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Crystallisation driven self-assembly of polylactide containing block copolymers synthesised by combination of ROP and RAFT
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Petzetakis, Nikolaos (2012) Crystallisation driven self-assembly of polylactide containing block copolymers synthesised by combination of ROP and RAFT. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b2661198~S1
Abstract
Chapter 1 is the main introduction of this work and it features the two main
concepts of this study. First living polymerisation techniques are introduced with a
special focus into RAFT and ROP. Secondly solution self-assembly is briefly
discussed.
In Chapter 2 we describe the synthesis of an amphiphilic block copolymer where
the two blocks are connected through a reversible bond. A Diels-Alder (DA) adduct
consisted of a maleimide-furan pair was chosen as the reversible linker. The solution
self-assembly of this polymer was studied by TEM and DLS giving rise to the
unexpected formation of cylindrical micelles.
In Chapter 3 the main objective was to synthesise new amphiphilic block
copolymers without the DA motif in order to investigate their self-assembly
behaviour compared to those for DA containing polymers obtained in Chapter 2. To
further understand this self-assembly behaviour our method has been extended to the
synthesis of other hydrophilic blocks and end group modified polymers. In addition,
some key properties of the polymers synthesised have been investigated.
In Chapter 4 our main goal is to understand the origins of the cylindrical micelle
formation seen in Chapter 2. We investigated the aggregation behaviour under the
aqueous thermal conditions in which the PTHPA block hydrolysis is performed.
Studies at different concentrations and solvent mixtures provide valuable
information regarding the self-assembly mechanism. In addition, the polymers with
modified end groups and the triblock copolymers synthesised in Chapter 3 are
studied and all the results compared.
In Chapter 5 we explore the living crystallisation driven self-assembly of PLA-b-
PAA block copolymers in aqueous media towards the formation of cylindrical
micelles of controlled length.
Interestingly, in many of the unstained TEM images presented in this work the
particles demonstrate a non-uniform contrast along their width. This unexpected
result is fully investigated in Chapter 6.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Crystallization, Self-assembly (Chemistry), Block copolymers, Polymers, Polymerization, Ring-opening polymerization | ||||
Official Date: | September 2012 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | O'Reilly, Rachel K. | ||||
Extent: | vii, 229 leaves : illustrations, charts. | ||||
Language: | eng |
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