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Solution Properties of Dendronized Poly(Hydroxy Ethyl Methacrylate) Polymers
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-9372-0829
2006 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 44, no 11, 3674-3683 p.Article in journal (Refereed) Published
Abstract [en]

Four generations of dendronized polymers with a methacrylate backbone and hydroxy-functionalized aliphatic polyester dendrons based on 2,2-bis(methylol)propionic acid were studied in solutions by rheological measurements, dynamic light scattering, turbidimetry, and H-1 NMR self-diffusion measurements to reveal the effect of increasing hydrophilicity and molecular size on their solution properties. The studied polymers were interesting new amphiphiles with a hydrophobic main chain and a hydrophilic shell. Evidence of aggregation upon the heating of the first-generation polymer in an aqueous solution was obtained by dynamic light scattering and turbidimetry, reflecting the effect of the hydrophobic polymer backbone, whereas the higher generation polymers did not show aggregation upon heating. Although the dimensions of the polymers were observed to increase with increasing generation, all the polymers exhibited low viscosities and Newtonian flow behavior in both aqueous and dimethyl sulfoxide solutions. The relative viscosities of the polymers in water and dimethyl sulfoxide showed that the conformation of the polymers was somewhat more open in dimethyl sulfoxide, and this led to higher viscosities than those in water, in agreement with the H-1 NMR diffusion measurements, by which the dimensions were found to be larger for the polymers dissolved in dimethyl sulfoxide.

Place, publisher, year, edition, pages
2006. Vol. 44, no 11, 3674-3683 p.
Keyword [en]
dendrimers, NMR; viscosity, water-soluble polymers
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-5748DOI: 10.1002/pola.21471ISI: 000237704000024Scopus ID: 2-s2.0-33744832419OAI: oai:DiVA.org:kth-5748DiVA: diva2:10221
Note
QC 20100914Available from: 2006-05-17 Created: 2006-05-17 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Dendrimers and dendronized polymers: synthesis and characterization
Open this publication in new window or tab >>Dendrimers and dendronized polymers: synthesis and characterization
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

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.

Place, publisher, year, edition, pages
Stockholm: KTH, 2006. 66 p.
Series
Trita-FPT-Report, ISSN 1652-2443 ; 2006:10
Keyword
Dendrimers, dendronized polymers, atom transfer radical polymerisation, ring-opening metathesis polymerization, reversible addition-fragmentation chain transfer polymerization, 2, 2-bis(methylol)propionic acid, tri-block copolymers, rheology, differential scanning calorimerty, 1H-NMR self-diffusion
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-3970 (URN)91-7178-333-4 (ISBN)
Public defence
2006-06-02, D2, Lindstedsvägen 5, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100914Available from: 2006-05-17 Created: 2006-05-17 Last updated: 2010-09-14Bibliographically approved

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