Two series of aliphatic hyperbranched (HB) polyesters have been synthesized from 2,2-bis(hydroxymethyl)propionic acid and di-trimethylolpropane using pseudo-one-step or one-step procedure. The structure and properties of these HB polyesters, investigated with different characterization techniques in solution, melt and solid state, were compared between each other, with commercial Boltorn HB polyesters and samples obtained by modification of the end -OH groups with ß-alanine or stearic acid. Seven HB polyesters were fractionated in order to obtain three fractions of each sample. The experimental results obtained from NMR spectroscopy, acid and hydroxyl number titration, GPC, vapour pressure osmometry, MALDI TOF and ESI mass spectrometry indicate that during the synthesis reactivity of terminal and linear -OH groups was not the same and that side reactions occurred in significant amount, which led to the lowering of the number average molar mass and broadening of the molar mass distribution. According to the results obtained from viscosimetry of diluted solutions and dynamic light scattering the best solvents for these HB polyesters are 0.7 mass % solution of LiCl in N,N-dimethylacetamide and N-methyl-2-pyrrolidinon (NMP). The limiting viscosity number and the hydrodynamic radius of the samples increase up to the sixth pseudo generation in these two solvents. Investigated HB polyesters behave as Newtonian liquids in concentrated solutions (c < 50 mass % in NMP) at T < 55 °C. The same was observed for the samples from fourth till sixth pseudo generation in melt at T > 70 °C. At all other experimental conditions used in this work these polymers show shear-thinning behaviour due to the high ability for the aggregation. Thermal stability of investigated HB polyesters increases with increasing number of the pseudo generation. The influence of the procedure for the synthesis and type of end groups on the properties of these polymers is discussed.
| Identifer | oai:union.ndltd.org:uni-osnabrueck.de/oai:repositorium.ub.uni-osnabrueck.de:urn:nbn:de:gbv:700-2006112416 |
| Date | 22 November 2006 |
| Creators | Vuković, Jasna |
| Contributors | Prof. Dr. Manfred D. Lechner, Prof. Dr. Slobodan Jovanovic |
| Source Sets | Universität Osnabrück |
| Language | English |
| Detected Language | English |
| Type | doc-type:doctoralThesis |
| Format | application/zip, application/pdf |
| Rights | http://rightsstatements.org/vocab/InC/1.0/ |
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