RESUMO
A combination of statistical and triblock copolymer properties is explored to produce stable aqueous polymer dispersions suitable for the film formation. In order to perform an extensive structural characterization of the products in the dissolved, dispersed, and solid states, a wide range of symmetrical poly(acrylic acid-stat-styrene) x -block-poly(butyl acrylate) y -block-poly(acrylic acid-stat-styrene) x , poly(AA-st-St) x -b-PBA y -b-poly(AA-st-St) x , (x = 56, 108 and 140, y = 100-750; the AA:St molar ratio is 42:58) triblock copolymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) solution polymerization using a bifunctional symmetrical RAFT agent. It is demonstrated that the amphiphilic statistical outer blocks can provide sufficient stabilization to largely hydrophobic particles in aqueous dispersions. Such a molecular design provides an advantage over copolymers composed only of homoblocks, as a simple variation of the statistical block component ratio provides an efficient way to control the hydrophilicity of the stabilizer block, which ultimately affects the copolymer morphology in solutions and solid films. It was found by small-angle X-ray scattering (SAXS) that the copolymers behaved as dissolved chains in methylethylketone (MEK) but self-assembled in water into stable and well-defined spherical particles that increased in size with the length of the hydrophobic PBA block. These particles possessed an additional particulate surface structure formed by the statistical copolymer stabilizer block, which self-folded through the hydrophobic interactions between the styrene units. SAXS and atomic force microscopy showed that the copolymer films cast from the MEK solutions formed structures predicted by self-consistent field theory for symmetrical triblock copolymers, while the aqueous dispersions formed structural morphologies similar to a close-packed spheres, as would be expected for copolymer particles trapped kinetically due to the restricted movement of the blocks in the initial aqueous dispersion. A strong correlation between the structural morphology and mechanical properties of the films was observed. It was found that the properties of the solvent cast films were highly dependent on the ratios of the hard [poly(AA-st-St)] and soft (PBA) blocks, while the aqueous cast films did not show such a dependence. The continuous phase of hard blocks, always formed in the case of the aqueous cast films, produced films with a higher elastic modulus and a lower extension-to-break in a comparison with the solvent-cast films.
RESUMO
A range of amphiphilic statistical copolymers is synthesized where the hydrophilic component is either methacrylic acid (MAA) or 2-(dimethylamino)ethyl methacrylate (DMAEMA) and the hydrophobic component comprises methyl, ethyl, butyl, hexyl, or 2-ethylhexyl methacrylate, which provide a broad range of partition coefficients (logâ¯P). Small-angle X-ray scattering studies confirm that these amphiphilic copolymers self-assemble to form well-defined spherical nanoparticles in an aqueous solution, with more hydrophobic copolymers forming larger nanoparticles. Varying the nature of the alkyl substituent also influenced self-assembly with more hydrophobic comonomers producing larger nanoparticles at a given copolymer composition. A model based on particle surface charge density (PSC model) is used to describe the relationship between copolymer composition and nanoparticle size. This model assumes that the hydrophilic monomer is preferentially located at the particle surface and provides a good fit to all of the experimental data. More specifically, a linear relationship is observed between the surface area fraction covered by the hydrophilic comonomer required to achieve stabilization and the logâ¯P value for the hydrophobic comonomer. Contrast variation small-angle neutron scattering is used to study the internal structure of these nanoparticles. This technique indicates partial phase separation within the nanoparticles, with about half of the available hydrophilic comonomer repeat units being located at the surface and hydrophobic comonomer-rich cores. This information enables a refined PSC model to be developed, which indicates the same relationship between the surface area fraction of the hydrophilic comonomer and the logâ¯P of the hydrophobic comonomer repeat units for the anionic (MAA) and cationic (DMAEMA) comonomer systems. This study demonstrates how nanoparticle size can be readily controlled and predicted using relatively ill-defined statistical copolymers, making such systems a viable attractive alternative to diblock copolymer nanoparticles for a range of industrial applications.
RESUMO
Polymerization-induced self-assembly (PISA) has become a widely used technique for the rational design of diblock copolymer nano-objects in concentrated aqueous solution. Depending on the specific PISA formulation, reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization typically provides straightforward access to either spheres, worms, or vesicles. In contrast, RAFT aqueous emulsion polymerization formulations often lead to just kinetically-trapped spheres. This limitation is currently not understood, and only a few empirical exceptions have been reported in the literature. In the present work, the effect of monomer solubility on copolymer morphology is explored for an aqueous PISA formulation. Using 2-hydroxybutyl methacrylate (aqueous solubility = 20 g dm-3 at 70 °C) instead of benzyl methacrylate (0.40 g dm-3 at 70 °C) for the core-forming block allows access to an unusual "monkey nut" copolymer morphology over a relatively narrow range of target degrees of polymerization when using a poly(methacrylic acid) RAFT agent at pH 5. These new anisotropic nanoparticles have been characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, shear-induced polarized light imaging (SIPLI), and small-angle X-ray scattering.