A new PISA formulation has been explored for the generation of both phosphonate- and phosphonic acid-stabilized spheres, worms and vesicles. More specifically, three poly(methacryloyloxymethyl dimethylphosphonate) [PMP] macro-CTAs with mean degrees of polymerization of 24, 32, and 42 were synthesized via RAFT solution polymerization and converted into the corresponding poly(methacryloxymethyl phosphonic acid) [PMPA] macro- CTAs via ester hydrolysis. Subsequent chain extension with BzMA via RAFT methanolic dispersion polymerization at 20% w/w solids enabled construction of detailed phase diagrams for both types of macro-CTAs. Systematic variation of the target degree of polymerization of the PBzMA provides access to diblock copolymer spheres, worms and vesicles, as well as mixed phases. Comparing the performance of the same macro-CTA in its non-ionic and anionic forms allowed the effect of stabilizer charge density on self-assembly in non-aqueous media (i.e.
methanol) to be assessed for the first time. GPC studies indicate high blocking efficiencies and low final polydispersities for all non-ionic PMPx-PBzMAy diblock copolymers. However, for the
anionic PMPAx macro-CTAs, blocking efficiencies could only be assessed indirectly via chain
extension experiments conducted using a water-soluble monomer (glycerol monomethacrylate) as the second block. Transfer of selected diblock copolymer nano-objects from methanol to water via dialysis did not result in any discernible changes in copolymer morphology, as judged by TEM and DLS. Aqueous electrophoresis studies confirmed the highly anionic character of the phosphonic acid-stabilized nano-objects in aqueous media. Examination of both sets of copolymer nano-objects as crystal growth additives showed that anionic worms and vesicles
were occluded within calcite crystals during the crsytal growth, while the corresponding non- ionic phosphonate-stabilized vesicles were not. These findings emphasize the importance of appropriate surface chemistry in promoting occlusion of organic nanoparticles within inorganic host crystals.
ASSOCIATED CONTENT
Supporting Information. 31P NMR spectra and GPC data for the three PMPA macro-CTAs, GPC and DLS data for kinetics of dispersion polymerization experiments, GPC data for all PMPx-PBzMAy diblock copolymers, additional TEM images, DLS data for aqueous dispersion
polymerizations conducted using binary mixtures of macro-CTAs, and Raman spectra for selected CaCO3 occlusion experiments. This material is available free of charge via the Internet
at http://pubs.acs.org
AUTHOR INFORMATION Corresponding Author
*E-mail [email protected].
ACKNOWLEDGMENT
EPSRC is acknowledged for postdoctoral support of A.H. (EP/K006290/1) and A.N.K. (EP/K006304/1). The authors thank André H. Gröschel for the preparation of the nano-object illustrations.
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