Some peculiarities of cationic polymerization of trioxane

Enikolopyan, N. S.; Irzhak, V. J.; Kravchuk, I.P.; Plechova, O.A.; Rakova, G. V.; Romanov, L.M.; Savushkina, G.P.

doi:10.1002/polc.5070160456

J. polym. sci., C Polym. symp.

1967

DOI: 10.1002/polc.5070160456

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Some peculiarities of cationic polymerization of trioxane

N. S. Enikolopyan¹,

V. J. Irzhak²,

I.P. Kravchuk³

et al.

Abstract: The polymerization of trioxane in various solvents and in the presence of different catalysts has been investigated. Effect of the catalyst on the induction period was studied and the kinetic criterium for establishing the nature of the induction period was suggested. The maximal rate of polymerization is first order with respect to the catalyst concentration and of different high orders with respect to the monomer concentration, depending on the solvent. The polymer molecular weight is proportional to the ext… Show more

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Cited by 7 publications

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Über die Polymerisation von Trioxan in 1,4‐Dioxan

Švec¹,

Vollmert²

1975

Angew. Makromol. Chem.

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SUMMARY:The cationic polymeriz~tion of trioxane in 1,4-dioxane, initiated by BF,.EtlO has been investigated. In order 10 start the polymerization a relatively large concentration of initiator is necessary. A considerable part of the BFJ.EtzO-initiator (ZY~",;,) does not take part in the polymeriration. Another result of our experiments is that during the polymeriiration a depolymcrization of polymer molecules takes place. Comparing depolyrnerization-experiments of the prepared polyoxymethylen-samples at 180°C have shown that the stability mainly depends on the molecular weight and not on the type of solvcnf (dioxane or nitrobenzcne) present during the polymeri7ation. kin k i t ling

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Über die Polymerisation von Trioxan in 1,4‐Dioxan

Švec¹,

Vollmert²

1975

Angew. Makromol. Chem.

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Electrochemically initiated cationic polymerization of trioxane in acetonitrile. Part I

Mengoli¹,

Vidotto²

1973

Makromol. Chem.

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Trioxane, dissolved in acetonitrile solvent containing tetrabutylammonium perchlorate as background electrolyte, has been polymerized under continuous current supply at the anode of an electrolytic cell with separated anodic and cathodic compartments. The polymerization rate and the molecular weight of the polymers obtained are functions of the current intensity and the reaction temperature.At 20°C the reacting system presents a poor autocatalytic trend and may be described by the hypothesis of the steady state for the active species.The thermal stability of the polyoxymethylenes obtained in acetonitrile solvent is improved by the electrochemical copolymerization of trioxane with 1,3-dioxolane. ZUSAMMENFASSUNG:Trioxan, gelost in Acetonitril, das Tetrabutylammoniumperchlorat als Leitsalz enthielt, wurde an der Anode einer elektrolytischen Zelle, bei der Anodenraum und Kathodenraum getrennt waren, unter kontinuierlicher Stromzufuhr polymerisiert. Die Polymerisationsgeschwindigkeit und das Molekulargewicht der entstandenen Polymeren sind Funktionen der Stromstirke und der Reaktionstemperatur.Bei 20 O C zeigt das Reaktionssystem eine schwach autokatalytische Tendenz und kann unter Annahme eines Gleichgewichtszustandes fiir die aktiven Spezies beschrieben werden.Die thermische Stabilitat des Polyoxymethylens, das in Acetonitril als Losungsmittel erhalten wurde, wird durch die elektrochemische Copolymerisation des Trioxans mit 1,3-Dioxolan verbessert.

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Electrochemically initiated cationic polymerization of trioxane in benzonitrile and nitrobenzene. Part II

Mengoli¹,

Vidotto²

1973

Makromol. Chem.

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Electrochemically initiated cationic polymerizations of trioxane in benzonitrile and in nitrobenzene have been carried out. In both of these solvents the polymerizations go on even when the current is switched off. In benzonitrile the polymerizations are affected, however, by a slow termination reaction probably involving the solvent. This leads to a satisfactory thermal stability of the polyoxymethylenes. Based on certain assumptions the specific propagation rate constants of trioxane polymerizations in both solvents and the corresponding activation energies have been deduced from the initial polymerization rates of experiments carried out at various concentrations of initiating species and at various temperatures. ZUSAMMENFASSUNG:Es wurde eine elektrochemisch initiierte, kationische Polymerisation von Trioxan in Benzonitril oder in Nitrobenzol durchgefiihrt. I n jedem der beiden Losungsmittel schreitet die Polymerisation auch dann fort, wenn der Strom abgeschaltet wird; jedoch wird die Polymerisation in Benzonitril durch eine langsame Abbruchreaktion beeinfldt, bei der wahrscheinlich Losungsmittel mitreagiert ; diese Reaktion verleiht den Polyoxymethylenen eine zufriedenstellende thermische Stabilitat. Unter gewissen Voraussetzungen wurden die spezifischen Wachstumskonstanten und die entsprechenden Aktivierungsenergien der Trioxanpolymerisationen in beiden Losungsmitteln aus den Anfangspolymerisationsgeschwindigkeiten von Experimenten abgeleitet, die bei verschiedenen Konzentrationen der initiierenden Spezies und bei verschiedenen Temperaturen durchgefiihrt wurden.

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Some peculiarities of cationic polymerization of trioxane

Cited by 7 publications

References 9 publications

Über die Polymerisation von Trioxan in 1,4‐Dioxan

Über die Polymerisation von Trioxan in 1,4‐Dioxan

Electrochemically initiated cationic polymerization of trioxane in acetonitrile. Part I

Electrochemically initiated cationic polymerization of trioxane in benzonitrile and nitrobenzene. Part II

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