Reactivity of poly(chlorotrifluoroethylene) (PCTFE) oil and PCTFE derivatives with phenyllithium and phenyl Grignard reagents

Beaver, Larry G.; Danielson, Neil D.

doi:10.1007/bf00296233

Cited by 6 publications

(1 citation statement)

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“…Taylor et al extensively reported the modification of PCTFE particularly in the presence of a cobalt(II) trapping agent generated in situ from the chloro(pyridine)cobaloxime(III)/magnesium redox couple (Schemes and ). Using a substitution of the PCTFE chlorine atom, it was possible to introduce various functional groups such as carboxylic acid, − aldehyde, alcohol, , aromatic, − pyridine, alkyl, ,, allylic, , and mercapto . Cais and Kometani also used a displacement mechanism for the dechlorination of PCTFE in order to obtain poly(CTFE- co -trifluoroethylene) or poly(trifluoroethylene) using tributyl tin hydride.…”

Section: Well-defined Copolymers Based On Ctfementioning

confidence: 99%

(Co)polymers of Chlorotrifluoroethylene: Synthesis, Properties, and Applications

2013

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Section: Well-defined Copolymers Based On Ctfementioning

confidence: 99%

(Co)polymers of Chlorotrifluoroethylene: Synthesis, Properties, and Applications

2013

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Simultaneous fluorine elimination and alkylation of poly(tetrafluoroethylene)

Hlavatý

Kavan

Bastl

1996

Angew. Makromol. Chem.

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PTFE (powder or foils) was defluorinated and derivatized in a one-step process by alkyl-and aryllithium in the presence of tetramethylethylenediamine" (TMEDA) as a catalyst. As evidenced by infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and elemental analysis the C,H9-, C8HI7-, CI2Hz5-or phenyl groups were attached to a partly defluorinated macromolecular chain. Analogous reactions with dilithioaryl or dilithioalkyl agents presumably lead to crosslinking of the polymeric chains through alkyl or aryl groups. When the PTFE powder is treated with more concentrated RLi (>3 mol L-I) at temperatures >150°C, the defluorination is almost quantitative even in the absence of the catalyst. The TMEDA-catalyzed reaction proceeds via elimination and nucleophilic addition. On the other hand, more concentrated RLi in the absence of the catalyst seems to react via a radical mechanism. ZUS AMMENFASSUNG:PTFE (Pulver oder Folien) wurde mit Alkyl-und Aryllithium in Gegenwart von Tetramethylethylendiamin (TMEDA) bei erhohter Temperatur in einem Schritt defluoriert und derivatisiert. Die Ankniipfung von C4H,-, CBH17-, CI2H2,-oder Phenylgruppen an die teilweise defluorierte makromolekulare Kette wurde mit IR-und XPS-Spektroskopie sowie Elementaranalysen nachgewiesen. Die Einwirkung von Dilithiumaryl-oder Dilithiumalkylverbindungen auf PTFE unter identischen Reaktionsbedingungen fiihrte vermutlich zu iiber die Alkyl-oder Arylgruppen vernetzten Polymerketten. Beim Einsatz von konzentrierten RLi-Losungen (>3 M) bei Temperaturen >150°C verlauft die Reaktion auch ohne TMEDA. Es bildet sich ein fast fluorfreies nichtalkyliertes Produkt. Die Reaktion unter Zugabe von TMEDA verlauft iiber eine Eliminierung und eine nukleophile Addition. Dagegen verlauft die Einwirkung konzentrierter Lithiumverbindungen ohne TMEDA iiber einen radikalischen Mechanismus.

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