2,2,6,6-tetramethylpiperidyl-1-thiyl

Bennett, John E.; Sieper, Helmut; Tavs, P.

doi:10.1016/s0040-4020(01)82568-0

Cited by 52 publications

(35 citation statements)

References 5 publications

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“…were supplied by BASF, products 1, 2, 4, 6, 10, 12, 13 were purchased from Sigma Aldrich Corporation and compounds 5 [52], 7 [53], 8 [54], 9 [55] were prepared according to previously described procedures. For comparison a commercial alkoxyamine Flamestab®NOR116 (supplier BASF SE) was used.…”

Section: Methodsmentioning

confidence: 99%

Disulfides – Effective radical generators for flame retardancy of polypropylene

Pawelec

Holappa

Tirri

et al. 2014

Polymer Degradation and Stability

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The potential of thirteen aliphatic, aromatic, thiuram and heterocyclic substituted organic disulfide derivatives of the general formula R-S-S-R' as a new group of halogen-free flame retardants (FR) for polypropylene films have been investigated. According to DIN 4102-1 standard ignitibility test, for the first time it has been demonstrated that many of the disulfides alone can effectively provide flame retardancy and self-extinguishing properties to polypropylene (PP) films at already very low concentrations of 0.5 wt%. In an effort to elucidate the mechanism of the thermal decomposition of disulfide derivatives the fragmentation patterns of the evolved gases from a thermogravimetric analyzer (TGA) have been analyzed by simultaneous mass spectrometry (MS) and Fourier transform infrared spectrometry (FTIR). The main decomposition products initiated by homolytic scission of the S-S bond and/or scission of the C-S bond were identified as thiols, aliphatic and aromatic hydrocarbons, isothiocyanates (depending on the disulfide structures) with further evolution of elemental sulfur and sulfur dioxide at temperatures of above 300 o C and 450 o C, respectively. Based on this preliminary study, we have shown that disulfides represented by e.g. diphenyl disulfide (1), 5,5'-dithiobis(2-nitrobenzoic acid) (2), bis(1-phenyl-1H-tetrazol-5yl)-disulfide (4), 2-bisbenzothiazole-2,2′-disulfide (6) and N,N-dithiobis-(phtalimide) (10) constitute a new halogen-free family of additives for flame retarding of polypropylene.

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Section: Methodsmentioning

confidence: 99%

Disulfides – Effective radical generators for flame retardancy of polypropylene

Pawelec

Holappa

Tirri

et al. 2014

Polymer Degradation and Stability

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“…In contrast to its oxy-analogue 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), TEMPS usually exists in the dimer form, bis(2,2,6,6-tetramethylpiperidin-1-yl)disulfide(BiTEMPS), owing to localization of the spin density on the sulfur atom instead of the nitrogen due to differences in electronegativity. [34,35] BiTEMPS was first reported by Bennett et al in 1967 to be thermally and reversibly dissociable under moderate heating (Scheme 1a). [34] Thed etailed dissociation kinetics and additional characteristics of BiTEMPS and other thionitroxide dimers were subsequently investigated by other groups.…”

mentioning

confidence: 99%

“…[34,35] BiTEMPS was first reported by Bennett et al in 1967 to be thermally and reversibly dissociable under moderate heating (Scheme 1a). [34] Thed etailed dissociation kinetics and additional characteristics of BiTEMPS and other thionitroxide dimers were subsequently investigated by other groups. [35,36] These studies revealed that the bond dissociation energy (BDE) of the SÀSb ond in BiTEMPS (26-31 kcal mol À1 )i sa pproximately half of that in dialkyldisulfides (60-70 kcal mol À1 ), [35] which creates ad rastic difference in the intrinsic thermal dissociability between these two classes of compounds (Scheme 1a).…”

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confidence: 99%

Thermally Adjustable Dynamic Disulfide Linkages Mediated by Highly Air‐Stable 2,2,6,6‐Tetramethylpiperidine‐1‐sulfanyl (TEMPS) Radicals

2017

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Intrinsically exchangeable dynamic covalent bonds that can be triggered by readily usable stimuli offer easy incorporation of their dynamic properties in various molecular systems, but the library of such bonds is still being developed. Herein, we report the dynamic covalent chemistry of 2,2,6,6-tetramethylpiperidine-1-sulfanyl (TEMPS) dimers derived from thermally reversible homolytic dissociation of disulfide linkages. High air stability of TEMPS was observed even at 100 °C, affording facile employment of thermal dissociation-association equilibria and adjustable bond exchange properties under atmospheric conditions. We also established an efficient synthetic route for a modifiable derivative of the dimer that enabled incorporation of dynamic properties into linear and network polymer structures. The obtained polymers showed controllable molecular weights, temperature-dependent swelling properties, healing ability, and recyclability, reflecting the thermally tunable dynamics of the dimer.

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“…We used bis(2,2,6,6‐tetramethylpiperidin‐1‐yl)disulfide (BiTEMPS) as a DCB moiety and designed CLPs with either DCBs or conventional covalent bonds at their crosslinking points to test our hypothesis (Figure ). BiTEMPS units behave as stable covalently bound structures at room temperature, while they can be homolytically cleaved at the central S−S bond and undergo exchange at temperatures higher than 80 °C. Furthermore, BiTEMPS can be applied to exchange reactions in air because of the high stability of the dissociated TEMPS radical toward oxygen and olefins.…”

Section: Figurementioning

confidence: 99%

Fusion of Different Crosslinked Polymers Based on Dynamic Disulfide Exchange

et al. 2020

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Crosslinked polymers (CLPs) exhibit exceptional mechanical properties as well as good chemical and solvent resistance. However, their reprocessing, recycling, and modification remain difficult. One promising approach to overcome this limitation is to introduce dynamic covalent bonds that enable chain‐exchange reactions and network‐structure rearrangements in identical polymer networks (A–A fusion), resulting in self‐healing and reprocessing properties. Reported here is the fusion of two distinct polymer networks (A–B fusion) by the dynamic behavior of bis(2,2,6,6‐tetramethylpiperidin‐1‐yl)disulfide (BiTEMPS) at the interface between different CLPs. The appearance, swelling behavior, and mechanical properties of the fused samples indicate exchange reactions of the BiTEMPS units and the formation of topological bonds at the interface, commensurate with the generation of a CLP that exhibits tunable properties.

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2,2,6,6-tetramethylpiperidyl-1-thiyl

Cited by 52 publications

References 5 publications

Disulfides – Effective radical generators for flame retardancy of polypropylene

Disulfides – Effective radical generators for flame retardancy of polypropylene

Thermally Adjustable Dynamic Disulfide Linkages Mediated by Highly Air‐Stable 2,2,6,6‐Tetramethylpiperidine‐1‐sulfanyl (TEMPS) Radicals

Fusion of Different Crosslinked Polymers Based on Dynamic Disulfide Exchange

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