THE CHEMISTRY OF HYDROPEROXIDES. V. THE THERMAL DECOMPOSITION OF tert-ALKYL PEROXIDES

Kharasch, M. S.; Fono, Andrew; Nudenberg, W.

doi:10.1021/jo01141a017

Cited by 64 publications

(33 citation statements)

References 7 publications

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“…With the conditions used in rheo‐Raman experiments, we described styrene polymerization by a kinetic scheme similar to that used previously replacing thermal initiation by thermal decomposition of DCP (Scheme ). The rate constant of DCP thermal decomposition calculated on the basis of literature data …”

Section: Resultsmentioning

confidence: 99%

In situ monitoring of styrene polymerization using Raman spectroscopy. Multi‐scale approach of homogeneous and heterogeneous polymerization processes

Brun

Youssef

Chevrel

et al. 2013

J Raman Spectroscopy

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International audienceFree radical polymerization of styrene was monitored in situ by combining Raman spectroscopy to other experimental techniques (gravimetry and rheology). Three different processes were investigated: bulk, emulsion and miniemulsion polymerization. A complete analysis of the evolution of Raman spectrum during the course of reaction showed that a lot of information about molecular dynamics could be extracted and related to chemical phenomena. In addition, we report for the first time the coupling of Raman spectroscopy to a rheometer in order to monitor styrene bulk polymerization both at the scale of chemical bonds and at the scale of macroscopic phenomena (viscosity variation)

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Section: Resultsmentioning

confidence: 99%

In situ monitoring of styrene polymerization using Raman spectroscopy. Multi‐scale approach of homogeneous and heterogeneous polymerization processes

Brun

Youssef

Chevrel

et al. 2013

J Raman Spectroscopy

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“…DCP was chosen for its desirable decomposition rate at this temperature. 14 The resultant chromatograms are presented in Figure 2b. Clearly, the polymerization proceeded faster, and M n and conversion exceeded 10 000 and 50%, respectively, at 6 h. The polydispersity remained as small as that in the system without DCP.…”

Section: Resultsmentioning

confidence: 99%

Kinetic Study on Nitroxide-Mediated Free Radical Polymerization of tert-Butyl Acrylate

Goto

Fukuda

1999

Macromolecules

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The kinetics of nitroxide-mediated free radical polymerization of tert-butyl acrylate (tBA) was studied. It was demonstrated that the polymerization rate can be increased by addition of a proper amount of a radical initiator, dicumyl peroxide (DCP), without causing any appreciable broadening of the polydispersity. The use of di-tert-butyl nitroxide (DBN) allowed the controlled polymerization of tBA to proceed at a lower temperature than the polymerization controlled by a TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy) derivative, which was conducted by Georges et al. [Macromolecules 1996, 29, 8993]. The pseudo-first-order activation rate constant k act of the poly(tBA)-DBN adduct was also determined by the GPC curve-resolution method to be 1.0 × 10 -3 s -1 at 120°C, which indicates that the adduct experiences activation-deactivation cycles frequently enough to afford a low polydispersity. Nevertheless, the polydispersity markedly increased and the rate of polymerization decreased at later stages of polymerization due to the decomposition of the alkoxyamine and the subsequent hydrogen transfer.

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“…during thermochemical reactions of PE crosslinkThe reaction mechanisms in crosslinking have ing were easily detected, and the effect of antioxibeen thought to be free radical reactions, [1][2][3][4] but dant can be analyzed. the reaction conditions have been selected empirically.…”

Section: Introductionmentioning

confidence: 99%

ESR study on chemical crosslinking reaction mechanisms of polyethylene using a chemical agent?II. The effect of phenolic antioxidants

Yamazaki

Seguchi

1997

J. Polym. Sci. A Polym. Chem.

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The effect of antioxidant on the reaction mechanism of chemical crosslinking of polyethylene (PE) with dicumyl peroxide (DCP) at high temperatures was investigated by electron spin resonance (ESR). The antioxidant reacts with the alkyl radicals in PE formed by the thermal decomposition of DCP above 120°C, and disturbs the crosslinking. A phenolic type antioxidant produced the phenoxy radical by the reaction with alkyl radicals formed in PE. It is suggested that the selection of a suitable antioxidant for PE crosslinking can be made by ESR analysis. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2431–2439, 1997

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THE CHEMISTRY OF HYDROPEROXIDES. V. THE THERMAL DECOMPOSITION OF tert-ALKYL PEROXIDES

Cited by 64 publications

References 7 publications

In situ monitoring of styrene polymerization using Raman spectroscopy. Multi‐scale approach of homogeneous and heterogeneous polymerization processes

In situ monitoring of styrene polymerization using Raman spectroscopy. Multi‐scale approach of homogeneous and heterogeneous polymerization processes

Kinetic Study on Nitroxide-Mediated Free Radical Polymerization of tert-Butyl Acrylate

ESR study on chemical crosslinking reaction mechanisms of polyethylene using a chemical agent?II. The effect of phenolic antioxidants

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