Block copolymers of poly(ethylene oxide) and poly(methyl methacrylate)

A series of five AB block copolymers of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) has been synthesised by the coupling of mono-functional homopolymers by an esterification reaction. In this series polymers all contain a PMMA component of number average molecular weight 908 gmo1·1, as measured by end group analysis, and the PEO components have number average molecular weights of 596, 689, 979, 2023 and 2884 gmol·1, as measured by proton nuclear magnetic resonance spectroscopy. Aqueous "solutions" of these copolymers have been prepared both by direct mixing and via methanol, a solvent for both blocks of the copolymer. Cloud points for these copolymers have been determined and range from 275K to 368K for the lowest and highest PEO blocks respectively. Small angle X-ray scattering (SAXS) of aqueous solutions has been interpreted in terms of a core - shell model and dimensions determined for both. Radii of gyration for the micellar cores have been shown to vary very little with variations in copolymer composition, concentration and temperature up to the cloud point. Fringe thicknesses show a dependence on PEO block length and relating measured fringe thicknesses to calculated chain conformations indicates that the the chain conformation is best described as an unperturbed chain. The measured fringe thickness is not altered by concentration or temperature up to the cloud point. Above the cloud point it is not possible to interpret the SAXS data in terms of a core shell micellar model. Significant differences in the SAXS data have been observed depending upon the mode of addition of copolymer to water. This can be interpreted as differences in micellar II structure With the exception of the lowest molecular weight copolymer all of the copolymers could be used as steric stabilisers for the aqueous emulsion polymerisation of methyl methacrylate. Polymerisations were only successful if the copolymer was introduced to the aqueous phase either via methanol or via the monomer. Direct addition of copolymer to water resulted in low polymerisation rates and unstable/flocculated products. Emulsions produced have been shown to be stable at pH levels where the electrophoretic mobility was zero, ie. the emulsions were sterically stabilised with no contribution from ionic I dipole interactions.