The mechanism of radiation-induced polymerizations in the solid state has been a subject mostly open to speculation. As radiation usually generates several kinds of active species (radicals and ions) it is difficult to find out, which of these actually causes polymerization. We have developped a method distinguishing between cationic and anionic active centers. Cationic polymerizations are terminated by addition of a base such as sodium alkoxide in a suitable solvent. The alkoxide is incorporated into the polymer as an endgroup. This endgroup is determined analytically after isolation and purification of the polymer. The incorporation of alkoxy endgroups into the polymer is a proof of the o…

Über den Mechanismus der Entstehung von 1.3.5-Trioxacycloheptan bei der kationischen Polymerisation von 1.3-Dioxolan

Die von MIKI, HIGASHIMURA und OKAMURA beschriebene Bildung von Trioxacycloheptan wahrend der kationischen Polymerisation von Dioxolan wird durch Spuren von Wasser verursacht und ist nicht auf die von MIKI et al. postulierte backbiting-Reaktion zuruckzufuhren. Wasser fuhrt durch Polymerisationsubertragung zu Hemiformal-Endgruppen, aus welchen Formaldehyd abgespalten wird, der dann zusammen mit Dioxolan Trioxacycloheptan ergibt. Die Trioxacycloheptankonzentration steigt schon nach kurzen Polymerisationszeiten nicht weiter an und ist direkt proportional der Menge an zugesetztem Wasser; dadurch ist eine bequeme und sehr empfindliche Bestimmung des Gesamtwassergehaltes im Polymerisationsansatz m…

In order to determine the concentration of active centers, polymerizations are terminated by addition of sodium alkoxide. This yields alkoxy endgroups which after acid hydrolysis of the isolated and purified polymers are determined by gaschromatography of the produced alcohol. In cationic polymerization of anhydrous formaldehyde at −78°C under certain reaction conditions a fast and quantitative initiation reaction and no kinetic chain termination have been observed. Presumably living polymers are obtained. The unexpected decrease in the rate of polymerization after a certain conversion is ascribed to hindrance of monomer diffusion in the crystalline polymer in which the active centers are i…