Using anionic polymerisation techniques, a series of poly(methyl methacrylate)
polymers bearing a variety of end-functions has been synthesised. The use of a delocalised
and sterically hindered initiator, I,I-diphenylhexyllithium in conjunction with lithium
chloride has allowed the production of polymers of well defined molecular weight and
narrow molecular weight distributions (Mw/Mn=1.1).
End-group functionality has been incorporated by the use of terminating agents
bearing a functional group. Functionalities achieved by this method include nitrobenzoyl
and nitrobenzyl. The degree of functionality has varied between 50 and 85 %. By the use
of selective reduction, these end-groups have been converted to amine functions.
Significant loss of functionality occurred during the reduction process and overall amine
functionality varied between 20 and 50 %.
The use of a functional initiator bearing a protected amme function, 1-(4-
benzophenone iminophenyl)-I-phenylethylene has allowed the incorporation of an imine
end-function. Mild acid-catalysed hydrolysis has then given quantitative amine endfunctionalisation
Charaterisation of functionalised PMMA polymers has been by IH and I3C NMR
spectroscopy, GPC and MALDI-TOF-MS. The combined use of NMR spectroscopy and
MALDI-TOF-MS has allowed the full characterisation of all end-groups present on low
molecular weight samples.
Grafting reactions of the amine functionalised PMMA have then been investigated.
Grafting onto epoxidised natural rubber, a styrene-maleic anhydride copolymer and epoxy
surface-functionalised emulsion particles have been attempted. GPC and modulated
temperature DSC have been used to characterise these products.
A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.