Comb graft copolymers : synthesis, micellisation and dispersant behaviour
thesisposted on 20.09.2012, 13:15 by Mark G. Branch
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 structure. 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.