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A. Duda, T. Biela, A. Kowalski, J. Libiszowski

Amines as (co)initiators of cyclic esters' polymerization (in English)

Polimery 2005, No 7-8, 501




Summary

A review reports on application of amines as (co)initiators in the ring-opening polymerization of aliphatic cyclic esters. First, the use of tertiary amines (R3N) as initiators of the controlled polymerization of highly strained, four-membered b-lactone (b-propiolactone, PL) is described [equation (1)]. Then attempts at the high temperature polymerizations of the medium strained, six- and seven-membered d- and e-lactones initiated with primary amines (RNH2) or a-amino acids are briefly discussed. Finally, it is shown in more detail that the best results have been obtained recently in the processes catalyzed additionally with tin(II) octoate [Sn(Oct)2]. Mechanisms of these polymerizations are also discussed. Results of the kinetic studies [equation (9) and (10)] as well as 1H NMR, MALDI TOF mass spectrometry, and size exclusion chromatography (SEC) measurements, carried out in the authors’ laboratory, indicate that polymerizations of e-caprolactone (CL) or L,L-lactide (LA) initiated with RNH2/Sn(Oct)2 fulfill living process criteria and therefore allow to fully control the syntheses of the corresponding polymers. The selected syntheses applications, such as preparation of the copolymers N-carboxyanhydrides of a-aminoacids and LA [equation (7)] or star-shaped polymers based on polyamino dendrimers [formula (I) and (II)] are also described.


Key words: e-caprolactone, L,L-lactide, b-lactones, a-amino acids, amines, tin(II) octoate, ring-opening polymerization, aliphatic polyesters, star-shaped polymers


A. Duda, T. Biela, A. Kowalski, J. Libiszowski (1.18 MB)
Amines as (co)initiators of cyclic esters' polymerization (in English) (part I)
A. Duda, T. Biela, A. Kowalski, J. Libiszowski (1.12 MB)
Amines as (co)initiators of cyclic esters' polymerization (in English) (part II)