The mechanism of cationic polymerization of lactones in the presence of hydroxyl-containing compounds (hydroxomechanism) has been studied taking as an example the polymerization of &propiolactone, 8-caprolactone, glycolide and lactide. In this mechanism chain propagation proceeds via preliminary chain transfer t o the monomer. This transfer accelerates the process, decreases the molecular weight of the polymer, narrows the molecular-mass distribution and enhances the general stability of the system.
Die kationische Polymerisation von Laetonen in Gegenwart von hydroxylhaltigenVerbindungen Der Mechanismus der kationischen Polymerisation von Lactonen in Gegenwart hydroxylhaltiger Verbindungen (Hydroxomechanismus) wurde am Beispiel der Polymerisation von 8-Propiolacton, e-Caprolacton, Glycolid und Lactid untersucht. Bei diesem Mechanismus erfolgt das Kettenwachstum iiber eine vorhergehende Kettenubertragung auf das Monomer. Diese ffbertragungsreaktion beschleunigt den Prozell, verringert die rel. Molekulmasse des Polymers, verschmalert die Molekulmassenverteilung und erhoht die allgemeine Stabilitat des Systems. Icamuonnas nonuncepuaayua naxmnoe e npucymemeuu z u a p o m w o a e p w a q u x coeaunenuii Ha IIpFlMepe UOJIFlMepFla~FlH ~-llpOllFlOJIaKTOHa, &-KallpOJIaKTOHa, rJIHKOJIklAa Fl JIaKTHAa PaCCMOTpeH MeXaHL13M KaTllOHHOa llOJIHMepH3a~FlFl JlaKTOHOB B IlPHCYTCTBHH rFl~pOKCFlJICO~ep?Ka~HX COenFlHeHMa -, ,~HAPOKCOMeXaHH3M". B TOM ~e x a~~l a~e POCT qenn ~~O F~C X O A F~T nyTena npensapmenbHo€i nepefiaqa qenti H a MoHoMep. nepexon Ha Hero ysennwsaeT CKOPOCTH npoqecca, yMemruaeT MoneKympHsxe Macm nonmepa, cymaeT MoseKynspHo-Maccosoe paCllpe~eJIeHFle Fl YBenFlqFlBaeT 06rqym CTa6FlJIbHOCTb CFlCTeMbI. in the presence of hydroxyl-containing compounds K%z: process without HC Acta Polymeriu 34 (1983) Heft 11/12
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