Die durch BF,-Etherat ausgeloste Reaktion zwischen Trioxan und Polydioxolan fiihrt zum Einbau von Oxymcthylen in die tote Polymerkette. Von theoretischen Uberlegungen zum Spaltungsmechanismus ausgehend, wird die Zeitabhangigkeit der Ausbildung der Mikrostruktur bchandelt. Moglichkeiten des Ablaufes der Umvertcilung uber Kettensegmente und Monomere wcrden mitcinander verglichen. Die kinetische bzw. thermodynamische Kontrolle wird diskuticrt. Aus den Aktiviwungsparametern wird auf einen SN1-Mechanismus geschlossen.M c c n e d o s a~u~ peaxyuu ncpenoca yenu HU nonuwep e npoyecce cononuwepuaa~uu mpuoxcana u 1 .d-duoxconaua. I I I . h" nepepacnpede.nemlo o~c~.~e r n u~~e n o s b i x u ox~u3mu.nenosbzx cmpyxmypmzx e3unuy npu peaxyuu mpuoxcana c nonudU0KCOJZUHO. M klHMqHpyeMaR 3@MpaTOM BF, PeaKqHR TpHOKCaHa C IIOJIM~MOKCOJIaHOM IIPMBOAHT K BKJIIOY€?HHH) OKCHMeTMJIeHa B , ,MepTBYIO" nOJIHMepHyIO qenb. klCXOAH H 3 TeOpeTMYeCKHX c o o 6 p a~e~~f i OTHOCMTejIbHO MeXaHR3Ma pa31qerIJIeHHl3, PaCCMaTpHBaeTCR BpeMeHHaR 3aBHCHMOCTb 06pa30BaHHR MHKPOCTPYHTYPbI H CPaBIIHBaIOTCR BOSMOXHOCTA np0-TeKaHHR IIepepaCIIpeAeJIeHHR IIO CerMeHTaM qelIH H no MOHOMepaM. 0 6 c y m~a e~c~ KHHeTMqeCHHfi M TepMOAHHaMH~c~n f i HoHTponb ~T H X npoqeccoB. 1.13 napaMeTpoB aKTHBaqm AenaeTcH ~~K J I I O Y~H M~ o H a m m m SN l -~e x a~m~a . Investigation on the transfer reaction to the polymer in the copolymerization of trioxane and 1.3-dioxolane I I I . The redistribution of the structural units in oxymethylene and oxyethylene in the reaction of trioxane and polydioxolaneThe reaction of trioxan and polydioxolane initiated by BF,-etherate introduces oxymethylene into the inactive polymer chain. Based on theoretical considerations of the splitting mechanism, the time-dependence of microstructure formation is discussed. Possible redistribution processes of chain segments and monomers are compared. The kinetic and thermodynamic control is considered. The values of the activation parameters suggest a SN1 mechanism.
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