Li, Guang-Zhao (2012) Synthesis and application of some novel functional polymers via controlled radical polymerization and click chemistry. PhD thesis, University of Warwick.

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Abstract

The objective of this thesis was to prepare thermoresponsive PEG-based
homopolymers and copolymers by combination of cobalt-mediated catalytic
chain-transfer polymerization (CCTP) and thiol-ene “click” chemistry and
prepare well-defined glycopolymers via “living” polymerization and “click”
chemistry.
The effect of different catalysts for the nucleophilic mediated thiol-ene
reaction was investigated using model compounds, both monomers and
oligomers obtained by CCTP. Different catalysts, including pentylamine and
hexylamine (primary amines), triethylamine (tertiary amine), and two different
phosphines, dimethylphenylphosphine (DMPP) and tris(2-carboxyethyl)
phosphine (TCEP), were investigated in the presence of different thiols. The
optimum reaction conditions for nucleophile mediated thiol-ene click reactions
were investigated.
Thermoresponsive PEG-based homopolymers and copolymers of
OEGMEMA obtained by CCT were modified using thiol-ene click chemistry
with a variety of different functional thiol compounds to yield functional
thermoresponsive polymers in high yield. The effect of different solvent systems
for based catalyzed thiol-ene reaction was investigated in the presence of
different functional thiols.
The ATRP polymerization of TMS-PgMA and TIPS-PgMA and ROP
polymerization of aliphatic polyester were investigated. A maleimide functional
initiator was used in order to achieve post conjugation of nanoparticles for drug
delivery. Moreover, the disulfide based bifunctional initiator was introduced into
the midpoint of the polymer chain, which could break down to afford the
corresponding polymer chain with thiol end group under the reducing condition.
The thiol-terminated polymer was also post-functionalized via thiol-ene click
chemistry. In addition, the aliphatic polycarbonate is a biocompatible and
biodegradable polymer, which is widely used in medical and pharmaceutical
applications. The subsequent introduction of sugar moiety to the reactive
polymer chain via CuAAC click reaction and then the interactions between
glycopolymers and lectins were investigated by Surface Plasmon Resonance
(SPR) and Quartz Crystal Microbalance with Dissipation (QCM-D).
The controlled SET-LRP polymerization of TMS-PgMA and SET-RAFT
polymerization PgMA with the intact alkyne at ambient temperature were
investigated. A maleimide functional initiator and CPDB, as the chain transfer
agent have been employed. The introduction of maleimide moiety was to allow
for post polymerization conjugation to peptides via reaction with cysteines. The
subsequent introduction of sugar azides to click with the reactive polymer
containing alkyne group and the glycopolymers through CuAAC was also
investigated. The glycopolymer has been successfully prepared combining the
SET-LRP/SET-RAFT and CuAAc click chemistry at ambient temperature.

Item Type:	Thesis or Dissertation (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Polymerization, Combinatorial chemistry, Polymers
Official Date:	March 2012
Dates:	Date Event March 2012 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Haddleton, David M.
Extent:	xxxviii, 308 leaves : illustrations.
Language:	eng

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