The preparation of highly filled polystyrene/Laponite (PS/Lap) hybrid nanoparticles by the ad‐miniemulsion polymerisation technique, using conventional free‐radical polymerisation, is described. Laponite (Lap) is first modified with a polymerisable cationic surfactant. Then, using a second surfactant dispersions are prepared under sonication. A stable hybrid miniemulsion is obtained after mixing and co‐sonicating both miniemulsions. The polymerisation is conducted using an oil‐soluble initiator to obtain hybrid nanoparticles. PS/Lap hybrid nanoparticles are effectively prepared with clay contents as high as 50 wt%. TEM reveals that the highly filled hybrid latexes (≥30 wt%) exhibit encapsulated morphology with homogeneously distributed clay platelets.

The influence of clay platelet size and type of organic modifier (reactive or nonreactive) on highly filled hybrid latex morphology and physical properties of the resultant polymer/clay nanocomposites (PCNs) were investigated. The hybrid latexes, containing clay loadings between 30 and 50 wt % clay, were prepared using ad-miniemulsion polymerization. These materials have potential use in the packaging and coating industry since clay platelets are well-known for barrier property improvements. Comparative studies on the use of montmorillonite (MMT), a large clay platelet (average size: 50-500 nm), and Laponite (Lap), small-sized clay platelets (average size: 25-40 nm), were conducted. Two different clay modifiers were used to modify the clays, i.e., a conventional nonreactive modifier (cetyltrimethylammonium bromide (CTAB)) and a reactive modifier (vinylbenzyldodecyldimethylammonium chloride (VBDAC)). Transmission electron microscopy (TEM) imaging of the hybrid latexes clearly showed strong morphological dependency on both the type of modifier and the clay platelet size. Furthermore, TEM together with small-angle X-ray scattering (SAXS) showed that the extent of clay exfoliation was strongly dependent on the reactivity of the clay modifier, irrespective of the clay platelet size. Both the type of modifier and clay platelets size were found to have an influence on different physical properties of the resultant PCNs. The influence of clay size was clearly indicated by storage modulus and thermal stability behaviors, while that of the clay modifier was indicated by the T(g). Lap-based PCNs exhibited constant or increasing storage modulus and no change in thermal stability with increasing clay content, while MMT-based PCNs showed a decreasing trend in both storage modulus and thermal stability. PCNs based on clay modified with CTAB showed a decreasing T(g) with increasing clay content, while those based on clay modified with VBDAC showed an increasing trend. It was concluded that the clay platelet size and the type of modifier play a crucial part of both the latex morphology and the physical properties of the resultant PCNs.

A series of poly(acrylonitrile-co-methyl acrylate) copolymers of differing copolymer compositions are synthesized through free radical emulsion copolymerisation of methyl acrylate (MA) and acrylonitrile (AN) and by variation of the monomer feed ratios. The copolymers are characterized by NMR, SEC, WAXD, DMA, and positron annihilation lifetime spectroscopy. Results show that, there is a linear decrease in the glass transition temperature (T g ) of the copolymers and the MA content. There is also a progressive decrease in the crystallinity of the copolymers with increasing MA content. Positron results show a sigmoidal variation in the ortho positronium lifetime with an increasing MA content. The low MA content, semi-crystalline copolymers show a positive deviation from the linear additive relationship between the o-Ps lifetime and MA content, whereas the higher MA content amorphous copolymers show a negative deviation from the linear additive behavior. The o-PS intensity shows a linear behavior with MA content with a slight deviation from the additive linear behavior for the very high-content MA copolymer. These variations in the measured positron lifetime parameters are interpreted in terms of the copolymer morphology.

No abstract

Poly(acrylonitrile‐co‐methyl acrylate)/clay nanocomposites were prepared by free radical polymerization in emulsion using 2‐acrylamido‐2‐methyl‐1‐propanesulphonic acid (AMPS) as a compatibilizer. The resultant nanocomposites were of partially exfoliated morphology despite the variations in clay content among the nanocomposites, as confirmed by transmission electron microscopy and small‐angle X‐ray scattering analysis. Rheological studies of these materials were carried out using parallel plate geometry. The storage modulus increased monotonically with increasing clay content throughout the frequency range studied. However, the neat copolymer, poly(acrylonitrile‐co‐methyl acrylate) and its nanocomposites, exhibited long relaxation behavior as the storage modulus (G′) was greater than the loss modulus (G″) throughout the angular frequency range studied. The complex viscosity of the nanocomposites increased with increasing clay content and they exhibited shear‐thinning behavior. Despite the enhanced rheological properties observed, the copolymer and its nanocomposites underwent structural changes during oscillatory measurements due to cyclization reactions. POLYM. COMPOS., 32:59–66, 2011. © 2010 Society of Plastics Engineers