Styryl-terminated polystyrene macromonomers have been
synthesised by the anionic polymerisation of styrene.
Initiation was by sec-butyl lithium; termination involved the
addition of diphenylethylene prior to vinyl benzyl chloride.
Characterisation of the macromonomers was performed using gel
permeation chromatography (GPC) and proton nuclear magnetic
resonance spectroscopy (nmr).
Novel comb graft copolymers were synthesised by the
copolymerisation of the macromonomer with a comonomer. The
following comonomers were used: Z-vinylpyridine (Z-VP), 4-
vinylpyridine (4-VP) and N-(vinylbenzyl)pyrrolidone (VBP).
Graft copolymers were made with a range of compositions by
varying the feed ratios of the comonomer to the macromonomer.
Reactivity ratios were determined for the different graft
copolymer systems and compared to the simple statistical
copolymerisation of styrene with comonomer. Characterisation of
the graft copolymers was performed using GPC, nmr and membrane
osmometry. Micellar dispersions of the comb graft copolymers were
prepared in cyclohexane, toluene and methanol. These were
subsequently characterised by small-angle X-ray scattering
(SAXS) and transmission electron microscopy (TEM). Micellar
behaviour was related to graft copolymer composition and
The graft copolymers were subsequently used as steric
stabilisers in dispersion polymerisations of bis-hydroxyethyl
terephthalate in high boiling aliphatic hydrocarbon, methyl
methacrylate in cyclohexane, vinyl pyridine in
toluene/cyclohexane and styrene in methanol. A number of
parameters have been investigated including initiator,
stabiliser and monomer concentrations. Graft copolymer
composition and structure were shown to be important factors for the effective steric stabilisation of polymer particles in
conjunction with information on surface coverage data.
A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.