered with a case study involving the carbocationic polymerization of 2,4,6‐trimethylstyrene (TMS). With the polymerization mechanism originally proposed for this system, kp = 1.35 × 104 L mol−1 s−1 was extracted from experimental data with the Predici polyreaction package. The alternative mechanism yielded kp = 1.01 × 107 L mol−1 s−1, close to that predicted by Mayr's Linear Free Energy Relationship (LFER). We propose that true rate constants can only be obtained from direct competition experiments or from kinetic interpretation based on independently proven mechanisms. The second part of this review discusses critical analysis of the temperature and concentration dependence of various living IB systems. Comparison of the temperature dependence in systems initiated with 2‐ chloro‐2,4, 4‐ trimethylpentane (TMPCl)/TiCl4 from various laboratories yielded of ΔH ∼−25 and −34.5 kJ/mol for high and low TMPCl/TiCl4 ratios, respectively. Aromatic (cumyl‐type) initiators show ΔH ∼ −40 kJ/mol, whereas H2O/TiCl4 in the presence of the strong electron‐ pair donor dimethylacetamide gave ΔH = −12 kJ/mol. The significant differences indicate different underlying mechanisms with complex elementary reactions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5394–5413, 2005

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“…Before Roth and Mayr's article, it was asserted that reliable rate constants of attack on an alkenic monomer by an unpaired carbenium ion, solvated mainly by the monomer, were in the range of k

_{p}^{+}

Section: Introductionmentioning

confidence: 96%

Kinetics and mechanisms in carbocationic polymerization: The quest for true rate constants

Puskás

Chan

McAuley

et al. 2005

J. Polym. Sci. A Polym. Chem.

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Carbocationic Polymerization

Puskás

Kaszás

2003

Encyclopedia of Polymer Science and Technology

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This article summarizes fundamental and general aspects of carbocationic polymerizations, with a historical overview and up‐to‐date references. Following general considerations, the basic elements of carbocationic polymerization, such as monomers, initiating systems, solvents, and temperature, are discussed. Special attention is given to carbocation stability and monomer nucleophilicity, and dynamic interactions. The section on the kinetics of carbocationic polymerization presents current understanding of the elementary reactions—initiation, propagation, termination, and transfer reactions, and copolymerization. Controlled (living) carbocationic polymerization is discussed in a separate section. Finally, industrial carbocationic polymerizations are reviewed.

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Carbocationic Polymerization

Puskás¹,

Kaszás²

2016

Encyclopedia of Polymer Science and Technology

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This article summarizes fundamental and general aspects of carbocationic polymerizations, with a historical overview and up‐to‐date references. Following general considerations, the basic elements of carbocationic polymerization, such as monomers, initiating systems, solvents, and temperature, are discussed. Special attention is given to carbocation stability, monomer nucleophilicity, and dynamic interactions. The section on the kinetics of carbocationic polymerization presents current understanding of the elementary reactions—initiation, propagation, termination and transfer reactions, and copolymerization. Controlled (living) carbocationic polymerization is discussed in a separate section. Finally, industrial carbocationic polymerizations are also reviewed.

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Polymerisation reactions initiated by high electric fields. Kinetic applications in the field of free cationic polymerisations

Cited by 7 publications

References 20 publications

Kinetics and mechanisms in carbocationic polymerization: The quest for true rate constants

Kinetics and mechanisms in carbocationic polymerization: The quest for true rate constants

Carbocationic Polymerization

Carbocationic Polymerization

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