The rate of anodic polymerization of 1,3,5-trioxane in the ethylene dichloride solution of tetraethylammonium hexachloroantimonate increases with an increase of current density and of initial monomer concentration.The species responsible for initiating the polymerization has been found spectrophotometrically to be H+SbCI; which is generated "in situ" during electrolysis. The anodic oxidation of SbCI; ions produces SbCI', radicals which abstract hydrogen atoms from components of the reaction mixture to yield H 'SbCl;.Also FeCI,, deposited at the anode during the electrolysis of tetraethylammonium chloride at an iron anode, initiates the polymerization of 1,3,5-trioxane. The electrochemical polymerization of 1,3,5-trioxane occurs also at other reactive metal electrodes with the hexachloroantimonate salt. ZUSAMMENFASSUNG:Die Geschwindigkeit der anodischen Polymerisation von 1,3,5-Trioxan in einer 1,2-Dichlorathanlosung von Tetraathylammoniumhexachloroantimonat nimmt mit zunehmender Stromdichte und Ausgangsmonomerkonzentration zu.Die fur die Auslosung der Polymerisation verantwortliche Spezies ist, wie spektrophotometrisch gefunden wurde, H + SbCl;, welches wahrend der Elektrolyse ,,in situ" gebildet wird. Durch die anodische Oxidation von SbC1;-Ionen entstehen SbC1;-Radikale, die aus Komponenten der Reaktionsmischung Wasserstoffatome abspalten und H +SbCl ; bilden.Das wahrend der Elektrolyse von Tetraathylammoniumchlorid an der Eisen-Anode sich absetzende FeCI, lost die Polymerisation von 1,3,5-Trioxan ebenfalls aus. Eine elektrochemische Polymerisation von 1,3,5-Trioxan mit dem Hexachloroantimonatsalz tritt auch an anderen Elektroden aus reaktionsfahigen Metallen auf.

The electro-initiated anodic polymerization of indene in ethylene dichloride solutions of tetraethylammonium hexachloroantimonate and tetrabutylammonium perchlorate as background electrolytes was studied. The polymerization was conducted either under continuous electrolysis or by addition of the monomer to the pre-electrolysed solution of the salt. The polymer formation was affected by the amount of electricity, the monomer concentration, and the nature of the electrolytes. The rate and degree of polymerization with the hexachloroantimonate salt are relatively high in comparison with the perchlorate salt. The characteristically colored species, formed during polymerization, were investigated spectrophotometrically. Mechanisms for the initiation processes of both procedures were elucidated.

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The electrolytically initiated anodic polymerization of indene in the solutions of tetraethylammonium hexachloroantimonate and tetrabutylammonium perchlorate in nitrobenzene under constant electric current and constant potential electrolysis conditions was studied. The polymerization was followed either under continuous electrolysis or by addition of the monomer to the pre-electrolysed solution of the salt. The monomer consumption follows the first-order rate-law, Iog[M]o/[Mlt= kt, and the rate constant of the polymerization increases with increasing current level. The polymer formation was greatly affected by the change of the dielectric constant of the medium, the anode material, and the nature of the supporting electrolyte. The mode of initiation process depends upon the type of the salt. Mechanisms for the initiation reaction were elucidated. *) Part I : cf.').

The electroinitiating polymerization of 1,3,5-trioxane in solution and molten state with tetraethylammonium hexachloroantimonate has been investigated. Molecular weights of the polymers, as indicated by their viscosity numbers increase with increasing initial monomer concentration and decreasing current levels. The induction period of polymerization is dependent on the monomer concentration and reaction temperature. The overall activation energy of the polymerization was determined to be about 10, OO kcal/mol(41,83 kJ/mol). The true initiator appears to be the protonic acid formed in situ during the course of electrolysis. The polymerization of trioxane was also carried out chemically with SbC1, and H,O@SbCl:. ZUSAMMENFASSUNG:Es wurde die elektroinitiierte Polymerisation von 1,3,5-Trioxan (TO) mit Tetraethylammoniumhexachloroantimonat sowohl in Losung als auch im geschmolzenen Zustand untersucht. Die Molekulargewichte der Polymeren, charakterisiert durch die Grenzviskositatszahl, erhohen sich mit zunehmender Anfangskonzentration an Monomerem und abnehmender Stromstarke. Die Induktionsperiode der Polymerisation ist von der Monomerkonzentration und der Reaktionstemperatur abhangig. Die Bruttoaktivierungsenergie fur die Polymerisation wurde zu ungefahr 10 kcal/mol (41,83 kJ/mol) bestimmt. Der eigentliche Initiator scheint die Protonensaure zu sein, die in situ wahrend der Dauer der Elektrolyse gebildet wird.Die Polymerisation von TO wurde auch chemisch mit SbCl, und H,O@SbCl: durchgefuhrt.