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-PBAy-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.
Solution and Solid-State Behavior of Amphiphilic ABA Triblock Copolymers of Poly(acrylic acid-stat-styrene)-block-poly(butyl acrylate)-block-poly(acrylic acid-stat-styrene)
Thomas J. Neal 1, Robert D. Bradley 2, Martin W. Murray 2, Neal S. J. Williams 2, Simon N. Emmett 2, Anthony J. Ryan 1, Sebastian G. Spain 1 and Oleksandr O. Mykhaylyk 1
1. Department of Chemistry, The University of Sheffield, Dainton Building, Sheffield, South YourkshireS3 7HF, U.K.
2. AkzoNobel Decorative Paints, Wexham Road, Slough, BerkshireSL2 5DS, U.K.
Macromolecules 2022, 55, 21, 9726–9739
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