Dendrimers and dendronized polymers synthesis and characterization
Abstract: The goal of this work was to synthesize complex macromolecular architectures such as dendrimers and dendronized polymers, and evaluate the effect from the dendrons on the optical and material properties. The work presented in this doctoral thesis, Dendrimers and Dendronized Polymers - Synthesis and Characterization, is divided into one minor and one major part. The first part deals with the synthesis and characterization of two sets of dendritic porphyrins based on 2,2-bis(methylol)propionic acid (bis-MPA). The second part deals with the synthesis and characterization of dendronized poly(hydroxyl ethyl methacylate), dendronized poly(norbornene), and dendronized triblock copolymers, were the pendant dendrons are based on bis-MPA.Both free-base and zinc containing dendritic porphyrins was synthesized up to the fifth generation by employing iterative ester coupling utilizing the acetonide protected anhydride of bis-MPA as generic building block.First and second generation dendron bearing methacrylates based on 2-hydroxyethyl methacrylate were also synthesized by utilizing the acetonide protected anhydride of bis-MPA, and subsequently polymerized by atom transfer radical polymerization. By adopting a divergent “graft-to” approach starting from the first generation dendronized poly(hydroxyl ethyl methacrylate), well-defined dendronized polymers with acetonide, hydroxyl, acetate and hexadecyl surface functionality were obtained.By utilizing the same divergent iterative esterfication, first to fourth generation dendron functionalized norbornenes were synthesized. These monomers were polymerized by ring-opening metathesis polymerization, utilizing either Grubbs´ first or second generation catalyst.Acrylate functional first to fourth generation monomers were synthesized by the copper(I) catalyzed “click” coupling of azido functional dendrons and propargyl acrylate. The monomers were polymerized to dendronized triblock copolymers by reversible addition-fragmentation chain transfer polymerization, utilizing a difunctional poly(methyl methacrylate) as macro chain transfer agent.The bulk properties of the dendronized poly(hydroxyl ethyl methacrylate) and poly(norbornene) were investigated by dynamic rheological measurements and differential scanning calorimetry. It was found that all the acetonide functional bis-MPA based dendronized polymers had glass transitions temperatures in a similar range. The rheological behaviour showed that for the dendronized polymers having the same backbone length the complex viscosity as a function of functionality was independent of the surface functionality of the polymer. The generation number of the polymer had a profound influence on the complex viscosity, changing form a Newtonian behaviour to a shear thinning behaviour when the generation of the dendrons was increased from two to four. The dendronized poly(norbornene) had increasingly shorter backbone lengths for each generational increase, and for the materials set with comparably lower degree of polymerization, the G’ part of the complex modulus was mostly affected by attaching larger dendrons. In the case of the sample set of higher degree of polymerization, the second, third, and fourth generation samples had similar slopes of the G’ and G” curves, indicating a similar relaxation behaviour.
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