Emulsion polymerization of 2-(diethylamino)ethyl methacrylate (DEA) in the presence of a bifunctional cross-linker at pH 8-9 afforded novel pH-responsive microgels of 250-700 nm diameter. Both batch and semicontinuous syntheses were explored using thermal and redox initiators. Various strategies were evaluated for achieving colloidal stability, including charge stabilization, surfactant stabilization, and steric stabilization. The latter proved to be the most convenient and effective, and three types of well-defined reactive macromonomers were examined, namely, monomethoxy-capped poly(ethylene glycol) methacrylate (PEGMA), styrene-capped poly[2-(dimethylamino)ethyl methacrylate] (PDMA50-St), and partially quaternized styrene-capped poly[2-(dimethylamino)ethyl methacrylate] (10qPDMA50-St). The resulting microgels were pH-responsive, as expected. Dynamic light scattering and 1H NMR studies confirmed that reversible swelling occurred at low pH due to protonation of the tertiary amine groups on the DEA residues. The critical pH for this latex-to-microgel transition was around pH 6.5-7.0, which corresponds approximately to the known pKa of 7.0-7.3 for linear PDEA homopolymer. The microgel particles were further characterized by electron microscopy and aqueous electrophoresis studies. Their swelling and deswelling kinetics were investigated by turbidimetry. The PDEA-based microgels were compared to poly[2-(diisopropylamino)ethyl methacrylate] (PDPA) microgels prepared with identical macromonomer stabilizers. These PDPA-based microgels had a lower critical swelling pH of around pH 5.0-5.5, which correlates with the lower pKa of PDPA homopolymer. In addition, the kinetics of swelling for the PDPA microgels was somewhat slower than that observed for PDEA microgels; presumably this is related to the greater hydrophobic character of the former particles.

2-(Dimethylamino)ethyl methacrylate (DMA) was block copolymerized with methyl methacrylate (MMA) using group transfer polymerization to give four AB diblock, ABA triblock, and BAB triblock copolymers of low polydispersity (Mw/Mn < 1.20). In addition, a near-monodisperse styrene-functionalized DMA-based macromonomer was synthesized via oxyanionic polymerization using a potassium 4-vinylbenzyl alcoholate initiator. These five well-defined, tertiary amine methacrylate-based copolymers were evaluated as steric stabilizers for the synthesis of polystyrene latexes via emulsion and dispersion polymerization. The most efficient steric stabilizers proved to be the DMA-MMA diblock copolymer and the DMA-based macromonomer. The polystyrene latexes were characterized in terms of their particle size and morphology, stabilizer content, surface charge, and surface activity using dynamic light scattering, scanning electron microscopy, 1H NMR spectroscopy, aqueous electrophoresis measurements, and surface tensiometry, respectively. The pH-dependent surface activity exhibited by selected latexes suggests potential applications as stimulus-responsive particulate emulsifiers for oil-in-water emulsions.

We report the surfactant-free synthesis of new, film-forming vinyl polymer/silica colloidal nanocomposites by copolymerization of 4-vinylpyridine (4VP) with either n-butyl acrylate (n-BuA) or n-butyl methacrylate (n-BuMA) in the presence of an ultrafine aqueous silica sol. Highly transparent, free-standing nanocomposite films were readily obtained by solution-casting from aqueous media at room temperature. Thermogravimetric analyses indicated silica contents ranging from 20% to 56%, depending on the nanocomposite formulation, and intensity-average particle diameters ranged from 139 to 305 nm. The influence of the synthesis conditions on the particle properties was also studied. Reducing the initial silica concentration at constant monomer concentration led to an increase in the particle size and reduced colloid stability, indicating that the ultrafine silica sol stabilized the colloidal nanocomposites. Colloidal nanocomposites were also prepared using a methacrylate-capped poly(ethylene glycol) (MPEGMA) macromonomer as a reactive steric stabilizer. The resulting sterically stabilized nanocomposites exhibited enhanced colloid stability, as expected. In addition, this polymeric stabilizer led to an increase in the silica content of the nanocomposites and lower minimum film-forming temperatures due to its plasticizing effect. ζ potential measurements indicated that the MPEGMA stabilizer was mainly located at the surface of the nanocomposite particles, as expected. 1 H NMR spectroscopy studies of the polymeric component extracted from selected nanocomposites confirmed the incorporation of both the 4VP and the film-forming comonomer (and also the MPEGMA macromonomer, where applicable). Transmission electron microscopy studies confirmed the presence of silica in the particles, and thin film cross-sections prepared by cryo-ultramicrotomy indicated that the surface of the nanocomposite particles was silica-rich, suggesting a core-shell morphology. However, X-ray photoelectron spectroscopy studies of the n-BuA-based nanocomposite films indicated that profound morphological changes occurred during film formation. The more hydrophobic copolymer component diffuses to the film/air interface and displaces the hydrophilic silica particles, leading to a surface excess of the copolymer component. This probably accounts for the relatively low water uptake by these nanocomposite films. LA010138A

The surfactant-free synthesis of vinyl polymer-silica nanocomposite particles has been achieved in aqueous alcoholic media at ambient temperature in the absence of auxiliary comonomers. Styrene, methyl methacrylate, methyl acrylate, n-butyl acrylate, and 2-hydroxypropyl methacrylate were homopolymerized in turn in the presence of three commercially available ultrafine alcoholic silica sols. Stable colloidal dispersions with reasonably narrow size distributions were obtained, with silica contents of up to 58% by mass indicated by thermogravimetric analysis. Particle size distributions were assessed using both dynamic light scattering and disk centrifuge photosedimentometry. The former technique indicated that the particle size increased for the first 1-2 h at 25 degrees C and thereafter remained constant. Particle morphologies were studied using electron microscopy. Most of the colloidal nanocomposites comprised approximately spherical particles with relatively narrow size distributions, but in some cases more polydisperse or nonspherical particles were obtained. Selected acrylate-based nanocomposites were examined in terms of their film formation behavior. Scanning electron microscopy studies indicated relatively smooth films were obtained on drying at 20 degrees C, with complete loss of the original particle morphology. The optical clarity of solution-cast 10 microm nanocomposite films was assessed using visible absorption spectrophotometry, with 93-98% transmission being obtained from 400 to 800 nm; the effect of long-term immersion of such films in aqueous solutions was also examined. X-ray photoelectron spectroscopy studies indicated that the surface compositions of these nanocomposite particles are invariably silica-rich, which is consistent with their long-term colloidal stability and also with aqueous electrophoresis measurements. FT-IR studies suggested that in the case of the poly(methyl methacrylate)-silica nanocomposite particles, the carbonyl ester groups in the polymer are hydrogen-bonded to the surface silanol groups. According to differential scanning calorimetry studies, the glass transition temperatures of several poly(methyl methacrylate)-silica and polystyrene-silica nanocomposites can be either higher or lower than those of the corresponding homopolymers, depending on the nature of the silica sol.

A pH-responsive, sterically-stabilised polystyrene latex is used as a particulate emulsifier for oil-in-water emulsions; demulsification occurs rapidly on lowering the solution pH and the original emulsion can be reformed on pH cycling.