Free radical reactions of polyarylenealkylenes and their hydroperoxides. Review

Chuchin, A.Ye.

doi:10.1016/0032-3950(79)90342-3

Cited by 5 publications

(3 citation statements)

References 82 publications

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“…Analysis of free energy profiles for each of these routes indicated that the minimum energy pathway (assuming absence of radicals at the beginning of the reaction) involves a peroxide intermediate, 4 , which essentially undergoes a homolytic cleavage to generate the

\dot{normalO} H

radical. Involvement of peroxide intermediates and the following homolytic cleavage was proposed in several earlier studies of different polymeric systems . Here, the intermediate 4 is formed by a radical quenching of 2 by the

\dot{normalO} O H

generated in the step 1 → 2 .…”

Section: Resultsmentioning

confidence: 99%

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Quantum Mechanical Computations and Microkinetic Modeling to Obtain Mechanism and Kinetics of Oxidative Degradation of a Polyimide

Kunnikuruvan

Parandekar²,

Prakash³

et al. 2015

Macro Theory & Simulations

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Improving the high-temperature long-term thermo-oxidative stability of high-performance polymers is crucial for their applications in aerospace industry. For designing novel polymers with improved oxidative stability, it is vital to identify the most reactive moiety of the polyimide toward oxidation and understand the mechanism of oxidation. Quantum chemical calculations and microkinetic analysis have been carried out here to obtain the molecular level details of the oxidative degradation of a commercially important polyimide, PMR-15, at high temperatures. This study identifies the most vulnerable moiety of PMR-15 toward oxidation. Moreover, the rate-determining step in the oxidative degradation is also scrutinized. Mechanistic understanding of the reaction leads us to propose new modifications of PMR-15 with a better thermo-oxidative stability.

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\dot{normalO} H

\dot{normalO} O H

generated in the step 1 → 2 .…”

Section: Resultsmentioning

confidence: 99%

“…Involvement of peroxide intermediates and the following homolytic cleavage was proposed in several earlier studies of different polymeric systems. [16,26,33,34] Here, the intermediate 4 is formed by a radical quenching of 2 by the _ OOH generated in the step 1 ! 2.…”

Section: Resultsmentioning

confidence: 99%

Quantum Mechanical Computations and Microkinetic Modeling to Obtain Mechanism and Kinetics of Oxidative Degradation of a Polyimide

Kunnikuruvan

Parandekar²,

Prakash³

et al. 2015

Macro Theory & Simulations

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“…The possibility of such a biradical intermediate was introduced by Iratcabal and Cardy, based on their computational studies using the AM1 method . It is noted in passing that the formation of radicals at high temperature is observed in various polymers. − …”

Section: Introductionmentioning

confidence: 99%

Polymerization Mechanism and Cross-Link Structure of Nadic End-Capped Polymers: A Quantum Mechanical and Microkinetic Investigation

Kunnikuruvan

Parandekar²,

Prakash³

et al. 2017

Macromolecules

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The applications of norbornene or nadic end-capped high performance polymers (HPPs) are manifold and have been discussed in the literature for more than two decades. The cross-links formed from nadic end-cap determine the mechanical and thermal properties of these polymers. In spite of extensive studies, the cross-link structure and the cross-linking mechanism of nadic end-capped polymers remain elusive. Quantum chemical computations together with microkinetic modeling are used here to elucidate these aspects. Various possible polymerization pathways that contribute to the final cross-link structure of nadic end-capped polymers are proposed, and the distribution of cross-link structures is computed. The cross-linking mechanisms are modeled considering radical initialization, chain propagation, and termination, and our computations identify the most active cross-linking mechanism. The results of our study are then compared with the available experimental data.

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Relation between conditions of synthesis, structure and properties of polyarylene methylenes

Ivanilova¹,

Korshak²,

Gashnikova³

et al. 1982

Polymer Science U.S.S.R.

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Free radical reactions of polyarylenealkylenes and their hydroperoxides. Review

Cited by 5 publications

References 82 publications

Quantum Mechanical Computations and Microkinetic Modeling to Obtain Mechanism and Kinetics of Oxidative Degradation of a Polyimide

Quantum Mechanical Computations and Microkinetic Modeling to Obtain Mechanism and Kinetics of Oxidative Degradation of a Polyimide

Polymerization Mechanism and Cross-Link Structure of Nadic End-Capped Polymers: A Quantum Mechanical and Microkinetic Investigation

Relation between conditions of synthesis, structure and properties of polyarylene methylenes

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