Analysis of the self-heating process of tetrafluoroethylene in a 100-dm3-reactor

Ferrero, Fabio; Zeps, Robert; Beckmann-Kluge, M.; Schröder, V.; Spoormaker, Tom

doi:10.1016/j.jlp.2012.06.001

Cited by 10 publications

(5 citation statements)

References 5 publications

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“…TFE is dangerous to work with, and care must be taken to avoid subjecting TFE to conditions where it may autopolymerize or decompose. The mechanism of decomposition has been reported in detail. ,,− In summary, TFE does not exist in ethylenic form per se; that is, electronic and steric factors perturb the electron distribution in the π-orbital to such an extent that the molecule exists as a biradicalloid and not as a canonical ethylenic species . This in turn translates to a molecule that can very easily undergo addition reactions, and TFE may easily undergo self-addition to form cyclo-octafluorobutane (Δ H R = −103 kJ/mol) .…”

Section: Synthesis Of Tfe and Concomitant Safety Aspectsmentioning

confidence: 99%

“…This leads to tremendous pressure spikes and the concomitant explosion of the containing vessel. Studies on the thermal decomposition of TFE in both small- (1 L) and large-volume (100 L) vessels indicate that the autodecomposition temperature decreases with pressure and decreases with reactor volume. , …”

Section: Synthesis Of Tfe and Concomitant Safety Aspectsmentioning

confidence: 99%

“…Studies on the thermal decomposition of TFE in both small-(1 L) and largevolume (100 L) vessels indicate that the autodecomposition temperature decreases with pressure and decreases with reactor volume. 44,76 The effect of volume is inferred to be related to an increase in internal vessel surface area. The rearrangement reaction to form CF 4 and carbon may occur in the gas phase but requires high temperatures (which may also be induced by rapid changes in pressure).…”

Section: Chemical Reviewsmentioning

confidence: 99%

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Polytetrafluoroethylene: Synthesis and Characterization of the Original Extreme Polymer

2019

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This Review aims to be a comprehensive, authoritative, and critical review of general interest to the chemistry community (both academia and industry) as it contains an extensive overview of all published data on the homopolymerization of tetrafluoroethylene (TFE), detailing the TFE homopolymerization process and the resulting chemical and physical properties. Several reviews and encyclopedia chapters on the properties and applications of fluoropolymers in general have been published, including various reviews that extensively report copolymers of TFE (listed below). Despite this, a thorough review of the specific methods of synthesis of the homopolymer, and the relationships between synthesis conditions and the physicochemical properties of the material prepared, has not been available. This Review intends to fill that gap. As known, PTFE and its marginally modified derivatives comprise some 60−65% of the total international fluoropolymer market with a global increase of ca. 7% per annum of its production. Numerous companies, such as Asahi Glass, Solvay Specialty Polymers, Daikin, DuPont/Chemours, Juhua, 3F, 3M/ Dyneon, etc., produce TFE homopolymers. Such polymers, both high-molecular-mass materials and waxes, are chemically inert and hydrophobic and exhibit an excellent thermal stability as well as an exceptionally low coefficient of friction. These polymers find use in applications ranging from coatings and lubrication to pyrotechnics, and an extensive industry (electronic, aerospace, wires and cables, and textiles) has been built around them. South Africa, being the third largest producer of fluorspar (CaF 2 ), the precursor to hydrogen fluoride and fluorine, has embarked on an industrial initiative to locally beneficiate its fluorspar reserves, with the local production of fluoropolymers being one projected outcome. As our manuscript focuses specifically on the homopolymerization of TFE (the starting point for all fluoropolymer industries), it will be of considerable use to start-up companies and other commercial entities looking to enter the fluoropolymer market, as well as to end-user companies. The manuscript commences with a short discussion on the synthesis and production of TFE (both at industrial and laboratory scales), including the safety aspects surrounding handling (because that monomer is regarded as explosive if brought into contact with oxygen due to the formation of peroxides), transport, and storage, and then expands into detailed discussions dealing with aspects such as the various additives used (buffers, chain transfer agents, surfactants, etc.), the solvent environment, and the reaction conditions. A further section reports the properties of PTFE with respect to the polymerization conditions as well as an overview on the specialized techniques used to characterize PTFE. Finally, the applications of PTFE in various fields, ranging from electrical insulation to tribological to medical applications, as well as chemically resistant coatings and pyrotechnics, are discussed.

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Section: Synthesis Of Tfe and Concomitant Safety Aspectsmentioning

confidence: 99%

Section: Synthesis Of Tfe and Concomitant Safety Aspectsmentioning

confidence: 99%

Section: Chemical Reviewsmentioning

confidence: 99%

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Polytetrafluoroethylene: Synthesis and Characterization of the Original Extreme Polymer

2019

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“…GWP value (100 years) lower than 300 Acute toxicity with an LC 50 value of 20,000 ppm or higher per Organisation for Economic Co-operation and Development (OECD) guidelines Non-or mildly-flammable Performance equivalent to R-410A This paper provides physical properties and theoretical cycle data, compatibility with oils, and performance studies of HFO-1123 mixtures as an alternatives for R-410A. HFO-1123 is known to undergo disproportionation in the presence of an ignition source (Equation 1: Lisochkin and Poznyak 2006;Ferrero et al 2012). This reaction is a self-decomposing reaction accompanied by large heat generation, and there is a risk of causing destruction of air conditioning equipment; therefore, evaluations to determine whether it can be used as a refrigerant safely are a key factor to its practical application.…”

Section: Introductionmentioning

confidence: 99%

Development of New Low-GWP Refrigerants–Refrigerant Mixtures Including HFO-1123

Hashimoto

Otsuka

Fukushima

et al. 2019

Science and Technology for the Built Environment

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New refrigerants with low global warming potential (GWP) are currently being developed to replace conventional higher GWP refrigerants. Recently, we have developed binary and ternary refrigerant mixtures, HFO-1123/HFC-32 and HFO-1123/HFC-32/HFO-1234yf. They showed azeotropic-like behavior and the potential to be an alternative to R-410A used in domestic and commercial air-conditioners. This work investigated the physical properties of these new refrigerants, including the critical parameters, PVT relation and compatibility with oils, and performed the theoretical cycle analysis. Equations of state developed from the physical properties were used in the theoretical analysis. The analysis showed that the performance of these new refrigerants are comparable to the performance of conventional ones. In addition, this work closely studied the selfdecomposition of HFO-1123 and confirmed that it does not occur in the ordinary operating range of airconditioning equipment.

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“…To our knowledge, the synthetic routes to well-defined perfluorometallacyclopentanes all involve the oxidative coupling of TFE, as outlined in eq . ,,,− ,,,,, This oxidative coupling reaction appears to be common for other late transition metals, as complexes 2 – 6 (Chart ) are all formed upon reaction of an appropriate metal precursor with TFE. Such routes are problematic for discovery research today as TFE has become increasingly unavailable for purchase due to the explosion hazards associated with its handing. − TFE can be prepared inexpensively on a reasonable scale from the thermal pyrolysis of waste polytetrafluoroethylene (PTFE), − but such routes typically involve temperatures above 600 °C and the use of a quartz furnace connected to a vacuum manifold. Moreover, the pyrolysis route does not eliminate the detonation hazards accompanying the recondensed TFE or the problems associated with the acute toxicity of octofluoroisobutylene, − which can be formed as a byproduct in the thermal degradation of PTFE. ,, Other methods exist to generate TFE more expensively on a small scale, , but require gas handling techniques that can complicate experimental protocols.…”

Section: Introductionmentioning

confidence: 99%

Mild, Safe, and Versatile Reagents for (CF₂)_n Transfer and the Construction of Fluoroalkyl-Containing Rings

Kaplan

Chen

et al. 2013

Organometallics

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The preparation of new dizinc reagents [(MeCN) 2 Zn((CF 2 ) n ) 2 Zn(MeCN) 2 ] (n = 3, 4, and 6) is reported. We show that the C4 reagent can readily transmetalate nickel to form a mononuclear perfluoronickelacycle. We also demonstrate that the reagents can be used to prepare novel fluoroorganics containing either perfluoroalkyl ring systems or perfluoroalkyl linked arenes under relatively mild conditions.

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Analysis of the self-heating process of tetrafluoroethylene in a 100-dm3-reactor

Cited by 10 publications

References 5 publications

Polytetrafluoroethylene: Synthesis and Characterization of the Original Extreme Polymer

Polytetrafluoroethylene: Synthesis and Characterization of the Original Extreme Polymer

Development of New Low-GWP Refrigerants–Refrigerant Mixtures Including HFO-1123

Mild, Safe, and Versatile Reagents for (CF₂)_n Transfer and the Construction of Fluoroalkyl-Containing Rings

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Analysis of the self-heating process of tetrafluoroethylene in a 100-dm3-reactor

Cited by 10 publications

References 5 publications

Polytetrafluoroethylene: Synthesis and Characterization of the Original Extreme Polymer

Polytetrafluoroethylene: Synthesis and Characterization of the Original Extreme Polymer

Development of New Low-GWP Refrigerants–Refrigerant Mixtures Including HFO-1123

Mild, Safe, and Versatile Reagents for (CF2)n Transfer and the Construction of Fluoroalkyl-Containing Rings

Contact Info

Product

Resources

About

Mild, Safe, and Versatile Reagents for (CF₂)_n Transfer and the Construction of Fluoroalkyl-Containing Rings