pH-responsive microgel dispersions contain cross-linked polymer particles that swell when the pH approaches the pKa of the ionic monomer incorporated within the particles. In recent work from our group, it was demonstrated that the mechanical properties of degenerated intervertebral discs (IVDs) could be restored to normal values by injection of pH-responsive microgel dispersions (Saunders, J. M.; Tong, T.; LeMaitre, C.; Freemont, A. J.; Saunders, B. R. Soft Matter 2007, 3, 486). These dispersions change from a fluid to a gel with increasing pH. The present work investigates the pH-dependent properties of dispersions of microgel particles containing MAA (methacrylic acid) and also the effects of added Ca2+. Two microgels are discussed: microgel A is poly(EA/MAA/AM) (EA and AM are ethyl acrylate and allyl methacrylate), and microgel B is poly(EA/MAA/BDDA) (butanediol diacrylate). The pH-dependent particle properties investigated include hydrodynamic diameters and electrophoretic mobilities. The critical coagulation concentrations (CCC) of dilute dispersions and the elastic modulus (G') of concentrated, gelled microgel dispersions were also investigated. In the absence of added Ca2+, the particle swelling and G' were smallest and largest, respectively, for microgel A. The changes in hydrodynamic diameter and mobility with pH were explained in terms of a core-shell swelling mechanism. Added Ca2+ was found to significantly decrease the CCCs, extents of particle swelling, and magnitude of the electrophoretic mobility. This was attributed to the ionic cross-linking of neighboring RCOO- groups by Ca2+. It is suggested that the formation of ionic cross-links is inefficient within the microgel particles because of the presence of covalent cross-links that oppose the large-scale conformational rearrangement of neighboring RCOO- groups. The effect of Ca2+ on the properties of the gelled dispersions is important from the viewpoint of potential application in vivo. Rheological studies of the gelled microgel dispersions showed that added Ca2+ did not have a specific influence on G'. The differences observed in the presence of Ca2+ were attributed to ionic strength effects (screening). The key parameter that controls G' of the gelled microgel dispersions is pH. The results from this work suggest that the elasticity of the gels would be slightly reduced in vivo as a consequence of the high ionic strength present.

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Ionomers are polymers containing a low mole fraction of ionic groups bound to the polymer backbone. These ionic groups produce major changes in their structure and mechanical properties. Recently, we introduced a new family of crosslinked poly(Bd)/poly(Bd-co-MAA) core shell nanoparticles (1,3butadiene and methacrylic acid) that could be ionically crosslinked and cast as nanostructured ionomer films from aqueous dispersions [Pinprayoon et al., Soft Matter, 2011, 7, 247]. The MAA units in the core-shell particles were neutralised by Zn 2+ . Here, we explore the structure-property relationships for these new architecturally controlled nanocomposites by investigating 6 new poly(Bd)/poly (Bd-co-MAA) dispersions and films. In this study we varied the extent of covalent crosslinking in the core and the shell at constant ionic crosslinking for the first time. We used dynamic mechanical thermal analysis to establish a general phase map for the new nanostructured ionomers. Stress-strain data show that our nanostructured films have well controlled, and adjustable, modulus and strain at break values. The data show that the core-shell nanoparticle geometry allows the often observed trade-off between elasticity and ductility to be tuned in a manner that is not possible for conventional ionomers. We show that the chain transfer agent (CTA) concentrations used during the preparation of the nanoparticle cores and shells can be used to independently tune the mechanical properties of the films. This is due to variation of the extents of covalent crosslinking. The results of this study should apply to other covalently crosslinked core-shell nanoparticles containing RCOOH groups in the particle shells.