Maleic anhydride (MA) is a strong electron acceptor and so homopolymerises
with difficulty. Copolymerisations with electron donor monomers are however facile.
Free-radical and controlled radical polymerisation (CRP) techniques have been used to
probe the structure and mechanism of MA alternating copolymers.
Conventional free-radical polymerisation was used to synthesise poly
(octadecene -alt- MA) (PODMA). Molar masses ranging from 4,000 g morl to 61,000
g morl were successfully prepared by variation of polymerisation conditions. Molar
mass characterisation was by size exclusion chromatography (SEC) and dilute solution
viscometry. Calculation of monomer reactivity ratios revealed PODMA to have a
strictly alternating structure. NMR analysis indicated that PODMA had 100% trans
stereochemistry and the initiation and termination mechanisms were elucidated. The
optimised copolymerisation was scaled up from gram to kilo scale, providing an
important precursor for high performance crankcase oil dispersants.
MA has proved to be a challenging monomer for CRP. Reverse addition
fragmentation transfer (RAFf) copolymerisation was used to copolymerise MA with
styrene (St) monomers. Kinetic studies indicated controlled copolymerisation and living
characteristics were observed such as predetermined molar mass, narrow molar mass
distribution and chain extension to form novel block copolymers. The RAFT
mechanism and its effectiveness in producing controlled copolymers incorporating MA
A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University