Acta Polymerica 38 (1987) Nr. (0 585ing that o w method gives the diffusion coefficients of the chains with the higher degree of polymerization, but from the inspection nf the conservation law of segment density it bccomes more ohvious [9].

Die rnetallalkoxid-katalysierte I'olyesterhildung w u d c rnittels kinctischcr und niclitkinctiscber Methodeu untersucht. Die rnikrokinrtischen Geschwindigkeitskonstalltcll werden aus Polylrondensationsversuchen in dunnen Schmelzeschichten erhalten. Spektroskopische Untersuchungeii von Benzoesiiureester-Metallalkoxid-Modellsystemen zeigten keine direkten Wechselwirkungen des Mctalls mit den Estergruppen an. Die Ka talysatoren heeinflussen die inter-und intramolekularen Wasserstoffbruckenhindungcn tlcr u)-Hydroxyalkylestergruppen. Die Aktivierung der Polykondensationsreaktion erfolgt durch Alkoxosaurcn, die aus den Metallalkoxiden und den im System vorhandenen Hydroxyalkylestergruppen gebildet werden. ~arna~duae obpa30sanu.~ noaua$upoa anicoiccuaawu MemamaKIIHeTHYeCKHM11 II HeKAHeTHYeCKKMM MeTOAaMH MCCJIeAOBaJIOCb 06pa30BaHHe IIOJIM3@pOB, KaTaJIH3HpOBaHHOe aJIHOKC11gaMII MeTaJIJla. MHKPOKHHeTHYeCKHe KOHCTaHTbI CKOPOCTII peaKqHH IIOJIyYeHbI 113 OIIbITOB IIOJIHKOHAeHCaqHll B TOHKHX CJIORX PaCIIJIaBa. CneRTpOCKOIIHYeCKHe HCCJIenOBaHHH MOgeJIbHbIX CHCTeM 3@Hp 6eH3011H08 KHCJIOTbI/ H a HHTep-H RHTpaMOJIeKyJIRpHbIe BO,C(OpOnHbIe CBR311 w-rHApOKCHaJIKHJI3~IIpHbIX rpynn. YCHOpeHlle peaKU11ll IIOJIHKOHgeHCaqHH IIpOIICXOAHT 38 CYeT aJIHOKCOHHCJIOT, KOTOpbIe 0 6 p a 3 y m~c~ H 3 aJIHOKCHAOB MeTaJIJIa H HMeIoILWXCR B CIICTeMe r H n P O K C I I a J I K 1 1~3~H p H b I X FpyIIII. anKoHcHn MeTama He yxa3b1sann H a n p m o e s a a a~o n e i c~~~e MeTanna c ~@IIPHOB rpynnoi. K a~a~~~s a~o p b r B n m m Metalalkoxide catalysis in the formation of polyestersBased on kinetic and non-kinetic methods, the metalalkoxidc catalysis in Llic formation of polyesters was examined. The rnicrokinetic rate constants for several polyester/catalyst systems were determined by polycondensation in thin layers of the melt. Spectroscopic investigations of benzoic acid esters/rnetalalkoxide model systems showed that no direct interactions between metal and ester groups are possible. The catalysts influence the inter-and intramolecular hydrogen bridge bonds of the w-hydroxyalkylestcr groups. The polycondensation reaction was activated by alkoxid acids. These acids were formed from metal alkoxids and the hydroxyallryl ester groups contained in the system.