Synthesis, Morphology, and Particle Size Control of Acidic Aqueous Polyurethane Dispersions.

A range of charge-stabilized aqueous polyurethane (PU) dispersions comprising hard segments formed from hydrogenated methylene diphenyl diisocyanate (HMDI) with dimethylolpropionic acid (DMPA) and ethylenediamine, and soft segments of poly(tetramethylene oxide) of different molecular weights are synthesized. Characterization of the dispersions by mass spectrometry, gel permeation chromatography, small-angle X-ray scattering, atomic force microscopy, and infrared spectroscopy shows that they are composed of PUs self-assembled into spherical particles (primary population) and supramolecular structures formed by hydrogen-bonded HMDI and DMPA acid-rich fragments (secondary population). Analysis of the scattering patterns of the dispersions, using a structural model based on conservation of mass, reveals that the proportion of supramolecular structures increases with DMPA content.

Solution and Solid-State Behavior of Amphiphilic ABA Triblock Copolymers of Poly(acrylic acid--styrene)--poly(butyl acrylate)--poly(acrylic acid--styrene).

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--styrene) --poly(butyl acrylate) --poly(acrylic acid--styrene) , poly(AA--St) --PBA --poly(AA--St) , ( = 56, 108 and 140, = 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.

Effect of Monomer Solubility on the Evolution of Copolymer Morphology during Polymerization-Induced Self-Assembly in Aqueous Solution.

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.

Time-resolved small-angle X-ray scattering studies of polymer-silica nanocomposite particles: initial formation and subsequent silica redistribution.

Small angle X-ray scattering (SAXS) is a powerful characterization technique for the analysis of polymer-silica nanocomposite particles due to their relatively narrow particle size distributions and high electron density contrast between the polymer core and the silica shell. Time-resolved SAXS is used to follow the kinetics of both nanocomposite particle formation (via silica nanoparticle adsorption onto sterically stabilized poly(2-vinylpyridine) (P2VP) latex in dilute aqueous solution) and also the spontaneous redistribution of silica that occurs when such P2VP-silica nanocomposite particles are challenged by the addition of sterically stabilized P2VP latex. Silica adsorption is complete within a few seconds at 20 °C and the rate of adsorption strongly dependent on the extent of silica surface coverage.

When does silica exchange occur between vinyl polymer-silica nanocomposite particles and sterically stabilized latexes?

The redistribution of silica nanoparticles between "core-shell" polymer-silica nanocomposites and sterically stabilized latexes is investigated using a combination of electron microscopy, disk centrifuge photosedimentometry (DCP), and X-ray photoelectron spectroscopy (XPS). Facile exchange of silica nanoparticles occurs on addition of sterically-stabilized polystyrene (or poly(2-vinylpyridine)) latex to polystyrene-silica (or poly(2-vinylpyridine)-silica) nanocomposite particles previously prepared by heteroflocculation. In contrast, no silica exchange occurs after such a latex "challenge" if similar polymer/silica nanocomposite particles are prepared via in situ polymerization.

Unexpected facile redistribution of adsorbed silica nanoparticles between latexes.

Addition of excess sterically stabilized P2VP latex to a colloidal dispersion of P2VP-silica nanocomposite particles (with silica shells at full monolayer coverage) leads to the facile redistribution of the silica nanoparticles such that partial coverage of all the P2VP latex particles is achieved. This silica exchange, which is complete within 1 h at 20 degrees C as judged by small-angle x-ray scattering, is observed for nanocomposite particles prepared by heteroflocculation, but not for nanocomposite particles prepared by in situ copolymerization. These observations are expected to have important implications for the optimization of nanocomposite formulations in the coatings industry.

Packing efficiency of small silica particles on large latex particles: a facile route to colloidal nanocomposites.

The adsorption of small silica particles onto large sterically stabilized poly(2-vinylpyridine) [P2VP] latex particles in aqueous solution is assessed as a potential route to nanocomposite particles with a "core-shell" morphology. Geometric considerations allow the packing efficiency, P, to be related to the number of adsorbed silica particles per latex particle, N. Making no assumptions about the packing structure, this approach leads to a theoretical estimate for P of 86 +/- 4%.